This project developed from an industrial need for a plasticiser for explosives formulations which is easier to manufacture, more stable than those presently employed, but still based on a polynitroaromatic nucleus. The major aim of this programme was to produce new liquid or low melting polynitroaromatic compounds by simple routes. A literature search highlighted various molecular features which appeared to produce a low melting temperature in polynitroaromatic compounds. Using these features, four categories of compounds were identified as target compounds for a synthetic programme to produce low melting polynitroaromatic compounds. (A: Alkyltrinitrobenzenes; B: trinitrophenylpropanoate esters; C: 3-alkylpicrylethers; D: 3-alkyltrinitrobenzoate esters). 2,4,6-Trinitrotoluene (the preferred starting material for category A and B compounds) forms an anion in basic solution, which has been suggested as having nucleophilic characteristics 3. In fact, this work has shown that it displays very poor nucleophilic qualities, though reaction with p-nitrobenzyl bromide was successful. An ultraviolet and nmr spectroscopic study of this reaction provided evidence to suggest that O'-adduct formation facilitates an ionic substitution reaction; whereas in other cases such O-complex formation is not favoured and radical decomposition of TNT occurs. Three 3-alkylpicryl chlorides have been prepared from 3-alkylphenols as precursors for category C and D compounds. Attempts to prepare such compounds from TNT were unsuccessful. Partial reduction of TNT, to 2,4-diamino-6-nitrotoluene was achieved, but bromination of this compound proved to be uncontrollable, with 2,4-diamino-3,5-dibromo-6-nitrotoluene being the only product. The mechanism of this reaction is discussed. The preparation of 3-alkylpicryl ethers (category C compounds) was successfully achieved and numerous liquids or low melting solids were produced. 3-t-Butylpicryl chloride in reaction with certain alkoxides, displayed a competition between nitro group and halogen substitution, with up to 30% nitro group substitution being observed; a novel reaction in systems of this type. A series of low melting compounds have been prepared from 3-alkylpicryl halides using various sulphur and nitrogen nucleophiles.

A common problem whit Polyvinyl chloride (PVC) is that plasticisers tend to migrate during use. When the plasticisers migrate the material gets stiffer, this can for example cause cracks in the PVC material. Some PVC tends to crack more easily than other; finding out what is causing this problem would bring answers to a number of questions.We have done a study in cooperation with VCC. Former studies, by VCC, with variable results have been executed trying to solve the problem with cracks. We wanted to design a new test method to see if we were able to provoke cracks. If we were able to provoke these cracks, we could see when and why cracks appear in the current PVC item.During our work, we evaluated two different PVC coated materials; PVC1 and PVC2. Both materials had two different structures - with foam backing and without foam backing. We performed mechanical, thermal and chemical treatments on the materials and with help from those experiment we were able to provoke cracks in one of our PVC coated materials.According to our results, PVC1 shows a higher tendency to crack in comparison with PVC2, which only developed wrinkles. In PVC1 we could see cracks in an early stage during our mechanical testing. We evaluated our result by using a microscope and we observed a pattern in the tendency to develop cracks. PVC1 with foam backing had a higher tendency to crack in comparison with PVC1 without foam. Materials that have been abraded before flexing also tend to crack more easily.In order to see if the plasticisers migrated into the foam during our experimental work we performed an extraction of PVC1, according to the results the plasticisers might have migrated to the foam.The major conclusion from this study of PVC1 and PVC2 is that PVC1 tends to crack more easily than PVC2. The foam seems to have a negative effect on the PVC. The abrasion before ageing also have a negative effect on the PVC coated material. We could not see that the chemicals affected the materials.One of the main purposes with this study was to find a new test method for PVC coated items. We think that our test method with the ageing of the material in combination with the mechanical tests as Martindale and Ballyflex is a suitable test method while testing PVC coated materials. / Program: Textilingenjörsutbildningen

Starch is a natural polymer occurring in the seeds, tubers and stems of many plants, including maize. It is a mixture of two polymers: linear amylose and highly branched amylopectin. The ratio and the molar masses of the two polymers depend on the starch source, giving rise to different starch properties. Thermoplastic starch (TPS) was obtained by gelatinising a dry-blend mixture of maize starch, water, plasticisers and additives in a single-screw laboratory extruder. The TPS formed is a translucent amorphous material that could be shaped into pellets and injection-moulded into a variety of articles, just like conventional plastics [Shogren et al., 1994]. The advantages of TPS are that it is cheap and fully biodegradable. However, because of its hydrophilic nature, its properties and dimensional stability are influenced by moisture (humidity). It is also not easily processed like conventional plastics and the freshly moulded material ages, i.e. its properties change over time. The latter is caused by retrogradational structural changes which include helix formation and the crystallisation that occurs above the glass transition temperature [Myllärinen et al., 2002]. The unacceptable physical and processing properties of TPS were improved by blending with other polymers. The objective of this work was to determine the effects of water and glycerol content and the starch source or type on the mechanical properties of maize-based TPS. In addition, the effect of gypsum filler and polyamides or polyvinyl butyral (PVB) as modifying agent was also investigated. The PVB was based on material recycled from automotive windscreens. As with the thermoplastic starch, the thermoplastic/polymer blends, e.g. polyvinyl butyral, were also prepared using a single-screw extruder. After pelletisation, the materials were conditioned at 30 °C and a relative humidity of 60%. Tensile test specimens were prepared by injection moulding. Samples were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and tensile testing. The effect of environmental conditions (temperature and humidity or water submersion) on the ageing of the samples was investigated using tensile properties as a measure. Initial extrusion and moulding trials revealed that the TPS compounds were very difficult to process. Difficulties were encountered with feeding the dry blends into the compounding extruder. The moulded samples adhered strongly to the mould walls, especially the sprue part. These problems were overcome by adding 2,5% precipitated silica to improve the flowability of the dry blends and stearyl alcohol at ca. 1,5% as a processing aid. The latter performed as an external lubricant and mould-release agent. Nevertheless, for some compositions it was also necessary to use ‘Spray-and-Cook’ as mould-release agent during injection moulding. The results show that HiMaizeTM, a high-amylose maize starch, provided the best properties in TPS and its blends. Further improvements in properties were obtained by blending with low-molecular-weight hot-melt adhesive-grade polyamides (Euremelt 2138 and 2140), engineering polyamide (EMS Grilon CF 62 BSE) or low amounts of PVB. The properties of all the compounds investigated were affected by moisture content and also by ageing. The TPS-PVB blends showed highly non-linear composition-dependence. SEM and DMA revealed a phase separation for all the TPS-PVB blend compositions investigated. The tensile properties were negatively affected by ageing in a high-humidity environment and they deteriorated rapidly when the samples were soaked in water. Synergistic property enhancement was observed for a compound containing 22% thermoplastic starch. It featured a higher tensile strength, showed better water resistance and was significantly less affected by ageing. At higher PVB levels, the property dropped to values that were lower than expected from the linear blending rule. / Thesis (PhD)--University of Pretoria, 2008. / Chemical Engineering / unrestricted

This work is oriented on the preparation of high-voluable sulphate binder based on gypsum waste. One of the potential mineral resources in Moravia is Pregips chemical gypsum, produced by Precheza. This is the raw material, which is characterized by high purity, high quality and is economically acceptable. Beta burned gypsum plaster from this, however, need to modify due to suppression of the high needs of water mixing, which is determined by its morphology. The need for mixing water has a large impact on the strength of gypsum binders. Therefore it is necessary to find a suitable additive, which would reduce the coefficient of water in the preparation of porridge normal consistency.

A key trend in the PVC market is to replace or decrease the amount of phthalate plasticisers used due to increasing health concerns. Therefore, the demand for non-phthalate based plasticisers is growing rapidly. Mineral oils are used in a variety of rubber and polymer applications as plasticisers; however, due to the lower polarity their applicability in PVC compounds is limited. Therefore, these materials are typically used as secondary plasticiser along with a primary for the purpose of improved properties and cost reduction. Some of the non-phthalate based solutions are fast fusing plasticisers, which act like solvents and have too rapid and too high plasticizing effect. This makes the compounding difficult and could cause problems in production. These substances have good compatibility with mineral oils, and using them together in PVC compounds can help the compounding issue by reducing the solvent power and increasing the fusion time to a level where the production parameters are similar to compounding with phthalates.   The aim of this study was to evaluate the use of mineral oils as a secondary plasticiser in a non-phthalate system for PVC. Four different grades of mineral oil and three non-phthalate plasticisers were used in compounding and compression moulding of PVC sample films. Mechanical, physical and chemical testing were done to assess the properties in a comparative study with phthalate plasticized PVC.   Tensile testing and hardness measurements showed that the mineral oils did not contribute with any plasticizing effect for the non-phthalate plasticisers tested in the study. The hardness was instead slightly increased for all the sample films that contained mineral oil. This indicates that the mineral oil either is less efficient than the primary plasticiser or that it affects the primary plasticisers intramolecular shielding between the PVC chains.       The shrinkage test showed that the migration of mineral oil was acceptable, especially the thicker grades of mineral oils had low migration. Colour stability test showed that the thicker mineral oil grades had some problems with discolouration. The discolouration is probably related to content of polyaromatics and oxidation stability.

På grund av ökad användning av plast har biobaserade polymerer som förpackningsmaterialfått stor uppmärksamhet de senaste åren på grund av miljöhänsyn. Flera proteinmaterial, t.ex.vetegluten har varit i fokus för betydande forskning kring ny biobaserad plast och resultatenär lovande. Det idag stora intresset för biobaserad och miljövänlig plast beror påväxthuseffekten från konventionell petroleumbaserad plast. Ett proteinmaterial från undersöktes här för dess plastmaterialegenskaper. Proteinrenheten varca. 65%. Filmerna skapades genom att först mala proteinflingorna till ett fint pulver ochblanda det med glycerol. Glycerolhalten var 30 %. Därefter varmpressades materialet. För atttesta plasten användes flera tekniker och metoder. TGA, DSC, FT-IR, WVTR, OTR ochdragprovning. I allmänhet var materialet relativt svagt. Liksom de flesta proteinplaster hadedet också dåliga vattenbarriäregenskaper, men hade relativt goda syrebarriäregenskaper. Sammanfattningsvis är det ett material som kan ha en ljus framtid eftersom det är tillverkat avbiomassa istället för petroleum, vilket innebär att det är mer miljövänligt. Med modifieringkan det bli en bra plast för flera ändamål. / Due to increase use of plastics, bio-based polymers as packaging materials have garneredmuch attention in recent years due to environmental concerns. Several protein materials, e.g.wheat gluten, have been in focus for significant research towards new biobased plastics andresults are promising. Bio-based and environmentally friendly plastics gather much interestand attention today due to the green-house generating effects of conventional petroleum-basedplastics. A protein material was investigated here for its plastic material properties. The protein puritywas ca. 65 %. The films were created by first grinding the protein flakes to a fine powder andmixing it with glycerol. The glycerol content was 30 %. The material was subsequently hotpressed.To test the plastic, multiple techniques and methods were used. TGA, DSC, FT-IR, WVTR,OTR and tensile testing. In general, the material was relatively weak. As most protein plasticsit had also poor water barrier properties, however it had relatively good oxygen-barrierproperties. In conclusion it is a material that could have a bright future as it is made from biomass insteadof petroleum, which means that it is more environmentally friendly. With modification andimprovement, it can be a good plastic for several applications in future.

Plasticizers are synthetic organic chemicals that are used in different products to make them flexible, elastic, and durable. Plasticizers are not attached to the products by covalent bonds, as a result, they leach out from the products leading to environmental contamination. The most widely used plasticizer, Di-(2-ethyl hexyl) phthalate (DEHP), have been restricted from general use in the EU, Canada, and the USA due to their reported toxicity. The alternative plasticizer, Di-(isononyl) cyclohexane-1,2-dicarboxylate (DINCH), was introduced to the European market as a safer alternative for endocrine-disrupting phthalates such as DEHP, and diisononyl phthalate (DINP).  According to the current toxicological data, DINCH is neither an endocrine disruptor and nor a reproductive toxicant. Thus, DINCH was approved for use in food contact containers, and in children’s toys.  The increase in global demand for alternative plasticizers led to their buildup in the environment and an increase in DINCH exposure. The lack of toxicity data and safety assessment of DINCH has raised the concern to human and animal health. Due to the similar structure of DEHP, DINP, and DINCH, we suggest that DINCH can be classified as a metabolic disruptor that alters fat metabolism and induces adipogenesis. In this study, we investigated the negatives effects of DINCH (at concentrations ranging from 0.01 to 10 μM) compared it to phthalates DINP, DEHP, Dibutyl phthalate (DBP), and Diethyl phthalate (DEP) at the early developmental stages of zebrafish. We further analyzed DINCH and DINP using the mouse preadipocyte cells  3T3L1. We found that DINCH and DEHP caused hatching delay in a dose-dependent manner. Behavioral analysis of larvae demonstrated that DEHP, DBP, DEP, and DINCH impair motor activity. The Oil Red O lipid staining showed a slight lipid accumulation in larval zebrafish at different DINP and DINCH concentrations. To further confirm the findings, qPCR was performed to analyze lipid metabolism genes. DINCH and DINP altered lipid metabolism genes including, fasn, srebp, pparg etc.  The oxidative stress state imposed by DINCH exposure was shown by a slight increase in superoxide dismutase enzymatic activity and the alteration on stress-related genes. In 3T3L1 cells, 10 and 100 μM of DINCH and DINP exposure induced lipid droplets formation like that induced by 100 nM rosiglitazone. Genes associated with lipid metabolism and lipid transport were altered by DINCH and DINP. These results indicate that DINCH exposure could induce physiological and metabolic toxicity. The data presented in this thesis could provide crucial information for further toxicological assessment.

Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.

Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.