Equilibrium swelling measurements of network and semicrystalline polymers in supercritical carbon dioxide using high-pressure NMR

The extent of swelling of cross-linked poly(dimethylsiloxane) and linear low-density poly(ethylene) in supercritical CO2 has been investigated using high-pressure NMR spectroscopy and microscopy. Poly(dimethylsiloxane) was cross-linked to four different cross-link densities and swollen in supercritical CO2. The Flory-Huggins interaction parameter, x, was found to be 0.62 at 300 bar and 45 degrees C, indicating that supercritical CO2 is a relatively poor solvent compared to toluene or benzene. Linear low-density poly(ethylene) was shown to exhibit negligible swelling upon exposure to supercritical CO2 up to 300 bar. The effect Of CO2 pressure on the amorphous region of the poly(ethylene) was investigated by observing changes in the H-1 T-2 relaxation times of the polymer. These relaxation times decreased with increasing pressure, which was attributed to a decrease in mobility of the polymer chains as a result of compressive pressure.

Enzyme catalysed modification of polymers

The aim of this project was to investigate the enzyme catalysed modification of synthetic polymers. It was found that an immobilised lipase from Candida antartica (Novozyme 435) catalysed the selective epoxidation of poly(butadiene) in the presence of hydrogen peroxide and catalytic quantities of acetic acid. The cis and trans double bonds of the backbone were epoxidised in yields of up to 60 % whilst the pendent vinyl groups were untouched. The effect of varying a number of reaction parameters was investigated. These studies suggested that higher yields of epoxide could not be obtained because of the conformational properties of the partially epoxidised polymer. Application of this process to the Baeyer-Villiger reaction of poly(vinyl phenyl ketone) and poly(vinyl methyl ketone) were unsuccessful. The lack of reactivity was found to be a property of the polymer rather than the enzymatic system employed. Attempts to modify hydroxyl containing polymers and polymers bearing active esters close to the polymer backbone were unsuccessful. Steric factors appear to be the most important influence on the outcome of the reactions.

Reactive processing methods for functionalisation of polymers and in-situ compatibilisation of poly(ethylene terephthalate)-based blends

One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

Atom transfer radical polymerisation - towards the synthesis of a fully-functional photorefractive polymer

Atom transfer radical polymerisation (ATRP) of styrene in xylene solution initiated with 1-phenylethyl bromide and mediated by CuBr/N-propyl-2- pyridinemethanimine catalyst complex was studied. The polymerisation was ill-controlled, yielding polymers with broad molecular weight distributions and values of number average molecular weight considerably higher than the theoretical values calculated from 100% initiator efficiency. The degree of control afforded over the polymerisation was enhanced by use of a more soluble catalyst complex, CuBr/N-octyl-2-pyridinemethanimine. Furthermore, the use of a more polar solvent, diglyme, generated a homogeneous catalyst complex that facilitated the production of polymers having narrow molecular weight distributions (1.10 < PDi < 1.20). The kinetics of the atom transfer radical polymerisation of methyl methacrylate at 90°C in diglyme solution initiated with ethyl-2-bromoisobutyrate and mediated by CuBr/N-octyl-2-pyridinemethanimine was studied and the orders of the reaction were established. The effect on the rate of polymerisation of the ratio of CuBr:N-octyl-2-pyridinemethanimine was also determined. The temperature dependencies of the rate of polymerisation of methyl methacrylate in diglyme solution and xylene solution were studied, and were found to be non-linear and dependent upon the polarity of the solvent. The use of highly polar aprotic solvents, such as N,N-dimethylformamide and dimethylsulphoxide, was found to be detrimental to the degree of control afforded over the polymerisation of methyl methacrylate. This was circumvented by use of a 5-fold excess, over that conventionally used, of catalyst complex. The atom transfer radical polymerisation of (4-nitrophenyl)-[3-[N-[2- (methacryloyloxy)ethyl]carbazolyl]]diazene in dimethyl sulphoxide solution was studied. Although homopolymerisation yielded only oligomers, copolymerisation of this monomer with methyl methacrylate was found to be readily achievable. Keywords: ATRP, Styrene; Methyl methacrylate; Polar solvents; Fully-functional photorefractive polymer. 2

Chemical modification of polymers

Based on the knowledge of PVC degradation and stabilisation, chemical modifications were imposed on degraded PVC and raw PVC with the aim of obtaining non-migrating additives. The modifications were carried out mainly in the presence of dibutyl maleate (DBM), and the resulting polymer contained dibutyl maleic residues. Such modifications result in a polymer which contain substantive additives which resist migration under aggressive environments. Previous studies have shown that stable nitroxyl radicals function as stabilisers in polymer during processing (e.g. PP, PVC) by deactivating a large number of kinetic chains via a redox process whereby the concentrations of the nitroxyl and its reduced form, the hydroxylamine, fluctuate reciprocally and rhythmically. In order to understand the major reactions involved in such systems, a simulation method was used which resulted in a mathematical model and some rate constants, explaining the kinetic behaviour exhibited by such system. In the process of forming a suitable model, two nonlinear oscillators were proposed, which could be of interest in the study of nonlinear phenomenon because of their chaotic behaviour.

Mechanisms of antifatigue agents used in natural rubber

A large number of compounds containing quinonoid or hindered phenol functions were examined for their roles as antifatigue agents. Among the evaluated quinones and phenols expected to have macroalkyl radical scavenging ability, BQ, αTOC, γTOC and GM showed relatively good performance for fatigue resistance (although their performance was slightly less effective than the commercial aromatic amine antioxidants, IPPD and 6PPD). The compounds which were shown to have higher reactivity with alkyl radicals (via calculated reactivity indices) showed better fatigue resistance. This fact supports the suggestion that strong alkyl radical scavengers should be also effective antifatigue agents. Evidence produced based on calculation of reactivity indices suggests that the quinones examined react with alkyl radicals on the meta position of the quinone rings producing phenoxyl radicals. The phenoxyl radicals are expected either to disproportionate, to recombine with a further alkyl radical, or to abstract a hydrogen from another alkyl radical producing an olefine. The regeneration of quinones and formation of the corresponding phenols is expected to occur during the antifatigue activity. The phenol antioxidant, HBA is expected to produce a quinonoid compound and this is also expected to function in a similar way to other quinones. Another phenol, GM, which is also known to scavenge alkyl radicals showed good antifatigue performance. Tocopherols had effective antifatigue activity and are expected to have different antifatigue mechanisms from that of other quinones, hence αTOC was examined for its mechanisms during rubber fatiguing using HPLC analysis. Trimers of αTOC which were produced during vulcanisation are suggested to contribute to the fatigue activity observed. The evidence suggests that the trimers reproduce αTOC and a mechanism was proposed. Although antifatigue agents evaluated showed antifatigue activity, most of them had poor thermoxidative resistance, hence it was necessary to compensate for this by using a combination of antioxidants with the antifatigue agents. Reactive antioxidants which have the potential to graft on the polymer chains during reactive processing were used for this purpose. APMA was the most effective antioxidant among other evaluated reactive antioxidants. Although high ratio of grafting was achieved after optimisation of grafting conditions, it is suggested that this was achieved by long branches of APMA due to large extent of polymerisation. This is expected to cause maldistribution of APMA leading to reducing the effect of CB-D activity (while CB-A activity showed clear advantages for grafting). Further optimisation of grafting conditions is required in order to use APMA more effectively. Moreover, although synergistic effects between APMA and antifatigue agents were expected, none of the evaluated antifatigue agents, BQ, αTOC, γTOC and TMQ, showed significant synergism both in fatigue and thermoxidative resistance. They performed just as additives.

The polymerization of lactic acid anhydrosulphite by anionic initiators

This thesis is primarily concerned with the synthesis and polymerization of 5-methyl-1;3, 2-dioxathiolan-4-one-2-oxide (lactic acid anhydrosulphite (LAAS)) using anionic initiators under various conditions. Poly(lactic acid) is a biodegradable polymer which finds many uses in biomedical applications such as drug-delivery and wound-support systems. For such applications it is desirable to produce polymers having predictable molecular weight distributions and crystallinity, The use of anionic initiators offers a potential route to the creation of living polymers. The synthesis of LAAS was achieved by means of an established route though the procedure was modified to some extent and a new method of purification of the monomer using copper oxides was introduced, Chromatographic purification methods were also examined but found to be ineffective. An unusual impurity was discovered in some syntheses and this was identified by means of 1H and 13C NMR, elemental analysis and GC-MS. Since poly-α-esters having hydroxyl-bearing substituents might be expected to have high equilibrium water contents and hence low surface tension characteristics which might aid bio-compatibility, synthesis of gluconic acid anhydrosulphite was also attempted and the product characterised by 1H and 13C NMR. The kinetics of the decomposition of lactic acid anhydrosulphite by lithium tert-butoxide in nitrobenzene has been examined by means of gas evolution measurements. The kinetics of the reaction with potassium tert-butoxide (and also sec-butyl lithium) in tetrahydrofuran has been studied using calorimetric techniques. LAAS was block co-polymerized with styrene and also with 1,3-butadiene in tetrahydrofuran (in the latter case a statistical co-polymer was also produced).

Time controlled photo-oxidation of polyolefins by polymer bound additives

A variety of iron compounds containing vinyl or thiol functional groups (used as photoactivators) have been synthesised and some of these were successfully bound to both polyethylene and polypropylene backbones during processing in the presence of peroxide and interlinking agent. Concentrates (masterbatches) of the photoactivators in PP and PE were prepared and the pro-oxidant effect of the diluted masterbatches in absence and presence of an antioxidant was evaluated. An antioxidant photoactivator (FeDNC ) was found to sensitise the photoactivity of pro-oxidants (Metone A / Metone M) whereas an antioxidant (ZnDNC) was found to stabilise the polymer (PP and PE) containing both of these combinations. It was observed that the lower concentration of FeDNC sensitises the stability of the polymer containing very small concentration of NiDNC whereas higher concentration of FeDNC stabilises the polymer (LDPE) containing same amount of NiDNC compared to FeDNC alone. The photostability of unstabilised PP containing FeAc could be varied by varying the concentration of ZnDEC. Both the induction period and the UV - life time of the polymer increased by increasing concentration of ZnDEC. It is suggested that ligand exchange reaction may take place between FeAc and ZnDNC. A polymer bound UV stabiliser (HAEB) and a thermal stabiliser (DBBA) were used with a non extractable photoactivator (FeAc) in PP. Small concentrations of the stabilisers (HAEB and DBBA) in combination with the photoactivator (FeAc) sensitise the polymer. The antioxidant present in commercial polymer (LDPE and PP) was found to be of a hindered phenol type, which was found to antagonise with ZnDNC when used in combination with the photoactivators.

Comparison of hydrophilic and hydrophobic active molecules release from polymer-phospholipid complexes

Hypercoiling polymers can be suited for application to living systems because they are similar in structure to the protein-based lipid assemblies found at fluid interfaces within the body. This leads to a range of exciting possibilities, not only in membrane transport applications but also in biosensors, drug delivery and mechanistic studies of biological membrane function. This study is focused in the study of the stability and suitability of nanostructures made of a hypercoiling polymer for drug delivery applications. The polymer poly (styrene-maleic acid) (PSMA) was combined with the phospholipid dimyristoylphosphatidylcholine (DMPC) to form amphiphilic nanostructures. The stability and suitability of these polymer-phospholipid nanocarriers for hydrophobic and hydrophilic molecules load and release was analyzed by several techniques. It was found that several of the studied molecules had a substantial effect on the surface charge and stability of the nanocarrier. It was also demonstrated that two types of nanocarriers, chemically modified and unmodified, were able to control the release of the molecules, especially in the case of hydrophobic compounds. In addition, as the hydrophobicity increased the release slowed down. These clear nanocarriers have the potential to behave very favorably at interfaces such as the tear lipid film were transparency is a requirement, giving a new way of controlled drug release in the eye.

Reactive processing of polymers:functionalisation of ethylene-propylene diene terpolymer (EPDM) in the presence and absence of a co-agent and effect of functionalised EPDM on compatibilisation of poly(ethylene terephthalate)/EPDM blends

Ethylene-propylene diene terpolymer (EPDM) was functionalized with glycidyl methacrylate (GMA) during melt processing by free radical grafting with peroxide initiation in the presence and absence of a reactive comonomer trimethylolpropane triacrylate (Tris). Increasing the peroxide concentration resulted in an increase in the GMA grafting yield, albeit the overall grafting level was low and was accompanied by higher degree of crosslinking of EPDM which was found to be the major competing reaction. The presence of Tris in the grafting system gave rise to higher grafting yield produced at a much lower peroxide concentration though the crosslinking reactions remained high but without the formation of GMA-homopolymer in either of the two systems. The use of these functionalized EPDM (f-EPDM) samples with PET as compatibilisers in binary and ternary blends of PET/EPDM/f-EPDM was evaluated. The influence of the different functionalisation routes of the rubber phase (in presence and absence of Tris) and the effect of the level of functionality and microstructure of the resultant f-EPDM on the extent of the interfacial reaction, morphology and mechanical properties was also investigated. It is suggested that the mechanical properties of the blends are strongly influenced by the performance of the graft copolymer, which is in turn, determined by the level of functionality, molecular structure of the functionalized rubber and the interfacial concentration of the graft copolymer across the interface. The cumulative evidence obtained from torque rheometry, scanning electron microscopy, SEM, dynamic mechanical analysis (DMA), tensile mechanical tests and Fourier transform infrared (FTIR) supports this. It was shown that binary and ternary blends prepared with f-EPDM in the absence of Tris and containing lower levels of g-GMA effected a significant improvement in mechanical properties. This increase, particularly in elongation to break, could be accounted for by the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET that would result in a graft copolymer which could, most probably, preferentially locate at the interface, thereby acting as an 'emulsifier' responsible for decreasing the interfacial tension between the otherwise two immiscible phases. This is supported by results from FTIR analysis of the fractionated PET phase of these blends which confirm the formation of an interfacial reaction, DMA results which show a clear shift in the T s of the blend components and SEM results which reveal very fine morphology, suggesting effective compatibilisation that is concomitant with the improvement observed in their tensile properties. Although Tris has given rise to highest amount of g-GMA, it resulted in lower mechanical properties than the optimized blends produced in the absence of Tris. This was attributed to the difference in the microstructure of the graft and the level of functionality in these samples resulting in less favourable structure responsible for the coarser dispersion of the rubber phase observed by SEM, the lower extent of T shift of the PET phase (DMA), the lower height of the torque curve during reactive blending and FTIR analysis of the separated PET phase that has indicated a lower extent of the interfacial chemical reaction between the phases in this Tris-containing blend sample. © 2005 Elsevier Ltd. All rights reserved.

Learning from mother nature:exploiting a biological antioxidant for the melt stabilisation of polymers

An overview of the antioxidant role of the biologically active form of vitamin E, α-tocopherol, in polyolefins is discussed. The effect of the vitamin antioxidant on the melt and colour stability of polyethylene (PE) and polypropylene (PP) is highlighted. It is shown that tocopherol is a highly effective antioxidant that results in superior melt stabilisation of polyolefins particularly when used at much lower concentration than that needed for conventional synthetic hindered phenol processing stabilisers. As with other hindered phenols,α-tocopherol imparts also some colour to the polymer but this is shown to be reduced drastically in the presence of other antioxidants, such as phosphites, or other additives, such as polyhydric alcohols.

High performance liquid level monitoring system based on polymer fiber Bragg gratings embedded in silicone rubber diaphragm

Liquid-level sensing technologies have attracted great prominence, because such measurements are essential to industrial applications, such as fuel storage, flood warning and in the biochemical industry. Traditional liquid level sensors are based on electromechanical techniques; however they suffer from intrinsic safety concerns in explosive environments. In recent years, given that optical fiber sensors have lots of well-established advantages such as high accuracy, costeffectiveness, compact size, and ease of multiplexing, several optical fiber liquid level sensors have been investigated which are based on different operating principles such as side-polishing the cladding and a portion of core, using a spiral side-emitting optical fiber or using silica fiber gratings. The present work proposes a novel and highly sensitive liquid level sensor making use of polymer optical fiber Bragg gratings (POFBGs). The key elements of the system are a set of POFBGs embedded in silicone rubber diaphragms. This is a new development building on the idea of determining liquid level by measuring the pressure at the bottom of a liquid container, however it has a number of critical advantages. The system features several FBG-based pressure sensors as described above placed at different depths. Any sensor above the surface of the liquid will read the same ambient pressure. Sensors below the surface of the liquid will read pressures that increase linearly with depth. The position of the liquid surface can therefore be approximately identified as lying between the first sensor to read an above-ambient pressure and the next higher sensor. This level of precision would not in general be sufficient for most liquid level monitoring applications; however a much more precise determination of liquid level can be made by linear regression to the pressure readings from the sub-surface sensors. There are numerous advantages to this multi-sensor approach. First, the use of linear regression using multiple sensors is inherently more accurate than using a single pressure reading to estimate depth. Second, common mode temperature induced wavelength shifts in the individual sensors are automatically compensated. Thirdly, temperature induced changes in the sensor pressure sensitivity are also compensated. Fourthly, the approach provides the possibility to detect and compensate for malfunctioning sensors. Finally, the system is immune to changes in the density of the monitored fluid and even to changes in the effective force of gravity, as might be obtained in an aerospace application. The performance of an individual sensor was characterized and displays a sensitivity (54 pm/cm), enhanced by more than a factor of 2 when compared to a sensor head configuration based on a silica FBG published in the literature, resulting from the much lower elastic modulus of POF. Furthermore, the temperature/humidity behavior and measurement resolution were also studied in detail. The proposed configuration also displays a highly linear response, high resolution and good repeatability. The results suggest the new configuration can be a useful tool in many different applications, such as aircraft fuel monitoring, and biochemical and environmental sensing, where accuracy and stability are fundamental. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.