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.

The synthesis of biodegradable polymers using aluminium alkoxide initiators

Alkyl aluminium alkoxides have been used as initiators for the ring opening polymerisation of ε-caprolactone and δ-valerolactone. The effect of the reaction solvent on the kinetics of the polymerisation of ε-caprolactone has been studied. The rate of polymerisation was found to be faster in solvents of lower polarity and donor nature such as toluene. In general solvents of higher polarity resulted in a decreased rate of polymerisation. However solvents such as THF or DMF with a lone pair of electrons capable of forming a complex with the aluminium centre slowed the polymerisation further. The size of the monomer also proved to be an important factor in the kinetics of the reaction. The six membered ring, δ-valerolactone has less ring strain than the seven membered ring ε-caprolactone and thus the polymerisation of δ-valerolactone is slower than the corresponding polymerisation of ε-caprolactone. Both the alkoxide and alkyl group structures have an effect on the polymerisation. In general bulkier alkoxide groups provide greater steric hindrance around the active site at the beginning of the reaction. This causes an induction or a build up period that is related to the both the steric hindrance and also the electronic effects provided by the alkoxide group. The alkyl group structure has an effect throughout the polymerisation because it remains adjacent to the active centre. The number of alkoxide groups on the aluminium centre is also important, using a dialkoxide as an initiator yields polymers with molecular weights approximately half that of the corresponding reactions using a mono alkoxide. Transesterification reactions have also been found to occur after most of the monomer has been consumed. These transesterification reactions are exaggerated as temperature increases. A method of producing tri-block co-polymers has also been developed. A di-hydroxy functional pre-polymer, PHBV, was reacted with an aluminium alkyl to form a di-alkoxide macroinitiator which was subsequently used as an initiator for the polymerisation of ε-caprolactone to form an ABA type tri-block co-polymer. The molecular weight and other properties were predictable from the initial monomer/initiator ratios.

Synthesis and evaluation of novel polymer modifiers for biodegradable polymers

The effects of ester plasticizers and copolymers on the mechanical properties of the natural biodegradable polymers, poly(3-hydroxybutyrate) [PHB] and poly(lactic acid) [PLA] have been studied after subjecting to melt processing conditions. Ester plasticizers were synthesized from citric, tartaric and maleic acids using various alcohols. A variety of PLA copolymers have also been prepared from poly(ethylene glycol) derivatives using stannous octanoate catalysed ring opening polymerisations of DL-lactide. A novel PLA star copolymer was also prepared from an ethoxylated pentaerythritol. The structures of these copolymers were determined by NMR spectroscopy. The plasticizing effect of the synthesised additives at various concentrations was determined. While certain additives were capable of improving the mechanical properties of PLA, none were effective in PHB. Moreover, it was found that certain combinations of additives exhibited synergistic effects. Possible mechanisms are discussed. Biotic and abiotic degradation studies showed that the plasticizers (esters and copolymers) did not inhibit the biodegradability of PHB or PLA in compost at 60°C. Simple toxicity tests carried out on compost extract and its ability to support the growth of cress seeds was established. PLA was found to be susceptible to limited thermal degradation under melt processing conditions. Conventional phenolic antioxidants showed no significant effect on this process, suggesting that degradation was not predominantly a free radical process. PLA also underwent photo-oxidative degradation with UV light and the process could be accelerated in the presence of a photoactivator such as iron (III) diisononyl dithiocarbamate. The mechanisms for the above processes are discussed. Finally, selected compounds were prepared on a pilot plant scale. Extruded and blown films were prepared containing these additives with conventional polymer processing equipment. The mechanical properties were similar to those obtained with laboratory produced compression moulded films.

Novel imprinted polymers as artificial enzymes

Derivatives of L-histidine were investigated as suitable models for the Asp-His couple found in the catalytic triad of serine proteases. A combination of molecular dynamics and IH NMR spectroscopy suggested that the most populous conformations of N-acetyl-L-histidine and the N-acetyl-L-histidine anion were predominated by those in which the carboxylate group was gauche to the imidazole ring overcoming steric and electrostatic repulsion, suggesting there is an interaction between the carboxylate group and the imidazole ring. Kinetic studies, using imidazole, N-acetyl-L-histidine and the N-acetyl-L-histidine anion showed that in a DMSO/H20 9: 1 v/v solution, the N-acetyl-L-histidine anion catalysed the hydrolysis of p-nitrophenyl acetate at a greater rate than using either imidazole or N-acetyl-L-histidine as catalyst. This indicates that the carboxylate group affects the nucleophilicity of the unprotonated imidazole ring. 31P MAS NMR spectroscopy was investigated as a new technique for the study of the template molecule environment within the polymer networks. It was found that it was possible to distinguish between template associated with the polymer and that which was precipitated onto the surface, though it was not possible to distinguish between polymer within imprinted cavities and that which was not. Attempts to study the effect of the carboxylate group/imidazole ring interaction in the imprinted cavity of a molecularly imprinted polymer network were hindered by the method used to follow the reaction. It was found though that in a pH 8.0 buffered solution the presence of imprinted cavities increased the rate of reaction for those polymers derived from L-histidine. Some preliminary investigations into the design and synthesis of an MIP which would catalyse the oxy-Cope rearrangement were carried out but the results were inconclusive.

Novel cationic polymers for use at biological interfaces

One of the main problems with the use of synthetic polymers as biomaterials is the invasion of micro-organisms causing infection. A study of the properties of polymeric antibacterial agents, in particular polyhexamethylene biguanide, has revealed that the essential components for the design of a novel polymeric antibacterial are a balance between hydrophilicity and hydrophobicity coupled with sites of cationicity. The effect of cation incorporation on the physical properties of hydrogels has been investigated. Hydrogel systems copolymerised with either N-vinyl imidazole or dimethylaminoethyl methacrylate have been characterised in terms of their water binding, mechanical and surface properties. It has been concluded that the incorporation of these monomers does not adversely affect the properties of such hydrogels and that these materials are potential candidates for further development for use in biomedical applications. It has been reported that hydro gels with ionic character may increase the deposition of biological material onto the hydrogel surface when it is in contact with body fluids. An investigation into the deposition characteristics of hydrogels containing the potentially cationic monomers has been carried out, using specific protein adsorption and in vitro spoilation techniques. The results suggest that at low levels of cationicity, the deposition of positively charged proteins is reduced without adversely affecting the uptake of the other proteins. The gross deposition characteristics were found to be comparable to some commercially available contact lens materials. A preliminary investigation into the development of novel antibacterial polymers has been completed and some novel methods of bacterial inhibition discussed. These methods include development of an hydrogel whose potential application is as a catheter coating.

Novel hydrogel polymers

Hydrogels are a unique class of polymers which swell, but do not dissolve in water. A range of 2-hydroxyethyl methacrylate based copolymer hydrogels have been synthesised and are described in this thesis. Initially, hydrogels were synthesised containing acryloylmorpholine, N,N-dimethyl acrylamide and N-vinyl pyrrolidone. Variations in structure and composition have been correlated with the sequence distribution, equilibrium water content (EWC) , mechanical and surface properties of the hydrogels. The sequence distribution was found to be dependant on the structure and reactivity of the monomers. The EWC was found to be dependant on the water structuring groups present in the hydrogel, although the water binding abilities were modified by steric effects. The mechanical properties were also investigated and were found to be dependant on the monomer structure, sequence distribution and the amount and nature of water in the hydrogel. The macroscopic surface properties of the hydrogels were probed using surface energy determinations and were found to be a function of the water content and the hydrogel composition. At a molecular level, surface properties were investigated using an in vitro ocular spoilation model and single protein adhesion studies. The results indicate that the sequence distribution and the polarity of the surface affect the adhesion of biological species. Finally, a range of 2-hydroxyethyl methacrylate based copolymer hydrogels containing both charged monomer groups and linear polyethers have been synthesised and described. Although variations in the EWC are observed with the structure of the monomers, it was observed that the EWC increased due to the polar character of the charged monomers and the chain length and hydrophilicity of the polyethers. Investigation of these hydrogel surfaces revealed subtle changes. The molecular surface properties indicate the significance of the effect of charge and molecular mobility of the groups expressed at the hydrogel surface.

The Synthesis and properties of functionalised polymers

The aim of this project was to synthesise fluorinated polymers that might act as hot material in a guest-host system for use in non-linear optical applications. These polymers would be expected to have the advantage over materials such as poly(vinylidene fluoride) which is known to be incompatible with many nlo active materials. A series of bicyclic fluorinated monomers was prepared by the reaction of fluorinated dienophiles with cyclopentadiene in a series of Diels-Alder reactions. The monomers were purified and then used in ring opening metathesis polymerisation. The materials were then characterised by gel permeation chromatography and nuclear magnetic resonance spectroscopy and cast as films for determination of their activities as nlo materials using a Nd/YAG laser system. The second harmonic intensity of each was measured relative to quartz. However no materials of significant activity were produced. In an attempt to produce polymers that might subsequently be functionalised the polymerisation of 1,2-methylenedioxybenzene and 1,4-benzodioxane was investigated.

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.

Migration of additives from thermoplastic polymers

A homologous series of ultra-violet stabilisers containing 2-hydroxybenzophenone (HBP) moiety as a uv absorbing chromophore with varying alkyl chain lengths and sizes were prepared by known chemical synthesis. The strong absorbance of the HBP chromophore was utilized to evaluate the concentration of these stabilisers in low density polyethylene films and concentration of these stabilisers in low density polyethylene films and in relevant solvents by ultra-violet/visible spectroscopy. Intrinsic diffusion coefficients, equilibrium solubilities, volatilities from LDPE films and volatility of pure stabilisers were studied over a temperature range of 5-100oC. The effects of structure, molecular weight and temperature on the above parameters were investigated and the results were analysed on the basis of theoretical models published in the literature. It has been found that an increase in alkyl chain lengths does not change the diffusion coefficients to a significant level, while attachment of polar or branched alkyl groups change their value considerably. An Arrhenius type of relationship for the temperature dependence of diffusion coefficients seems to be valid only for a narrow temperature range, and therefore extrapolation of data from one temperature to another leads to a considerable error. The evidence showed that increase in additive solubility in the polymer is favoured by lower heat of fusions and melting points of additives. This implies the validity of simple regular solution theory to provide an adequate basis for understanding the solubility of additives in polymers The volubility of stabilisers from low density polyethylene films showed that of an additive from a polymer can be expressed in terms of a first-order kinetic equation. In addition the rate of loss of stabilisers was discussed in relation to its diffusion, solubility and volatility and found that all these factors may contribute to the additive loss, although one may be a rate determining factor. Stabiliser migration from LDPE into various solvents and food simulants was studied at temperatures 5, 23, 40 and 70oC; from the plots of rate of migration versus square root time, characteristic diffusion coefficients were obtained by using the solution of Fick's diffusion equations. It was shown that the rate of migration depends primarily on partition coefficients between solvent and the polymer of the additive and also on the swelling action of the contracting media. Characteristic diffusion coefficients were found to approach to intrinsic values in non swelling solvents, whereas in the case of highly swollen polymer samples, the former may be orders of magnitude greater than the latter.

Synthetic polymers for ophthalmic applications

The contact lens represents a well-established important class of biomaterials. This thesis brings together the literature, mostly Japanese and American patents, concerned with an important group of polymers, `rigid gas permeable contact lens materials'. A comparison is made of similarities in the underlying chemical themes, centring on the use of variants of highly branched siloxy compounds with polymerizable methacrylate groups. There is a need for standard techniques to assess laboratory behaviour in relation to in vitro performance. A major part of the present work is dedicated to the establishment of such standardised techniques. It is apparent that property design requirements in this field (i.e. oxygen permeability, surface and mechanical properties) are to some extent conflicting. In principle, the structural approaches used to obtain high oxygen permeability lead to surface properties that are less than ideal in terms of compatibility with tears. PMMA is known to have uniquely good (but not perfect) surface properties in this respect; it has been used as a starting point in attempting to design new materials that possess a more acceptable compromise of transport and surface properties for ocular use. Initial examination of the oxygen permeabilities of relatively simple alkyl methacrylates, show that butyl methacrylate which has a permeability some fifty times greater than PMMA, represents an interesting and hitherto unexplored group of materials for ophthalmic applications. Consideration was similarly given to surface modification techniques that would produce materials having the ability to sustain coherent tear film in the eye without markedly impairing oxygen transport properties. Particular attention is paid to the use of oxygen plasma techniques in this respect. In conclusion, similar design considerations were applied to an extended wear hydrogel lens material in an attempt to overcome mechanical stability deficiencies which manifest themselves lq`in vivo' but not `in vitro'. A relatively simple structure modification, involving steric shielding of the amide substituent group, proved to be an effective solution to the problem.

Novel hydrogel polymers

Hydrogels may be conveniently described as hydrophilic polymers that are swollen by, but do not dissolve in water. In this work a series of copolymer hydrogels and semi-interpenetrating polymer networks based on the monomers 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and N'N' dimethyl acrylamide, together with some less hydrophilic hydroxyalkyl acrylates and methacrylates have been synthesised. Variations in structure and composition have been correlated both with the total equilibrium water content of the resultant hydrogel and with the more detailed water binding behaviour, as revealed by differential scanning calorimetry studies. The water binding characteristics of the hydrogels were found to be primarily a function of the water structuring groups present in gel. The water binding abilities of these groups were, however, modified by steric effects. The mechanical properties of the hydrogels were also investigated. These were found to be dependent on both the polymer composition and the amount and nature of the water present in the gels. In biological systems, composite formation provides a means of producing strong, high water content materials. As an analogy with these systems hydrogel composites were prepared. In an initial study of these materials the water binding and mechanical properties of semi-interpenetrating polymer networks of N'N'dimethyl acrylamide with cellulosic type materials, with polyurethanes and with ester containing polymers were examined. A preliminary investigation of surface properties of both the copolymers and semi-interpenetrating polymer networks has been completed, using both contact angle measurements and anchorage dependent fibroblast cells. Measurable differences in surface properties attributable to structural variations in the polymers were detected by droplet techniques in the dehydrated state. However, in the hydrated state these differences were masked by the water in the gels. The use of cells enabled the underlying differences to be probed and the nature of the water structuring group was again found to be the dominant factor.

Functionalised polymers

Synthetic routes to polymers possessing functional groups were studied. Direct functionalisation of poly(vinyltoluene) by lithiation and carboxylation resulted in the expected carboxylic acid but reaction was complicated by the production of a mixture of products. Reaction occurred both at the polymer backbone and at the pendant methyl group. Reaction with ethyl formate was also difficult to control and a secondary alcohol was formed even when an excess of the carbonyl compounds was employed. Grignard formation of poly(bromostyrene) was successful but once formed, the derivative rearranged resulting in chain scission and degradation of the polymer. Therefore subsequent reactions of the Grignard reagent with carbonyl groups were unsuccessful in producing functionalised polymers. Reactions of vinyltoluene monomer were more successful. Although complications arose when lithiation and carboxylation of the monomer were carried out using lithium diisopropylamide because the carboxylic acid product reacted with the excess lithium diisopropylamide present, metallation by potassium t-butoxide followed by reaction with 2-(3-chloropropyl)-2-methyl-1,3-dioxalane resulted in the formation of 2-methyl-2(4-(vinylphenyl)-butyl-1,3,-dioxalane. The butyllithium initiated anionic polymerisation of this protected monomer resulted in a polymer which had a very narrow molecular weight distribution (Mw/Mn= 1.05) and subsequent hydrolysis of the polymer resulted in poly(6(vinylphenyl)-hexan-2-one) which was derivatised with 2,4 dinitrophenyl-hydrazine. Functionalisation by modification of the siloxane derivative 3-(methylpropenoxycarbonyl)ltrimethoxysilane was unsuccessful. The acid catalysed exchange reactions of this monomer with alcohols such as eugenol, octan-1-ol, pentan-1-ol, and hexan-1-ol were inefficient, resulting in a mixture of products and unreacted starting materials.

Microencapsulation studies with P(HB-HV) polymers

Microencapsulation processes, based upon the concept of solvent evaporation, have been employed within these studies to prepare microparticles from poly--hydroxybutyrate homopolymers and copolymers thereof with 3-hydroxyvalerate [P(HB-HV) polymers]. Variations in the preparative technique have facilitated the manufacture of two structurally distinct forms of microparticle. Thus, monolithic microspheres and reservoir-type microcapsules have been respectively fabricated by single and double emulsion-solvent evaporation processes. The objective of the studies reported in chapter three is to asses how a range of preparative variables affect the yield, shape and surface morphology of P(HB-HV) microcapsules. The following chapter then describes how microcapsule morphology in general, and microcapsule porosity in particular, can be regulated by blending the fabricating P(HB-HV) polymer with poly--caprolactone [PCL]. One revelation of these studies is the ability to generate uniformly microporous microcapsules from blends of various high molecular weight P(HB-HV) polymers with a low molecular weight form of PCL. These microcapsules are of particular interest because they may have the potential to facilitate the release of an encapsulated macromolecule via an aqueous diffusion mechanism which is not reliant on polymer degradation. In order to investigate this possibility, one such formulation is used in chapter five to encapsulate a wide range of different macromolecules, whose in vitro release behaviour is subsequently evaluated. The studies reported in chapter six centre on the preparation and characterization of hydrocortisone-loaded microspheres, prepared from a range of P(HB-HV) polymers, using a single emulsion-solvent evaporation process. In this chapter, the influence of the organic phase viscosity on the efficiency of drug encapsulation is the focus of initial investigations. Thereafter, it is shown how the strategies previously adopted for the regulation of microcapsule morphology can also be applied to single emulsion systems, with profound implications for the rate of drug release.