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This thesis describes the techniques of anionic polymerisation and characterisation used in the synthesis of poly(methyl methacrylate)/poly(ethylene oxide) diblock copolymers, the various surface techniques used to examine the interfacial properties of these copolymers spread on water, and the dynamics of these copolymers in solution. The surface techniques used were surface pressure-concentration isotherm studies, neutron reflectivity, surface quasi-elastic light scattering, and ellipsometry. The thermodynamics of micellization and dynamic properties of the copolymer solutions were investigated using light scattering. The diblock copolymers had a target composition of 50:50 mole ratio and M(_W) = 50000. In addition, several copolymers had one or both blocks holly deuterated which was necessary for the neutron reflectivity studies where contrast variation was required to apply the kinematic approximation. Surface pressure isotherms give thermodynamic information about the behaviour of polymer segments at the interface. It has been possible to interpret this behaviour by using neutron reflectivity to obtain information concerning die thickness and distribution of the PMMA and PEO blocks, and water at the interface. The trends in layer thickness have been supported by the ellipsometric measurements and interpretation of the viscoelastic SQELS data has allowed conclusions about the hydrodynamics of the polymer chains at various surface concentrations.

Poly(methyl methacrylate) (PMMA) homopolymers synthesised using 'classical' anionic methods and subsequently studied by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) are discussed. Specifically, the attempts at different end-group functionalisation reactions, their varying degrees of success, and the characterisation of these functionalized polymers via MALDI are reported. Extra peaks were observed in the spectra of samples containing a tertiary amine end-group. A mechanism for the in situ elimination of H(_2)(g) involving these end-groups, which would fit the observations, is proposed. Two alternative, 'non-classical' routes to the desired materials were investigated, as difficulties in successfully performing capping reactions to give end functionalised PMMA were noted. The first method was a variation of standard anionic polymerisation that involved the use of lithium silanolates, which could be performed at a higher temperature than normal. The second was a controlled free-radical technique known as Reversible Addition-Fragmentation Chain Transfer (RAFT). A lack of control of the polymerisation to the desired degree was observed with the former method. A well-defined RAFT sample was observed to undergo in situ eliminadon also, for which a mechanism involving the dithioester end-group is proposed, and which is supported by MALDI-collision induced dissociation (CID) evidence. The synthesis of block copolymers of various compositions of MMA with r-butyl methacrylate (t-BMA) and hexyl methacrylate (HMA), along with their homopolymers, and their subsequent characterisation is reported. PHMA was analysed easily, in contrast to Pt-BMA. Only copolymers with a high PMMA content were analysed successfully and this has been rationalised in terms of the factors that affect cationisation. The characterisation of equimolar blends of various end-functionalised PMMA samples is reported also. Samples that favour the binding of a metal ion over protonation appear to have a higher ion yield. Once more, these observations are rationalised in terms of the factors that affect cationisation.

Novel amphiphilic graft copolymers with a backbone of poly(norbornene) (PNB) with poly(ethylene oxide) (PEO) grafts have been synthesised by a combination of ring opening metathesis and anionic polymerisation methods. The polymer has been prepared with hydrogenous and deuterated grafts and with grafts of different degrees of polymerisation. These graft copolymers spread at the air-water and air-PEO solution interface forming thin films and their organisation and dynamic behaviour is discussed. Monolayer behaviour was characterised from surface pressure isotherms and it was demonstrated that the shape of the isotherm is dependent on graft length and on the concentration of PEO in the subphase. Using neutron reflectometry the organisation of such spread films at the air-water interface have been obtained over a range of surface concentrations for each length of PEO graft. Data were analysed by both exact calculation methods and the partial kinematic approximation and the models adopted were verified by applying the model independent Bayesian analysis. All yield the same description i.e. the hydrophobic backbone remains at the uppermost surface while the PEO grafts penetrate the subphase. The PEO layer increases in thickness with increased surface concentration and graft length. In each case the rate of increase with surface concentration was initially rapid but above a critical concentration, a slower rate was observed. In this latter regime the variation of the tethered layer height scales with surface density (ơ) and degree of polymerisation of the graft (N) as, r(_s) = N(^1.06)ơ(^0.33),which agrees well with scaling and self consistent field theory of polymer brushes. The dynamic behaviour of each copolymer film spread on water has been studied using surface quasi-elastic light scattering. A resonance between the capillary and dilational waves is observed at identical surface concentrations for each copolymer film. The viscoelastic behaviour of the dilational mode is reminiscent of Kramers-Kronig relations. The phenomenon of resistive mode mixing was observed in frequency dependency studies.

The main aim of this project was to investigate the possibility of manufacturing 3D parts of polyamide (nylon or PA) 6 by inkjetting its monomer caprolactam (CL). The principle of this process was similar to the other rapid prototype (RP) and rapid manufacturing (RM) processes in which a 3D part is manufactured by layer on layer deposition of material. PA6 was used as the thermoplastic polymer in this work because of its good properties and also because PA6 can be produced by heating its monomer (i.e. plus catalyst and activator) in a short time. Two polymerisation mixtures of CL-catalyst (mixture A) and CL-activator (mixture B) are intended to be jetted separately using conventional jetting heads and polymerise shortly after heating. Anionic polymerisation of CL (APCL) was investigated in the bulk and on a smaller scale. Sodium caprolactamate (CLNa and C10) and caprolactam magnesium bromide (CLMgBr) were used as catalysts and N-acetylcaprolactam (ACL) and a di-functional activator (C20) were used as activators. The influence of polymerisation conditions was investigated and optimised. These were catalyst-activator concentration, polymerisation temperature and the influence of the polymerisation atmosphere. The physical properties (monomer conversion, crystallinity, and viscosity average molecular weight) of PA6 samples produced using each catalyst-activator combinations were measured and compared. Small scale polymerisation was carried out using a hotplate, by hot stage microscopy and using differential scanning calorimetry (DSC). The influence of heating strategy on small scale polymerisation was studied using DSC. The polymerisation mixture compositions were characterised using rheometry, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and optical microscopy to investigate their suitability in jetting for using the available jetting heads. It was shown that the combination of CLMgBr-ACL resulted in fast polymerisation which was not sensitive to moisture. The C10-C20 combination resulted in fast polymerisation with the best properties in a protected environment (nitrogen); however, the polymerisation was affected by moisture in air and the properties of polymer produced and rate of polymerisation decreased in air. Polymers produced using CLNa-ACL had the poorest properties and polymerisation did not occur in air. Material characterisation showed that micro-crystals of CLMgBr existed in CLMgBr-CL mixture at the jetting temperature (80oC) which were too large to be jetted. However, the mixture of C10 in CL could be partially jetted. The activator mixtures had similar properties to CL and were easily jetted. Drop on drop polymerisation was carried out by dripping droplets of mixtures A and B (at 80oC) on top of each other on a hotplate at the polymerisation temperature. Small scale polymerisation in a DSC showed that the monomer conversion increased with increase in polymerisation temperature from 140oC to 180oC and decreased from 180oC to 200oC. The crystallinity of the polymer produced in the DSC decreased with increase in polymerisation temperature. Hot stage microscopy produced evidence for simultaneous polymerisation and crystallisation processes on heating. Small scale polymerisation in an oven and analysed by DSC showed that increasing catalystactivator concentration resulted in increasing monomer conversion and decrease in crystallinity. Monomer conversion also increased with increase in polymerisation temperature and polymerisation time. Comparison between small scale and bulk polymerisations shows a good agreement between the two polymerisation rates. This shows that the polymerisation mechanism did not change significantly when the quantity of materials was reduced to less than 20mg. Finally, the polymerisation was carried out in a DSC after jetting C10-CL and C20-CL mixtures into a DSC pan using a jetting system, which was made in another work.

Els polímers són una sèrie de compostos que troben un ampli ventall d'aplicacions en la indústria actual. Un exemple són les espumes de poliuretà, estructures de tipus cel·lular obtingudes mitjançant la reacció química entre compostos de tipus isocianat i compostos de tipus poliol (polièters amb diferent nombre de grups hidroxil). És imprescindible l'ús d'additius d'estructura tensioactiva (surfactants de silicona) per estabilitzar el procés d'espumació i per proporcionar una estructura cel·lular ordenada i homogènia en mida i distribució. La síntesis i caracterització de les molècules precursores (polihidrosiloxans i polièters al·lílics), l'estudi de la reacció d'hidrosililació com a via d'obtenció dels diferents surfactants per reacció d'addició entre els polihidrosiloxans i els polièters al·lílics i la caracterització i avaluació en formulacions comercials de poliuretà dels surfactants sintetitzats han constituït els objectius del present treball.MEMÒRIALa Tesi Doctoral ha estat presentada seguint el següent esquema:CAPÍTOL I. INTRODUCCIÓ A LA QUÍMICA DEL POLIURETÀ.Es presenten els principis de la química del poliuretà, fent esment dels recents avenços en la síntesis i caracterització d'aquests compostos polimèrics, així com un apartat concret centrat en els surfactants de silicona. Es presenten les estructures habituals d'aquests compostos comercials i es detallen les reaccions de síntesi i les característiques físiques que aquests compostos proporcionen a les espumes de poliuretà.CAPÍTOL II. OBJECTIUS.1.- Síntesis y caracterització d'una àmplia gamma de poliglicols al·lílics i de polihidrosiloxans amb grups hidrur reactius, ambdós precursors d'estructures polimèriques de tipus surfactant.2.- Estudi de la reacció d'hidrosililació com a via de formació d'enllaços Si-C no hidrolitzables, mitjançant la reacció d'addició entre els substrats al·lílics insaturats i els polisiloxans amb grups hidrur reactius.3.- Caracterització de les estructures polimèriques de tipus surfactant sintetitzades i avaluació d'aquestes en formulacions de poliuretà, a fi de relacionar l'estructura química d'aquests oligómers amb els efectes físics que originen en l'espuma de poliuretà.CAPÍTOL III. SÍNTESI I CARACTERITZACIÓ DE SUBSTRATS AL·LÍLICS INSATURATS DE TIPUS POLIGLICOL.S'han caracteritzat per HPLC-UV una sèrie de polietilenglicols comercials. S'ha estudiat la reacció de derivatització al·lílica sobre els grups hidroxil dels polièters comercials (PEG, PPG i copolímers PEG-PPG) i s'han caracteritzat exhaustivament els productes sintetitzats (1H,13C-RMN, GC, GC-MS, FTIR, ESI-MS, HPLC-UV). S'ha iniciat un estudi de polimerització aniònica sobre nous epòxids amb un punt de diversitat molecular, sintetitzant-se i caracteritzant-se els corresponents nous polièters obtinguts. CAPÍTOL IV. SÍNTESI I CARACTERITZACIÓ DE POLIHIDROSILOXANS REACTIUS.S'estudia la síntesis de polihidrosiloxans amb grups hidrur reactius, mitjançant la reacció de polimerització aniònica d'obertura d'anell ("AROP, anionic ring opening polimerization") i mitjançant la reacció de polimerització per equilibració catiònica. Es presenta una caracterització exhaustiva dels productes sintetitzats i es descriu la naturalesa de la microestructura polimèrica a partir de la distribució bivariant dels copolímers PDMS-co-PHMS (poli(dimetilsiloxà)-co-poli(hidrometilsiloxà)).CAPÍTOL V. ESTUDI SISTEMÀTIC DE LA REACCIÓ D'HIDROSILILACIÓ.S'ha estudiat la reacció d'hidrosililació amb la finalitat de sintetitzar estructures copolimèriques poliglicol-polisiloxà a partir de la reacció de polisiloxans hidrur reactius i polièters al·lílics. S'han provat diferents catalitzadors (Pt/C 5%, cat. de Speier i cat. de Karstedt), s'han sintetitzat diferents estructures tensoactives (lineals i ramificades) i s'ha modelitzat les diferents reaccions secundàries observades, per presentar un estudi mecanístic de la reacció d'hidrosililació aplicada a la síntesis de molècules d'elevat PM a partir de la reacció entre substrats al·lílics insaturats i polihidrosiloxans.CAPÍTOL VI. AVALUACIÓ DELS SURFACTANTS EN FORMULACIONS DE POLIURETÀ.S'ha estudiat la idoneïtat dels surfactants de silicona sintetitzats en diferents formulacions de poliuretà comercials. S'ha relacionat el comportament físic d'aquests surfactants en les espumes de poliuretà amb la seva estructura química a partir de l'anàlisi per microscòpia electrònica de rastreig.CAPÍTOL VII. CONCLUSIONS.S'han esposat les conclusions extretes de cada capítol. / The present review has been structured in three parts, firstly a general introduction to polyurethane chemistry and the specific role that silicone surfactants develop, secondly a memory that contents a concise description of the PhD Thesis structure and finally the presentation of the results obtained and their discussion.1.- INTRODUCTIONPolyurethane is one of the most important polymers used in the industry worldwide. The reaction, discovered in 1937 by Otto Bayer, consists in a polyaddition reaction between hydroxyl compounds and isocyanate groups. This reaction forms the new urethane group (strictly a carbamat group) that provide the chemical structure of the polymer. In the presence of different amounts of water, another reaction is involved, between isocyanate groups and water, in order to obtain urea groups. This reaction is very important because, besides generates new polyurea structures it generates carbon dioxide (CO2), the blowing aggent mostly used in the formulations of polyurethane.Actually, a lot of applications of polyurethane products take advantage on the specific cellular structure that presents, specially flexible foams in mattresses, sofas, seats, rigid foams as insulation panels and semi-rigid foams in the automotive industry. The cellular structure is obtained in the foaming process of the reaction, which involves the generation of a gas (usually CO2 although other compounds like pentane, HCFC's and external CO2 had been used) and the growing of the cell because of the exothermic process. The foaming process is usually an unstable state that needs the participation of a surfactant, a silicone structure that provides the necessary stabilizing capacity in the foaming process. Moreover, another important feature of silicone surfactants is to improve the order and distribution of the cells in the foam.Generally, the chemical structure of silicone surfactants is co polymeric, consisting in an hydrophobic part composed by the polysiloxane group and an hydrophilic part, usually being made up of different types of polyether structures. This different physical behaviour in the same molecule provides the specific characteristics of silicone surfactants. In order to obtain commercially available surfactants, it has been necessary to study the synthesis and the characterization of the components in the surfactant molecule (the polyether and the polysiloxane groups) and to perform a study of the hydrosilylation, the chemical reaction that generates the co polymeric structure by the reaction between the polyether and the polysiloxane constituents.2.- PhD THESIS STRUCTUREThe thesis has been organized in seven chapters, being the first of them the introduction to polyurethane chemistry. In the second chapter are exposed the aims of the work. The third chapter is the synthesis and characterization of polyether type unsaturated substrates, the fourth is the synthesis and characterization of reactive polyhydrosiloxanes and the fifth is the systematic study on the hydrosilylation reaction. The evaluation of surfactants in different polyurethane formulations is described in the sixth chapter whereas the concluding remarks have been reported in the seventh chapter.3.- RESULTS AND DISCUSSIONThe first part of this study details the synthesis and characterization of unsaturated polyethers, substrates of the hydrosilylation reaction. Thus, the allylic modification of commercial monohidroxy polyethers has allowed the synthesis of this unsaturated substrates that can react through hydrosilylation reaction with Si-H bonds. In order to obtain new polyether structures, an investigation about the anionic polymerisation of new epoxies has been developed. These new polyether structures have been extensively characterized to estimate the polymerization degree and their molecular weight.The synthesis and characterization of reactive polysiloxane compounds (containing Si-H bonds in their structure) has been the second aim of this work. In order to obtain these polysiloxane structures, both anionic polymerization of cyclic trisiloxane compounds and cationic polymerization have been studied. Its interesting to emphasize that the results have shown that the microstructure of the copolymeric poly(dimethylsiloxane)-co-poly(hidromethylsiloxane) is statistical in the monomeric distribution (based on MALDI-TOF-MS and 29Si-RMN results), thus the chemical composition along the polymer chain become constant.Little information has been reported in the literature about the hydrosilylation as source of polymer structures. In order to clarify the synthetic behaviour of the reaction between polysiloxanes with Si-H bonds and allylic polyethers, an exhaustive study of the hydrosilylation as been developed. Different catalysts (Speier's, Karstedt's and an heterogeneous Pt/C 5% have been studied), concluding that the Karstedt catalyst has given the better behaviour.Finally, the evaluation of the surfactant structures synthesized in different commercially available polyurethane formulations as allowed obtaining a relation between the chemical structure of the silicone surfactant and the physical behavior in the foaming process. SEM has been the technique of choice to better characterize the otained foams.

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. However, MALDI-TOF-MS end group analysis showed that all synthesized macromonomers were a mixture of the macromonomer and the non-functionalized oligomer. The degree of functionalization varied from 55 to 75 %. The obtained macromonomers showed amphiphilic properties and formed micelles in water. The determined critical micellization (CMC) concentration for poly(glycidol) macromonomer (DP = 50) was ca. 10 g/L, while the poly(glycidol) block macromonomers with hydrophobic spacer showed CMC on the level 0,7 g/L. The conventional free radical and controlled free radical polymerisation (ATRP) were used for preparation of polymacromonomers with different properties. The radical polymerization of the macromonomers was carried out in water using AVA as initiator and in the mixture of water/benzene (10/1 v/v) using AIBN. Core-shell polymers of different character and molar masses with polydispersity indices from 1,4 -3,0 were obtained. The ATRP carried out in water using PEO macroinitiator led to polymacromonomers with polydispersity indices from 1,1 to 1,3 and desiried molecular weight. In all cases the conversion of macromonomer (able to polymerization) was close to 100%. The polymerization product could easily be separated from the unable to reaction residue.

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. However, MALDI-TOF-MS end group analysis showed that all synthesized macromonomers were a mixture of the macromonomer and the non-functionalized oligomer. The degree of functionalization varied from 55 to 75 %. The obtained macromonomers showed amphiphilic properties and formed micelles in water. The determined critical micellization (CMC) concentration for poly(glycidol) macromonomer (DP = 50) was ca. 10 g/L, while the poly(glycidol) block macromonomers with hydrophobic spacer showed CMC on the level 0,7 g/L. The conventional free radical and controlled free radical polymerisation (ATRP) were used for preparation of polymacromonomers with different properties. The radical polymerization of the macromonomers was carried out in water using AVA as initiator and in the mixture of water/benzene (10/1 v/v) using AIBN. Core-shell polymers of different character and molar masses with polydispersity indices from 1,4 -3,0 were obtained. The ATRP carried out in water using PEO macroinitiator led to polymacromonomers with polydispersity indices from 1,1 to 1,3 and desiried molecular weight. In all cases the conversion of macromonomer (able to polymerization) was close to 100%. The polymerization product could easily be separated from the unable to reaction residue.

New water soluble, attainable to ATRP polymerization Cl-terminated poly(glycidol) macroinitiators were prepared by modification of (Omega)-hydroxyl group of poly(glycidol acetal) using 2-chloropropionyl chloride fallowed by selective acidic deprotection of acetal groups. The obtained macroinitiators of different molar masses were successfully employed in ATRP of NIPAM and 4VP to give well-defined stimuli sensitive block copolymers of targeted molar ratio of blocks. The results obtained from light scattering methods showed formation of stable aggregates upon stimuli (pH or temperature) by all the obtained polymers. Additionally, photocrosslinkable block copolymers of glycidol and NIPAM having incorporated moieties of chromophore (2-(dimethyl maleinimido)-N-ethyl-acryl amide) were prepared using macroinitiator technique and used to synthesis of temperature sensitive microgels. Conjunction points have been successfully formed by UV irradiation of polymer water solution above cloud point. The influence of such parameters like block ratio, block length, amount of chromophore, concentration, irradiation time, temperature and heating rate on the properties of obtained microgels was investigated. The obtained core-shell structures were stable under critical conditions and showed continuous volume phase separation process upon increase of temperature, fully reversible and reproducible (no hysteresis effect). Thus, the proposed method not only gave the opportunity to control size or swelling degree of microgels, but also diminished gradient in crosslinking density (random chromophore distribution in polymer backbone), improved colloid stability (poly(glycidol) shell) and completely eliminated additives (surfactants, initiators, stabilizers).