The direct catalytic hydrogenation of nitrile butadiene rubber (NBR) in latex form was studied as a model system for the development of a new latex hydrogenation process for the modification of unsaturated diene-based polymers. NBR is a synthetic rubber of copolymerized acrylonitrile and butadiene produced in latex form by emulsion polymerization. The catalytic hydrogenation of NBR is an important post-polymerization process resulting in a more stable and tougher derivative, hydrogenated NBR (HNBR), which has been widely used in the automotive and oil drilling industry. The present commercial process involves a number of cumbersome steps to obtain solid NBR from the latex and subsequent dissolution of the solid NBR in a large amount of organic solvent followed by solvent recovery after coagulation of the hydrogenated NBR. Since NBR is produced in latex form, it is very desirable to directly hydrogenate NBR in the latex form which will significantly simplify the hydrogenation process and facilitate subsequent applications. As an economical and environmentally benign alternative to the commercial processes based on the hydrogenation of NBR in organic solution, this direct latex hydrogenation process is of special interest to industry. The objective of this project is to develop an efficient catalytic system in order to realize the direct catalytic hydrogenation of NBR in latex form. OsHCl(CO)(O2)(PCy3)2 was initially used as the catalyst to investigate the possibility of hydrogenation of NBR in latex form and to understand the major factors which affect the hydrogenation operation. It was found that an organic solvent which is capable of dissolving or swelling the NBR was needed in a very small amount for the latex hydrogenation using the Os catalyst, and gel occurred in such a catalytic system during hydrogenation. Wilkinson’s catalyst, RhCl(PPh3)3, was then used for the latex hydrogenation in the presence of a small amount of solvent successfully without gel formation. Further investigation found that Wilkinson’s catalyst has a high activity for NBR latex hydrogenation without the use of any organic solvent. The influences of various operation conditions on hydrogenation rate, such as catalyst and polymer concentrations, latex system composition, agitation, reaction temperature and hydrogen pressure, have been investigated. It was found that the addition of triphenylphosphine (TPP) has a critical effect for the hydrogenation of NBR latex, and the hydrogenation rate was mainly controlled by the amount of catalyst which diffused into the polymer particles. In the presence of TPP, NBR latex can be hydrogenated to more than 95% degree of hydrogenation after about 30 hours at 160oC using Wilkinson’s catalyst with a catalyst to NBR rubber ratio of 1 wt%, without the addition of any organic solvent. The apparent activation energy for such NBR latex hydrogenation over the temperature range of 152oC to 170oC was found to be 57.0 kJ/mol. In the present study, it was also found that there are some impurities within the NBR latex which are detrimental to the hydrogenation reaction and are suspected to be water-soluble surfactant molecules. Deliberately designed solution hydrogenation experiments were conducted to study the impurity issue, and proper latex treatment methods have been found to purify the latex before hydrogenation. To improve the hydrogenation rate and to optimize the latex hydrogenation system, water soluble RhCl(TPPMS)3 catalyst (TPPMS: monosulphonated-triphenylphosphine) was used for the latex hydrogenation of NBR. The latex hydrogenation using the water soluble catalyst with TPP can achieve more than 90% degree of hydrogenation within 20 hours at 160oC. Further experiments using RhCl3 with TPP proved that the water soluble RhCl3 can be directly used as a catalyst precursor to generate the catalytic species in situ for the latex hydrogenation, and a stable NBR latex with 96% degree of hydrogenation can be produced without any gel problem within 19 hours of reaction at 160oC. The catalyst mass transport processes for these Rh based catalysts in the latex system were investigated in order to further optimize the solvent-free latex hydrogenation process. While maintaining the emulsified state of the original latex, the direct catalytic hydrogenation of NBR latex can be carried out efficiently without any cross-linking problem to more than 92% degree of hydrogenation within 8 hours at 160oC. As a result of this research project, new latex hydrogenation technologies were successfully developed to fulfill all major requirements for a solvent-free polymer latex hydrogenation route, which is a significant milestone for the improvement of this polymer modification technology. The finding of TPP’s role as the “catalyst mass transfer promoter” is a breakthrough for the research field related to the hydrogenation of unsaturated diene-based polymers in latex form.

The direct catalytic hydrogenation of nitrile butadiene rubber (NBR) in latex form was studied as a model system for the development of a new latex hydrogenation process for the modification of unsaturated diene-based polymers. NBR is a synthetic rubber of copolymerized acrylonitrile and butadiene produced in latex form by emulsion polymerization. The catalytic hydrogenation of NBR is an important post-polymerization process resulting in a more stable and tougher derivative, hydrogenated NBR (HNBR), which has been widely used in the automotive and oil drilling industry. The present commercial process involves a number of cumbersome steps to obtain solid NBR from the latex and subsequent dissolution of the solid NBR in a large amount of organic solvent followed by solvent recovery after coagulation of the hydrogenated NBR. Since NBR is produced in latex form, it is very desirable to directly hydrogenate NBR in the latex form which will significantly simplify the hydrogenation process and facilitate subsequent applications. As an economical and environmentally benign alternative to the commercial processes based on the hydrogenation of NBR in organic solution, this direct latex hydrogenation process is of special interest to industry. The objective of this project is to develop an efficient catalytic system in order to realize the direct catalytic hydrogenation of NBR in latex form. OsHCl(CO)(O2)(PCy3)2 was initially used as the catalyst to investigate the possibility of hydrogenation of NBR in latex form and to understand the major factors which affect the hydrogenation operation. It was found that an organic solvent which is capable of dissolving or swelling the NBR was needed in a very small amount for the latex hydrogenation using the Os catalyst, and gel occurred in such a catalytic system during hydrogenation. Wilkinson’s catalyst, RhCl(PPh3)3, was then used for the latex hydrogenation in the presence of a small amount of solvent successfully without gel formation. Further investigation found that Wilkinson’s catalyst has a high activity for NBR latex hydrogenation without the use of any organic solvent. The influences of various operation conditions on hydrogenation rate, such as catalyst and polymer concentrations, latex system composition, agitation, reaction temperature and hydrogen pressure, have been investigated. It was found that the addition of triphenylphosphine (TPP) has a critical effect for the hydrogenation of NBR latex, and the hydrogenation rate was mainly controlled by the amount of catalyst which diffused into the polymer particles. In the presence of TPP, NBR latex can be hydrogenated to more than 95% degree of hydrogenation after about 30 hours at 160oC using Wilkinson’s catalyst with a catalyst to NBR rubber ratio of 1 wt%, without the addition of any organic solvent. The apparent activation energy for such NBR latex hydrogenation over the temperature range of 152oC to 170oC was found to be 57.0 kJ/mol. In the present study, it was also found that there are some impurities within the NBR latex which are detrimental to the hydrogenation reaction and are suspected to be water-soluble surfactant molecules. Deliberately designed solution hydrogenation experiments were conducted to study the impurity issue, and proper latex treatment methods have been found to purify the latex before hydrogenation. To improve the hydrogenation rate and to optimize the latex hydrogenation system, water soluble RhCl(TPPMS)3 catalyst (TPPMS: monosulphonated-triphenylphosphine) was used for the latex hydrogenation of NBR. The latex hydrogenation using the water soluble catalyst with TPP can achieve more than 90% degree of hydrogenation within 20 hours at 160oC. Further experiments using RhCl3 with TPP proved that the water soluble RhCl3 can be directly used as a catalyst precursor to generate the catalytic species in situ for the latex hydrogenation, and a stable NBR latex with 96% degree of hydrogenation can be produced without any gel problem within 19 hours of reaction at 160oC. The catalyst mass transport processes for these Rh based catalysts in the latex system were investigated in order to further optimize the solvent-free latex hydrogenation process. While maintaining the emulsified state of the original latex, the direct catalytic hydrogenation of NBR latex can be carried out efficiently without any cross-linking problem to more than 92% degree of hydrogenation within 8 hours at 160oC. As a result of this research project, new latex hydrogenation technologies were successfully developed to fulfill all major requirements for a solvent-free polymer latex hydrogenation route, which is a significant milestone for the improvement of this polymer modification technology. The finding of TPP’s role as the “catalyst mass transfer promoter” is a breakthrough for the research field related to the hydrogenation of unsaturated diene-based polymers in latex form.

Commodity and specialty-grade rubbers, such as styrene-butadiene (SBR) or nitrile-butadiene (NBR), are industrially produced in large trains of continuous reactors using an emulsion polymerization process. Both SBR and NBR systems are largely unstudied. Furthermore, the studies that have been published on NBR have been typically limited to issues concerning the characteristics of the product behaviour (i.e. oil/fuel resistance, tensile strength, hardness, compression set). In this work a detailed mathematical model has been developed in order to simulate the industrial production of NBR via emulsion copolymerization of acrylonitrile (AN) and butadiene (Bd) in batch, continuous and trains of continuous reactors. Model predictions include monomer conversion, polymerization rate, copolymer composition, number- and weight-average molecular weights, tri- and tetra-functional branching frequencies, and the number and average size of polymer latex particles. NBR is typically produced at low temperatures (5 to 10 degrees C) using a redox initiation system to generate free radicals. The system is typically composed of three phases, water, polymer particles, and monomer. Surfactants and electrolytes are used to stabilize the particle and monomer phases as polymerization proceeds. Of particular industrial importance, in today's world of tailor-made products, is detailed control over the polymerization reaction. Such control requires a deep understanding of the influence of various reactant feed rates and reactor operating conditions on the process response. In particular, policies to minimize copolymer composition drift and to control molecular weight, polydispersity and chain branching at desirable levels. The model is cast in a dynamic form using ordinary differential equations to describe the change of each species, the average number of particles, total average polymer volume, and the first three leading moments of the molecular weight distribution. With a multiphase system it is necessary to determine the concentration of each component in each phase. For this, a constant partition coefficient approach was adopted, as opposed to a purely thermodynamic approach. Particle generation was modelled considering both micellar and homogeneous mechanisms. Model parameters were obtained from the open literature or arrived at after sensitivity analysis. Simulations starting the reactors full of water, feeding all ingredients to the first reactor and using an average residence time of 60 minutes revealed considerable copolymer drift starting in the forth reactor (33% conversion), and heightened molecular weights and chain branching once the monomer phase disappeared (50% conversion). Further simulations revealed that both copolymer drift and the growth of molecular weight and branching could be controlled through additional feed streams of AN and chain transfer agent to downstream reactors. Furthermore, polymer productivity could be increased by appropriately splitting the total monomer feed between the first couple of reactors in the train.

Commodity and specialty-grade rubbers, such as styrene-butadiene (SBR) or nitrile-butadiene (NBR), are industrially produced in large trains of continuous reactors using an emulsion polymerization process. Both SBR and NBR systems are largely unstudied. Furthermore, the studies that have been published on NBR have been typically limited to issues concerning the characteristics of the product behaviour (i.e. oil/fuel resistance, tensile strength, hardness, compression set). In this work a detailed mathematical model has been developed in order to simulate the industrial production of NBR via emulsion copolymerization of acrylonitrile (AN) and butadiene (Bd) in batch, continuous and trains of continuous reactors. Model predictions include monomer conversion, polymerization rate, copolymer composition, number- and weight-average molecular weights, tri- and tetra-functional branching frequencies, and the number and average size of polymer latex particles. NBR is typically produced at low temperatures (5 to 10 degrees C) using a redox initiation system to generate free radicals. The system is typically composed of three phases, water, polymer particles, and monomer. Surfactants and electrolytes are used to stabilize the particle and monomer phases as polymerization proceeds. Of particular industrial importance, in today's world of tailor-made products, is detailed control over the polymerization reaction. Such control requires a deep understanding of the influence of various reactant feed rates and reactor operating conditions on the process response. In particular, policies to minimize copolymer composition drift and to control molecular weight, polydispersity and chain branching at desirable levels. The model is cast in a dynamic form using ordinary differential equations to describe the change of each species, the average number of particles, total average polymer volume, and the first three leading moments of the molecular weight distribution. With a multiphase system it is necessary to determine the concentration of each component in each phase. For this, a constant partition coefficient approach was adopted, as opposed to a purely thermodynamic approach. Particle generation was modelled considering both micellar and homogeneous mechanisms. Model parameters were obtained from the open literature or arrived at after sensitivity analysis. Simulations starting the reactors full of water, feeding all ingredients to the first reactor and using an average residence time of 60 minutes revealed considerable copolymer drift starting in the forth reactor (33% conversion), and heightened molecular weights and chain branching once the monomer phase disappeared (50% conversion). Further simulations revealed that both copolymer drift and the growth of molecular weight and branching could be controlled through additional feed streams of AN and chain transfer agent to downstream reactors. Furthermore, polymer productivity could be increased by appropriately splitting the total monomer feed between the first couple of reactors in the train.

Cette thèse de doctorat s’intéresse à la fatigue des élastomères, et plus particulièrement des caoutchoucs nitrile hydrogénés (sigle HNBR en anglais). Les HNBR sont des élastomères de haute performance,classiquement utilisés pour des applications industrielles à haute température où une bonne résistance chimique aux hydrocarbures est également requise.La thèse est divisée en trois parties principales.En premier lieu, des améliorations majeures pour les expériences de durée de vie en fatigue des élastomères sont proposées. Une approche expérimentale originale permettant le pilotage des essais en contrainte vraie est détaillée.Grâce à cette méthode, la première « vraie »courbe de Wöhler (contrainte vraie en fonction du nombre de cycles) pour des élastomères est tracée. Ensuite, des outils statistiques, issus de la recherche médicale, permettent une analyse probabiliste des résultats présentant une grande dispersion et des durées de vie censurées.Dans un second temps, ces nouveaux outils sont utilisés pour étudier l'effet de la formulation chimique – les taux d’acrylonitrile et d'hydrogénation notamment - sur la résistance en fatigue du HNBR à 120 oC. Ces résultats sont complétés par des expériences de propagation de fissure de fatigue et par une analyse de l'endommagement. Finalement, l'influence du vieillissement thermique sur la résistance en fatigue du HNBR est étudiée ; deux nouveaux essais sont développés : des essais simultanés de vieillissement et de fatigue, et des expériences de fatigue sur des échantillons préalablement vieillis.De plus, la cristallisation sous tension dans le HNBR est pour la première fois étudiée de manière quantitative / The present PhD thesis is devoted to investigation of fatigue in elastomers, andmore particularly of carbon black-filled hydrogenated nitrile butadiene rubber (HNBR).HNBR is a high performance elastomer classically used for high temperature industrial applications, where high resistance to industrial solvents is also required.The thesis is divided into three main parts.First, major improvements of testing procedures utilized in fatigue life testing ofelastomers are proposed. An original method to prescribe the true stress throughout fatigue experiments is developed; it permits to plot the first “true” Wöhler curve, i.e. true stress vs.number of cycles, for elastomers. Then,statistical tools, widely applied in medical research, are adopted for a comprehensive probabilistic analysis of fatigue life results that exhibit high scatter and censored lifetimes.Second, these novel tools are used to investigate the effect of chemical formulation -acrylonitrile content, percent hydrogenation,and of a composite blend - on fatigue resistance of HNBR at the service temperature of 120 oC. In addition to these fatigue life tests,fatigue crack propagation experiments and microscopic fatigue damage analysis are carried out. Third, the influence of thermal aging on fatigue performances of HNBR is investigated.To this end, two additional fatigue life tests are carried out: simultaneous aging and fatigue experiments, and fatigue experiments on preaged samples.Additionally, strain-induced crystallization in HNBR is studied; for the first time, quantitative relationships between crystallization, strain,and stress are established for unfilled HNBR blends.

Element Materials Technology in Linköping is an independent material testing company that performs testing of materials to several big sectors, such as the Swedish Armed Forces and the aerospace industry. There is of great importance to characterize aging of materials to ensure material performance. Element Materials Technology recently invested in a handheld FTIR equipment and it was of interest to see if this equipment might be an additional analysis technique to characterize aging of rubber materials. A nitrile butadiene rubber and two natural rubbers were thermally aged in 50°C and 70°C for six weeks. The hardness of the rubbers increased when the rubbers were thermally aged. The compression set decreased for the aged samples as well as the tensile strength and the elongation at break. An investigation of possible methods for collecting migrated additives on the rubber surface was performed, using two different solvents and a stationary FTIR equipment. More research needs to be performed to exclude the possibility that the solvents affect the material. Universal Attenuated Total Reflectance – Fourier Transform Infrared Spectroscopy, UATR-FTIR onto the rubber surface showed in some cases changes in the spectrums between unaged and aged samples. However, it could not be concluded weather the changes occurred due to migrating additives or due to changes in the backbone polymer. Four interfaces to the handheld FTIR equipment were investigated and an ATR interface gave best results. An analysis method was developed for the handheld FTIR equipment and the spectrums from the handheld FTIR were similar to spectrums from UATR-FTIR (stationary). It could be concluded from Micro Chamber analysis that volatile organic matters were emitted at elevated temperature. Thermogravimetric analysis could detect the relative composition of the rubbers. Further it could be concluded that the mechanical properties were affected by the thermal treatment. This study could however not establish a correlation between FTIR signals and the results seen from the other analysis. The fact that differences could be detected in the FTIR spectrums before and after aging could indicate that the FTIR analysis technique can possibly be used as an analysis method. However, a more thoroughly investigation needs to be performed before using this technique. / Element Materials Technology i Linköping utför materialutredningar åt en mängd olika typer av företag, där en stor sektor är den svenska Försvarsmakten och flygindustrin. Materialutredningar är essentiella för att säkerställa att rätt material används för rätt applikation. Element Materials Technology investerade nyligen i en handhållen FTIR utrustning. Det finns förhoppningar om att den nya utrustningen kan användas som ett komplement för att ålderskarakterisera gummimaterial. Ett nitril-butadien-gummi och två stycken naturgummin var termiskt åldrade i 50°C och 70°C i sex veckor. Hårdheten på provkroppar ökade efter den termiska åldringen. Sättningen, draghållfastheten och töjningen minskade för proverna åldrade i värme. En metod för att samla upp migrerade additiv från gummiytan utvecklades och undersöktes, genom att använda två olika lösningsmedel och en stationär FTIR utrustning. Ytterligare utredningar behöver däremot genomföras för att utesluta ifall de två lösningsmedel påverkar gummimaterialet och inte bara samlar upp additiv från gummiytan. UATR-FTIR visade på skillnader i spektrum mellan icke-åldrade och åldrade gummimaterial. Däremot kunde det inte avgöras om skillnaderna i spektrumen berodde på migration av additiv till gummiytan eller på förändring i huvudpolymeren. Fyra stycken olika tillbehör till den handhållna FTIR utrustningen prövades, där ATR-tillbehöret gav bra spektrum. En analyseringsmetod utvecklades för den handhållna FTIR-utrustningen och spektrum från dessa analyser gav liknande spektrum som spektrum från UATR-FTIR (stationär). Analys med Micro Chamber visade att flyktiga organiska ämnen lämnade gummimaterialet vid förhöjd temperatur. Termogravimetrisk analys, TGA visade förhållandet mellan gummimaterialets komponenter både före och efter åldring. Studien visade också att de mekaniska egenskaperna påverkades av den termiska åldringen. Analysmetoden FTIR kunde detekterad skillnad i spektrum före och efter åldring av gummimaterialen. Studien kunde däremot inte etablera ett samband mellan dessa FTIR-signaler och de övriga analysresultaten. Det kan däremot inte uteslutas att ett sådant samband finns. Ytterligare studier behöver utföras för att undersöka detta.

L’usage des élastomères en tant que matériau ne peut se concevoir sans l’utilisation de certaines charges dites renforçantes. Bien qu’une variété plutôt large de minéraux en poudre puisse être associée aux élastomères, deux charges sont très majoritairement utilisées de par leur haute capacité renforçante, les noirs de carbone et les silices actives et hautement structurées. L’utilisation de la silice n’a été envisagée, à partir des années 1980, que grâce à un contrôle fin de sa chimie de surface, de ses silanols hydrophiles et de son traitement par silanes spécifiquement dessinés pour satisfaire une application précise. La preuve expérimentale quantifiant les interactions charge – polymère est grandement souhaitée. C’est précisément le premier but que cette thèse tente d’approcher. Pour tenter d’atteindre cet objectif, nous proposons d’étudier dans ce travail l’évaluation de l’adsorption d'un polymère, une série de HNBR, sur des charges, noir de carbone et silice traitée ou non par des silanes spécifiquement désignés, d’un point de vue énergétique et moléculaire au moyen de la microcalorimétrie à écoulement (FMC). L'application de cet outil, relativement connu dans le cadre des interactions petite molécule – charge est plutôt original dans l’étude des couples polymère – charge. Notre deuxième but est donc, et grâce à une connaissance fine de la chimie des surface d'une silice, de ses traitements par des silanes, et de l'adsorption du polymère sur sa surface, d'explorer la corrélation entre le traitement et les propriétés macroscopiques dans le but d'établir une relation de cause à effet. / Most actual uses of elastomers are not even conceivable without the assistance of reinforcing filler. In this field, "silane-technology" brought into evidence the necessity of monitoring the competition that routinely rises between two determinant factors: polymer-filler interactions and filler-filler interactions. As a result, an important database founded essentially on the characterization of the surfaces chemistry and surface energy of the two antagonist elements had to be gathered. However, the determination of the consequence of such characters on the factual polymer-filler interactions remains rudimentary, such as bound rubber gravimetric measurements. Experimental prove which is able to quantify such interactions is badly needed. This is, actually, the first objective that we tried to achieve. In order to do so, we propose in this work to study, from the energy point of view using flow micro calorimeter (FMC), the evolution of the adsorption of a series of HNBR on the surface of carbon black (CB) and silicas unmodified and modified by selected silanes. If the goal of the silane technology is to design coupling agents that are able to satisfy a specific application, especially those related to the energy dissipation, the mechanism through which such a process is achieved is not fully understood. Thus, and based on a fine knowledge of surface chemistry, surface treatments and polymer adsorption, our second objective is to explore the cause-to-effect links that ought to exist between filler surface treatments and blends macroscopic properties.