Dissertations / Theses on the topic 'Alkyd resins'

Synthèse de nouveaux monomères RF phosphorés réactifs difonctionnels et étude de leur introduction dans la matrice polymère par copolymérisation. Essais de post-fonctionnalisation sur les résines polymères classiques puis évaluation des propriétés ignifugeantes du revêtement. Synthèse de nouveaux RF phosphorés réactifs issus de ressources renouvelables pour les intégrer à une formulation polymère partiellement biosourcée<br>Synthesis of new difunctional reactive phosphorus flame retardants monomers and study of their introduction into the polymer matrix by copolymerization. Tests of post-functionalization on conventional polymeric resins and evaluation of the flame retardant properties of the coating. Synthesis of new reactive phosphorus flame retardants from renewable resources to integrate in a partially biosourced polymer formulation

La famille des résines alkydes occupe une place prépondérante dans l'industrie des peintures et vernis. Leur élaboration s'effectue en milieu fondu à des températures supérieures à 180°C. Puis ces résines sont émulsionnées dans l'eau en présence de pigments, charges et de tensioactifs. L'objectif de cette thèse est d'effectuer la synthèse de ces alkydes à partir de monomères d'origine naturelle par polyestérification directement en émulsion dans l'eau et sous activation micro-ondes pour des gains de temps et d'énergie. La synthèse de ces alkydes a été réalisée tout d'abord en masse sous chauffage conventionnel, en utilisant des monomères issus principalement de la chimie verte. Puis les comportements énergétiques des émulsions de type huile/eau ou eau/huile ainsi que des solutions ioniques et micellaires ont été étudiés, permettant ainsi de comprendre la contribution de chacun des ses constituants. Avant d'effectuer la polyestérification des alkydes en émulsion dans l'eau, une étude modèle a été réalisée sous chauffage diélectrique MO en utilisant deux monomères de nature hydrophobes. Par comparaison avec le chauffage conventionnel, des polymères de masses molaires plus fortes sont obtenus en un temps plus court. La transposition de ce type de synthèse aux alkydes en utilisant deux principales voies de synthèses, en une seule ou deux étapes, nous a permis de sélectionner les bons tensioactifs permettant de maintenir des émulsions (huile /eau) stables à des températures allant jusqu'à 230°C. Cependant cette synthèse n'a abouti qu'à la formation d'un polymère de masse molaire de 3000 g/mole ce qui reste très faible par rapport à la synthèse en milieu fondu. Ceci est la conséquence directe de la compétition entre la réaction d'hydrolyse et la réaction de polyestérification. L'étude de la réaction d'hydrolyse des triglycérides provenant de l'huile de tournesol conduite en émulsion dans l'eau (eau/huile et huile/eau ) sous activation MO, montre une accélération de la réaction et par conséquent tout l'intérêt d'utiliser une activation micro-ondes<br>Alkyd resins are amongst the most important and widely used resins in coating sectors. Their preparation is carried out in bulk at elevated temperatures (˃180 ° C). These resins are then emulsified in water in the presence of pigments, fillers and surfactants. The objective of this thesis is to synthesis these alkyds directly in aqueous emulsion under microwaves activation to accelerate polyestrification reaction. The synthesis of these alkyds was performed in a molten state under conventional heating using monomers mainly from green chemistry. Then the energy behavior of emulsions, ionic and micellar solutions were studied, allowing understanding the contribution of each of their constituents. Before performing the polyesterification of alkyd emulsion in water, the polyesterification of hydrophobic compounds in aqueous emulsion was carried out under dielectric heating MO. Compared with conventional heating, polymers with molar masses higher are obtained in a shorter time. The transposition of this type of synthesis with Alkyd using two main synthetic routes, in one or two steps, we were able to select the surfactants to maintain emulsions (oil/water) stable at temperatures up to 230 °C. However, this synthesis led to the formation of polymer molar mass of 3000 g / mol, which is very low compared to the synthesis in the bulk conditions. This is a direct consequence of the competition between hydrolysis reaction and polyesterification reaction. The triglycerides hydrolysis study from sunflower oil in aqueous emulsion (water / oil and oil/water) under MO activation shows an acceleration of the reaction

The use of volatile organic compounds (VOC) in coating materials has adverse effects on both human health and the environment. Due to concern over these problems, coating industry has attempted to decrease the solvent contents of coating materials for the last three decades by developing water dispersed and powder paints. A recently developed method to make solvent free paint is to use highly branched polymers in high solid alkyd resins. Highly branched polymers help to achieve resins with viscosity much lower than its linear counterparts. In this study, a new alkyd based resin was formulated using long oil alkyd and melamine based hyperbranched polymer having 24 functional groups on its structure. The long oil alkyd was synthesized by using an oil mixture (40% linseed + 60% sunflower). Melamine was preferred as core molecule due to its excellent properties such as greater hardness, alkali and solvent resistance with thermal stability. The resin produced has low viscosity because its hyperbranched structure<br>therefore, it needs no solvent for its application. The chemical characterization of the resins with different compositions was performed using Fourier Transform Infrared Spectroscopy and thermal properties were determined by Differential Scanning Calorimetry. Physical and mechanical tests were conducted to determine hardness, flexibility, impact resistance, abrasion resistance, adhesion power, and gloss property of the samples. The viscosity of the resins decreased from 148 Pa.s to 8.84 Pa.s as the hyperbranched polymer to long oil alkyd ratio was increased from 1:3 to 1:24. On the other hand, the hardness values of the resins decreased from 198 Persoz to 43 Persoz. All resins showed excellent flexibility, formability, adhesion, and gloss.

Le comportement des encres sur machine depend essentiellement de leurs caracteristiques rheologiques. En particulier, l'augmentation considerable des vitesses d'impression implique la mise au point de compositions d'encre, adaptees aux contraintes qu'elles doivent supporter. Un objectif de ce travail est d'etablir des correlations entre la composition et les caracteristiques rheologiques de l'encre. Trois types de composants ont ete etudies: des huiles vegetales, ainsi que certains de leurs derives, des distillats petroliers, des resines alkydes et des vernis pour encres heat-set (rotatives avec secheurs). La loi de eyring decrit convenablement l'influence de la temperature sur la viscosite des oligomeres etudies. Sur des domaines de gradients relativement faibles (moins de 1000 s#-#1), le comportement rheologique des huiles, standolies et des resines alkydes est newtonien. Le comportement des vernis etudies est rheofluidifiant et peut etre modelise par l'equation de cross. Les caracteristiques viscoelastiques ont ete mesurees a l'aide d'un viscoanalyseur et traitees par le principe de superposition frequence-temperature, ce qui a permis de simuler les gradients de vitesse eleves, rencontres sur une presse. Ces mesures permettent en outre de mettre en evidence une correlation entre le tack de l'encre et ses proprietes elastiques. Par ailleurs, plusieurs systemes issus du monde industriel sont etudies: les caracteristiques de differents couples liant-pigments, l'utilisation de derives transesterifies de l'huile de colza comme substituant de distillats petroliers, l'utilisation de lignines papetieres comme additif modificateur de rheologie, la comparaison des proprietes rheologiques d'encres pour offset sans mouillage et d'encres offset conventionnelles

La modification chimique des 1,4-polydienes epoxydes et resines epoxyde thermodurcies par les acides di(alkyl ou aryl)phosphoriques a ete envisagee dans le but d'ameliorer leur tenue au feu. La fixation du principe actif est realisee par reaction entre la liaison acide p-oh de l'organophosphore et les cycles oxirane du polymere ou prepolymere. Une etude preliminaire sur des molecules modeles des polymeres etudies a permis la caracterisation des adduits formes en fonction des types d'epoxyde utilises, interne ou terminal. L'application de la reaction de modification aux 1,4-polydienes et au diglycidylether du bisphenol a (dgeba) a confirme les resultats obtenus avec les modeles et permis de prouver qu'une modification partielle des cycles oxirane par l'organophosphore peut se faire sans alterer les cycles residuels, resultat essentiel pour la reticulation ulterieure des systemes. Des systemes rigides tridimensionnels ont ete prepares par reticulation par l'anhydride methylnadique dans le cas des polydienes epoxydes et par la 4,4'-diaminodiphenylsulfone (dds) dans le cas des resines epoxyde du type dgeba. Des tests de tenue au feu et de stabilite thermique ont ete effectues sur ces systemes reticules. L'autoextinguibilite a l'air des polydienes reticules est observee quel que soit l'acide di(alkyl ou aryl)phosphorique utilise. Les meilleures tenues au feu sont toujours obtenues avec l'acide diphenylphosphorique, que ce soit pour les polydienes reticules ou pour les resines epoxyde thermodurcies. La formation d'un revetement carbone intumescent n'a ete observee que pour les systemes modifies dgeba/dds

Sizing (hydrophobization) is one of the most important process steps within the added-value chain of about 1/3rd of the worldwide produced paper & board products. Even though sizing with so-called reactive sizing agents, such as alkenyl succinic anhydride (ASA) was implemented in the paper industry decades ago, there is no total clarity yet about the detailed chemical and physical mechanisms that lead to their performance. Previous research was carried out on the role of different factors influencing the sizing performance, such as bonding between ASA and cellulose, ASA hydrolysis, size revision as well as the most important interactions with stock components, process parameters and additives during the paper making process. However, it was not yet possible to develop a holistic model for the explanation of the sizing performance given in real life application. This thesis describes a novel physico-chemical approach to this problem by including results from previous research and combining these with a wide field of own basic research and a newly developed method that allows tracing back the actual localization of ASA within the sheet structure. The carried out measurements and trial sets for the basic field of research served to evaluate the stock and process parameters that most dominantly influence the sizing performance of ASA. Interactions with additives other than retention aids were not taken into account. The results show that parameters, such as the content of secondary fibers, the degree of refining, the water hardness as well as the suspension conductivity, are of highest significance. The sample sets of the trials with the major impacting parameters were additionally analyzed by a newly developed localization method in order to better understand the main influencing factors. This method is based on optical localization of ASA within the sheet structure by confocal white light microscopy. In order to fulfill the requirements at magnification rates of factor 100 optical zoom, it was necessary to improve the contrast between ASA and cellulose. Therefore, ASA was pretreated with an inert red diazo dye, which does not have any impact on neither the sizing nor the handling properties of ASA. Laboratory hand sheets that were sized with dyed ASA, were analyzed by means of their sizing performance in correlation to measurable ASA agglomerations in the sheet structure. The sizing performance was measured by ultrasonic penetration analysis. The agglomeration behavior of ASA was analyzed automatically by multiple random imaging of a sample area of approx. 8650 µm² with a minimum resolution for particles of 500 nm in size. The gained results were interpreted by full factorial design of experiments (DOE). The trials were carried out with ASA dosages between 0% and 0.8% on laboratory hand sheets, made of 80% bleached eucalyptus short fiber kraft pulp and 20% northern bleached softwood kraft pulp, beaten to SR° 30, produced with a RDA sheet former at a base weight of 100 g/m² oven dry. The results show that there is a defined correlation between the ASA dosage, the sizing performance and the number and area of ASA agglomerates to be found in the sheet structure. It was also possible to show that the agglomeration behavior is highly influenced by external factors like furnish composition and process parameters. This enables a new approach to the explanation of sizing performance, by making it possible to not only examine the performance of the sizing agent, but to closely look at the predominant position where it is located in the sheet structure. These results lead to the explanation that the phenomenon of sizing is by far not a pure chemical process but rather a more physical one. Based on the gained findings it was possible so far to optimize the ASA sizing process in industrial-scale by means of ~ 50% less ASA consumption at a steady degree of sizing and improved physical sheet properties.

碩士<br>國立中興大學<br>森林學系所<br>102<br>In this study, Acacia confusa (Taiwan acacia) wood powders were liquefied in the mixture of ethylene glycol (EG)/ethylene carbonate (EC) with different weight ratios. H2SO4 was used as the catalyst and the liquefaction was undergone at 150oC for 60 min. The liquefied woods (LW) were then used as raw materials to react with adipic acid/phthalic anhydride (8/2; w/w) for synthesizing alkyd resins as alkyd polyols with the OH/COOH molar ratios of 1.6, 1.8 and 2.0. Furthermore, these alkyd resins were mixed with isocyanates (Desmodur N and Desmodur L) by the NCO/OH molar ratios of 1.2, 1.5 and 1.8 to prepare polyurethane resins (PU). The results show that the mixture of EG/EC could be used as a reagent for wood liquefying. Using the weight ratio of EG/EC as 5/5 had the better effect for liquefaction. TGA for unliquefied wood residues shows that lignin was more easily to be decomposition and dissolved than other components during liquefaction. The alkyd resins prepared with the OH/COOH molar ratio of 1.6 needed longer reaction time, and the prepared resin had higher viscosity and larger average molecular weight. DSC thermo-analysis shows that alkyd resins reacted with Desmodur N appeard more cross-linking reaction than that with Desmodur L. Comparison between alkyd resins with different OH/COOH molar ratios, the one prepared with the molar ratio of 2.0 needed more energy to accomplish the polymerization. Comparison between the liquefied reagents, LW-EG and LW-EC, the alkyd resins prepared with EG and EC liquefied wood, had higher reactivity than others. PU films that prepared by mixing alkyd resins with Desmodur N had the behavior of more flexibility, but it was stiffness for that with Desmodur L. PU films made with a larger NCO/OH molar ratio had higher tensile strength. On the other hand, alkyd resin prepared with a less OH/COOH molar ratio led the PU film having a larger breaking elongation. DMA thermo-analysis showed that Desmodur N-based PU films had a phase transfer occured at lower temperature. TGA showed that PU films prepared with Desmodur N as the raw material of isocyanate or with higher NCO/OH molar ratio both had a superior heat-resistance.

A Dissertation Submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the Degree of Master of Science in Polymer Chemistry.<br>The dissertation studies the synthesis, formulation development, crosslinking and spectral characterisation of dehydrated castor oil poly(glyceryl phthalate) alkyd resins for use as air-dry surface coating vehicles. Synthesis of alkyd resins involves simultaneous dehydration, alcoholysis and polyesterification reactions. Dehydration of castor oil is achieved in situ under phthalic anhydride catalysis. Alcoholysis of dehydrated castor oil by glycerol is also achieved in situ to form predominantly the monoglyceride. Polyesterification of the resultant mono- and diglycerides is realised through interaction with phthalic anhydride. The reaction is carried out at 280°C for 3 hours and at 225°C for 2 hours under azeotropic distillation with xylene. The parent poly(glyceryl phthalate) alkyd resin is synthesized by reaction of castor oil, glycerol and phthalic anhydride to a predetermined acid value. Formulation development experiments were carried out to study the effect of variations in the dibasic acid to polyol/oil and polyol to oil ratios on alkyd resin properties. Model formulations exhibiting the best alkyd performance were developed. Predictive model formulation equations were derived from model formulation data and their limits of reliability and applicability established. The formulation of water soluble alkyd resins is modified to introduce pendant carboxylic acid groups along the polymer skeleton. Water solubility is achieved by neutralisation of the residual pendant carboxylic acid groups by 'fugitive' amines to yield water soluble alkyd soaps. The effect of variations in the nature and level of incorporation of amine is investigated. Alkyd resin solubilisation and resin acidity guide formulae were studied and developed. Cross-linking chemistry of alkyd resins, both in the reactor (gelation) and on application (film formation) is investigated. Gelation manifested itself in two different forms, thermoplastic and thermosetting. An important alkyd constant, K, was established as an indispensable tool in control of premature gelation and in the prediction of resin drying characteristics. Autooxidation and solvent evaporation are the two competing curing mechanisms encountered in film formation. The nature and influence of each curing mechanism on the rate of cure and film characteristics is highlighted. Catalysis experiments were conducted with metallic driers (Co2 Mn2 and Pb2} to bring the rate of drying of resin films to economically feasible limits and catalyst addition levels were established. New spectral characterisation techniques based on Fourier Transform Infrared spectroscopy were investigated. An extensive study was carried out on FT IR spectral data to establish qualitative and quantitative relationships between transmission peak ratios and alkyd resin composition. Series dependent and series independent correlation equations, useful in quantifying alkyd resin components were derived. A new FT IR spectroanalytic characterisation method for dibasic acids is proposed. The method, if adopted, affords both qualitative and quantitative characterisation of the dibasic acid component in the alkyd resin matrix and it is envisaged the technique will supersede conventional methods in terms of speed and simplicity.'<br>Andrew Chakane 2021

碩士<br>長庚大學<br>化工與材料工程學系<br>100<br>In this study, alkyd resins are used for dye-sensitized solar cell working electrode preparation. The effects of the particle size, film thickness and film porosity on the photovoltaic conversion efficiency of the corresponding DSSC are discussed. Using a #200 stainless steel cloth screen with the squeegee printing speed of 11mm/s, the sintered working electrode film thickness is about 5~6μm. The DSSC using P90 TiO2 powders and alkyd resin for the preparation of the working electrode shows a photovoltaic conversion efficiency of 1.6%. Using a stencil screen with the same squeegee printing speed, the sintered working electrode film thickness is between 15~16μm. The DSSC using P25 and P90 powders and alkyd resins for the preparation of the working electrode shows a photovoltaic conversion efficiency of 3.4%.

Dissertação de mestrado integrado em Engenharia Biológica (área de especialização em Tecnologia Química e Alimentar)<br>Nos dias que correm, em qualquer indústria, há uma crescente preocupação com o impacto dos seus produtos no meio ambiente e na saúde humana. No caso do mercado das tintas, também existe essa preocupação, tendo-se desenvolvido tintas amigas do ambiente, com menor teor em compostos orgânicos voláteis (COVs), que reduzam a pegada de carbono e que tentem acompanhar e inovar nesta área, desenvolvendo novos produtos que marquem a diferença. As matérias-primas com maior incidência na formulação do produto deste projeto são as resinas alquídicas e é sobretudo nestas que há maior interesse, devido à possibilidade de incorporar maior quantidade de material de origem natural, como óleos vegetais e ácidos gordos. O principal objetivo do presente projeto é, pois, o desenvolvimento de uma tinta baseada em matérias-primas renováveis (RRM), com uma relação RRM/qualidade/preço satisfatória. Na persecução desse desiderato, foram desenvolvidas diversas tintas e no final foram comparadas com tintas padrão (P1 e P2) e tintas da concorrência internacional (C1 e C2). No decorrer do projeto foram testados antiespumas (AE1 e AE2), dispersantes (D1 e D2) e diversas resinas alquídicas (A a F). Após a definição do antiespuma (AE2) e dispersante (D2) a usar, foram testados diferentes teores de ligantes. Perante os resultados obtidos é possível afirmar que as tintas padrão apresentam um melhor desempenho em praticamente todos os ensaios, sendo que a tinta P2 tem melhor qualidade. No entanto, estes produtos têm na sua constituição uma menor quantidade de RRM. As tintas da concorrência internacional, de um modo geral, apresentaram performance inferior às tintas experimentais para todos os testes realizados e, no caso das experimentais, o produto com melhor comportamento corresponde à tinta 47 (Resina D). Esta apresenta um bom desempenho nas diversas características testadas, sendo a mais resistente às cinzas (ΔE = 1,6) e à esfrega húmida, e a que apresenta melhor relação RRM/qualidade/preço, relativamente aos produtos experimentais. Apresentando um teor de RRM igual a 51,8 % e em MBiobased igual a 20,3 %.<br>Nowadays, in any industry, there is a growing concern with the negative impacts of its products on the environment and human health. In the paint market, this concern it is also present, promoting the development of environment friendly paints with low content of volatile organic compounds (VOC’s), to reduce the carbon footprint and try to follow and innovate in this area, developing new products that makes the difference. The raw materials more focused on this project are the alkyd resins. These materials have special interest to the project because they provide the possibility of incorporating greater amount of natural material, such as vegetable oils and fatty acids. The main goal of this project is the development of a paint based on renewable raw materials (RRM), with a satisfactory relation RRM/performance/price. In pursuit of this goal, have been developed different paints and compared with standard paints (P1 and P2) and with other of international competition (C1 and C2). During the project, were tested different antifoams (AE1 and AE2), dispersants (D1 and D2) and various alkyd resins (A to F). After choosing the antifoam (AE2) and the dispersant (D2) to be used, were produced paints with different concentrations of binder. Analyzing the results, it is possible affirm that the standard paints have a better performance in almost every tests and P2 has better quality. However, these products have a minor amount of RRM in its composition. The international competition paints, in general, have a lower performance comparatively to the experimental paints at all the tests. In the case of experimental products, the product with better quality corresponds to the paint 47 (Resin D). Presenting a good performance in the multiple tests, being the most resistant to the ashes (ΔE = 1,6) and to the scrub wet, and the best relation RRM/performance/price, for experimental products. This product presents a RRM’s proportion of 51,8 % and 20,3 % of MBiobased.

碩士<br>國立中興大學<br>森林學系<br>84<br>In this study,Three kinds of drying oils for the manufacturing water soluble air-drying alkyd resins,then blend it with a high imino methylated melamine resin crosslinker, neutralizing agents and other additives for wood coatings and then the properties of paints were investigated. The molecular weight and its distribution were determined by Gel Permeation Chromatography (GPC). The rheological properties were measured by Viscometer, and the drying time of film was obtained by drying recorder. The crosslinking reaction and weatherability were determined by Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimeter (DSC) was used to evaluate the curing kinetics. It was found that the nature of drying oils, neutralizing agents, and cosolvents would significantly influence on the molecular weight, viscosity, stability, drying time and curing kinetics of the paints. When the tung/castor oil, was used as resin generally it showed a higher molecular weight and viscosity than those using soybean or linseed oil. The diethylamine neutralizing agent for paints exhibited the best stability and lower viscosity, In contrast, ammonia exhibited lower stability. The paints which included the resin that using linseed oil,ammonia and butyl cellosolve (EGMBE), showing the fastest drying time for coating film. However, the drying time of the film was found to be significantly decreased, due to blending it with high imino methylated melamine resin. But the crosslinking peak was very weak on the FTIR plot. It was also found that below 109 ℃ during the solvent evaporation stage,the endothermic peak occurred and it would suppress the DSC exotherm associated with the autooxidation crosslinking reaction. However,the temperature was above 109 ℃,the solvent would be completely evaporated,and exothermic reaction would occur,therefore the crosslinking reaction of amino alkyd resin at high temperature would be performed.It was found that the solvent may significantly influence on thermal behavior, and it was also found that the alkyd resin with more iodine value and lower preexponential constant (InZ) and lower activation energy, generally it would have a short drying time. The physical and chemical properties of the coating film depended on the rate of evaporation and stability of the neutralizing agent and the number of unsaturated double bond and hydroxyl group of oil modified alkyd resin. The paints those including the neutralizing agent and using ammonia, showed the best film hardness and water-resistance; but the paint using diethylamine system, exhibited a higher thermal degradation than that of the other 2 kinds of neutralizing agents. Regarding the evaluation of paint which contained a drying oil, linseed oil modified resin, it had a higher film hardness. In contrast, a blend of the drying oil which soybean oil was used as modified resin, it showed both better water-resistance and thermal degradation-resistance. In addition, whatever the substrate was used as coating, it was found that the film had good flexibility after 15 cycles of cold and hot treatment. In order to qualify the weatherability, the coated wood was placed in the artificially accelerated weatherometer (enclosed carbon-arc type) for 240 hours. The paint system which included ammonia and soybean oil modified resin still maintained a higher gloss retention than that of the other formulations. In addition,the film of the coated wood appeared to have better appearance after 240 hours of exposure. According to the SRS-FTIR measurement, the absorption peak of the methoxyl group (915cm-1) and alkyl group (1376cm-1) disappeared after 240 hours of exposure. The absorption peak of the triazine ring (1556cm-1) disappeared after 268 hours, while the absorption peaks of the carbonyl group(1710cm-1, 1721cm-1) increased after 268 hours. It was found that the fastest drying time for coating film in air was the alkyd resin containing 5% trimethylol propane diallyl ether (TMPDAE). Alkyd resin containing 10% or 15% had a longer drying time, therefore it would not have any improved effect. With a relative humidity under 65% and various temperature, it was found that in creasing the temperature resulted in an increased speed of the drying of the film. It also indicated the synergism of both temperature and relative humidity in affecting the drying rate of film. The alkyd resin coating containing 5% TMPDAE in air at 50 ℃ and under 45% RH, 2 hours drying time would be required. When UV illumination was applied, the drying time was reduced to 1 hour. Under these condition, the drying time of film was 9-18 times faster than drying in air at 25 ℃ and under 65%RH condition. With a DSC experiment, it was found that increasing the TMPDAE content, resulted in an increasing in the speed of the crosslinking reaction of the film. This indicated that the synergism of temperature and TMPDAE would affect the rate of crosslinking reaction.

碩士<br>大同工學院<br>化學工程研究所<br>87<br>In this study, liquid crystalline (LC) alkyd resins are prepared by the reaction of liquid crystalline monomer with an excess —OH or —COOH group of alkyd resins. These methods use dicyclohexylcarbodiimide (DCC) to promote esterification of PHBA and to remove water at room temperature. Pyridine is used as solvent, and catalytic amounts of p-toluensulfonic acid (p-TSA) are added to supress side reaction and to promote esterification monomer. In part 1, we choose 4-(4’-hydroxyphenol)benzoic acid to react with alkyd resins. And the LC alkyd resins provide the following benefits : polymer solution viscosity is reduced, dry-to-touch times are reduced and films have good resistance to water and acid. In part 2, terephthalic acid and hydroquinone were used to reacting with alkyd resins. It also showed good resistance to water and acid. The LC phenomenon of LC alkyd resins could be investigated differential scanning calorimeter (DSC) scan and polar microscopy. The Ti (clearing temperature) of LC phases is about 120-210 oC and the Tg (glass transition temperature) is in the range of 0 to 20 oC.

Sizing (hydrophobization) is one of the most important process steps within the added-value chain of about 1/3rd of the worldwide produced paper & board products. Even though sizing with so-called reactive sizing agents, such as alkenyl succinic anhydride (ASA) was implemented in the paper industry decades ago, there is no total clarity yet about the detailed chemical and physical mechanisms that lead to their performance. Previous research was carried out on the role of different factors influencing the sizing performance, such as bonding between ASA and cellulose, ASA hydrolysis, size revision as well as the most important interactions with stock components, process parameters and additives during the paper making process. However, it was not yet possible to develop a holistic model for the explanation of the sizing performance given in real life application. This thesis describes a novel physico-chemical approach to this problem by including results from previous research and combining these with a wide field of own basic research and a newly developed method that allows tracing back the actual localization of ASA within the sheet structure. The carried out measurements and trial sets for the basic field of research served to evaluate the stock and process parameters that most dominantly influence the sizing performance of ASA. Interactions with additives other than retention aids were not taken into account. The results show that parameters, such as the content of secondary fibers, the degree of refining, the water hardness as well as the suspension conductivity, are of highest significance. The sample sets of the trials with the major impacting parameters were additionally analyzed by a newly developed localization method in order to better understand the main influencing factors. This method is based on optical localization of ASA within the sheet structure by confocal white light microscopy. In order to fulfill the requirements at magnification rates of factor 100 optical zoom, it was necessary to improve the contrast between ASA and cellulose. Therefore, ASA was pretreated with an inert red diazo dye, which does not have any impact on neither the sizing nor the handling properties of ASA. Laboratory hand sheets that were sized with dyed ASA, were analyzed by means of their sizing performance in correlation to measurable ASA agglomerations in the sheet structure. The sizing performance was measured by ultrasonic penetration analysis. The agglomeration behavior of ASA was analyzed automatically by multiple random imaging of a sample area of approx. 8650 µm² with a minimum resolution for particles of 500 nm in size. The gained results were interpreted by full factorial design of experiments (DOE). The trials were carried out with ASA dosages between 0% and 0.8% on laboratory hand sheets, made of 80% bleached eucalyptus short fiber kraft pulp and 20% northern bleached softwood kraft pulp, beaten to SR° 30, produced with a RDA sheet former at a base weight of 100 g/m² oven dry. The results show that there is a defined correlation between the ASA dosage, the sizing performance and the number and area of ASA agglomerates to be found in the sheet structure. It was also possible to show that the agglomeration behavior is highly influenced by external factors like furnish composition and process parameters. This enables a new approach to the explanation of sizing performance, by making it possible to not only examine the performance of the sizing agent, but to closely look at the predominant position where it is located in the sheet structure. These results lead to the explanation that the phenomenon of sizing is by far not a pure chemical process but rather a more physical one. Based on the gained findings it was possible so far to optimize the ASA sizing process in industrial-scale by means of ~ 50% less ASA consumption at a steady degree of sizing and improved physical sheet properties.:Acknowledgment I Abstract III Table of Content V List of Illustrations XI List of Tables XVI List of Formulas XVII List of Abbreviations XVIII 1 Introduction and Problem Description 1 1.1 Initial Situation 1 1.2 Objective 2 2 Theoretical Approach 3 2.1 The Modern Paper & Board Industry on the Example of Germany 3 2.1.1 Raw Materials for the Production of Paper & Board 5 2.2 The Sizing of Paper & Board 8 2.2.1 Introduction to Paper & Board Sizing 8 2.2.2 The Definition of Paper & Board Sizing 10 2.2.3 The Global Markets for Sized Paper & Board Products and Sizing Agents 11 2.2.4 Physical and Chemical Background to the Mechanisms of Surface-Wetting and Penetration 13 2.2.4.1 Surface Wetting 14 2.2.4.2 Liquid Penetration 15 2.2.5 Surface and Internal Sizing 17 2.2.6 Sizing Agents 18 2.2.6.1 Alkenyl Succinic Anhydride (ASA) 19 2.2.6.2 Rosin Sizes 19 2.2.6.3 Alkylketen Dimer (AKD) 23 2.2.6.4 Polymeric Sizing Agents (PSA) 26 2.2.7 Determination of the Sizing Degree (Performance Analysis) 28 2.2.7.1 Cobb Water Absorption 29 2.2.7.2 Contact Angle Measurement 30 2.2.7.3 Penetration Dynamics Analysis 31 2.2.7.4 Further Qualitative Analysis Methods 33 2.2.7.4.1 Ink Stroke 33 2.2.7.4.2 Immersion Test 33 2.2.7.4.3 Floating Test 34 2.2.7.4.4 Hercules Sizing Tester (HST) 34 2.2.8 Sizing Agent Detection (Qualitative Analysis) and Determination of the Sizing Agent Content (Quantitative Analysis) 35 2.2.8.1 Destructive Methods 35 2.2.8.2 Non Destructive Methods 36 2.3 Alkenyl Succinic Anhydride (ASA) 36 2.3.1.1 Chemical Composition and Production of ASA 37 2.3.1.2 Mechanistic Reaction Models 39 2.3.1.3 ASA Application 42 2.3.1.3.1 Emulsification 42 2.3.1.3.2 Dosing 44 2.3.1.4 Mechanistic Steps of ASA Sizing 46 2.3.2 Physico-Chemical Aspects during ASA Sizing 48 2.3.2.1 Reaction Plausibility 48 2.3.2.1.1 Educt-Product Balance / Kinetics 48 2.3.2.1.2 Energetics 51 2.3.2.1.3 Sterics 52 2.3.2.2 Phenomena based on Sizing Agent Mobility 53 2.3.2.2.1 Sizing Agent Orientation 54 2.3.2.2.2 Intra-Molecular Orientation 55 2.3.2.2.3 Sizing Agent Agglomeration 55 2.3.2.2.4 Fugitive Sizing / Sizing Loss / Size Reversion 56 2.3.2.2.5 Sizing Agent Migration 58 2.3.2.2.6 Sizing Reactivation / Sizing Agent Reorientation 59 2.3.3 Causes for Interactions during ASA Sizing 60 2.3.3.1 Process Parameters 61 2.3.3.1.1 Temperature 61 2.3.3.1.2 pH-Value 62 2.3.3.1.3 Water Hardness 63 2.3.3.2 Fiber Types 64 2.3.3.3 Filler Types 65 2.3.3.4 Cationic Additives 66 2.3.3.5 Anionic Additives 67 2.3.3.6 Surface-Active Additives 68 2.4 Limitations of State-of-the-Art ASA-Sizing Analysis 69 2.5 Optical ASA Localization 71 2.5.1 General Background 71 2.5.2 Confocal Microscopy 72 2.5.2.1 Principle 72 2.5.2.2 Features, Advantage and Applicability for Paper-Component Analysis 74 2.5.3 Dying / Staining 75 3 Discussion of Results 77 3.1 Localization of ASA within the Sheet Structure 77 3.1.1 Choice of Dyes 77 3.1.1.1 Dye Type 78 3.1.1.2 Evaluation of Dye/ASA Mixtures 80 3.1.1.2.1 Maximum Soluble Dye Concentration 80 3.1.1.2.2 Thin Layer Chromatography 81 3.1.1.2.3 FTIR-Spectroscopy 82 3.1.1.3 Evaluation of the D-ASA Emulsion 84 3.1.1.4 Paper Chromatography with D-ASA & F-ASA Emulsions 85 3.1.1.5 Evaluation of the D-ASA Emulsion’s Sizing Efficiency 86 3.1.2 The Localization Method 87 3.1.2.1 The Correlation between ASA Distribution and Agglomeration 88 3.1.2.2 Measurement Settings 89 3.1.2.3 Manual Analysis 90 3.1.2.4 Automated Analysis 92 3.1.2.4.1 Automated Localization / Microscopy Measurement 92 3.1.2.4.2 Automated Analysis / Image-Processing 93 3.1.2.5 Result Interpretation and Example Results 96 3.1.2.6 Reproducibility 97 3.1.2.7 Sample Mapping 98 3.1.3 Approaches to Localization-Method Validation 102 3.1.3.1 Raman Spectroscopy 102 3.1.3.2 Confocal Laser Scanning Fluorescent Microscopy 102 3.1.3.3 Decolorization 103 3.2 Factors Impacting the Sizing Behavior of ASA 104 3.2.1 ASA Type 105 3.2.2 Emulsion Parameters 107 3.2.2.1 Hydrolyzed ASA Content 107 3.2.2.2 ASA/Starch Ratio 109 3.2.2.3 Emulsion Age 110 3.2.3 Stock Parameters 111 3.2.3.1 Long Fiber/Short Fiber Ratio 111 3.2.3.2 Furnish Type 112 3.2.3.3 Degree of Refining 114 3.2.3.4 Filler Type/Content 116 3.2.4 Process Parameters 119 3.2.4.1 Temperature 119 3.2.4.2 pH-Value 120 3.2.4.3 Conductivity 122 3.2.4.4 Water Hardness 123 3.2.4.5 Shear Rate 125 3.2.4.6 Dwell Time 127 3.2.4.7 Dosing Position & Dosing Order 128 3.2.4.8 Drying 130 3.2.4.9 Aging 131 3.3 Factors Impacting the Localization Behavior of ASA 132 3.3.1 Degree of Refining 132 3.3.2 Sheet Forming Conductivity 135 3.3.3 Water Hardness 136 3.3.4 Retention Aid (PAM) 137 3.3.5 Contact Curing 138 3.3.6 Accelerated Aging 139 3.4 Main Optimization Approach 141 3.4.1 Optimization of ASA Sizing Performance Characteristics 142 3.4.2 Emulsion Modification 144 3.4.2.1 Lab Trials / RDA Sheet Forming 146 3.4.2.2 TPM Trials 147 3.4.2.3 Industrial-Scale Trials 149 3.4.2.4 Correlation between Sizing Performance Optimization and Agglomeration Behavior on the Example of PAAE 152 3.5 Holistic Approach to Sizing Performance Explanation 154 4 Experimental Approach 157 4.1 Characterization of Methods, Measurements and Chemicals used for the Optical Localization-Analysis of ASA 157 4.1.1 Characterization of used Chemicals 157 4.1.1.1 Preparation of Dyed-ASA Solutions 157 4.1.1.2 Thin Layer Chromatography 157 4.1.1.3 Fourier Transformed Infrared Spectroscopy 157 4.1.1.4 Emulsification of ASA 158 4.1.1.5 Paper Chromatography 159 4.1.1.6 Particle Size Measurement 159 4.1.2 Optical Analysis of ASA Agglomerates 160 4.1.2.1 Microscopy 160 4.1.2.2 Automated Analysis 163 4.1.2.2.1 Adobe Photoshop 163 4.1.2.2.2 Adobe Illustrator 164 4.1.2.3 Confocal Laser Scanning Fluorescent Microscopy 166 4.2 Characterization of Used Standard Methods and Measurements 166 4.2.1 Stock and Paper Properties 166 4.2.1.1 Stock pH, Conductivity and Temperature Measurement 166 4.2.1.2 Dry Content / Consistency Measurement 167 4.2.1.3 Drainability (Schopper-Riegler) Measurement 167 4.2.1.4 Base Weight Measurement 168 4.2.1.5 Ultrasonic Penetration Measurement 168 4.2.1.6 Contact Angle Measurement 169 4.2.1.1 Cobb Measurement 169 4.2.1.2 Air Permeability Measurements 170 4.2.1.3 Tensile Strength Measurements 170 4.2.2 Preparation of Sample Sheets 171 4.2.2.1 Stock Preparation 171 4.2.2.2 Laboratory Refining (Valley Beater) 171 4.2.2.3 RDA Sheet Forming 171 4.2.2.4 Additive Dosing 173 4.2.2.5 Contact Curing 174 4.2.2.6 Hot Air Curing 174 4.2.2.7 Sample Aging 174 4.2.2.8 Preparation of Hydrolyzed ASA 175 4.2.2.9 Trial Paper Machine 175 4.2.2.10 Industrial-Scale Board Machine 177 4.3 Characterization of used Materials 178 4.3.1 Fibers 178 4.3.1.1 Reference Stock System 178 4.3.1.2 OCC Fibers 179 4.3.1.3 DIP Fibers 179 4.3.2 Fillers 180 4.3.3 Chemical Additives 180 4.3.3.1 ASA 180 4.3.3.2 Starches 181 4.3.3.3 Retention Aids 181 4.3.3.4 Poly Aluminum Compounds 181 4.3.3.5 Wet Strength Resin 181 4.3.4 Characterization of used Additives 182 4.3.4.1 Solids Content 182 4.4 Description of Implemented Advanced Data Analysis- and Visualization Methods 183 4.4.1 Design of Experiments (DOE183 4.4.2 Contour Plots 184 4.4.3 Box-Whisker Graphs 185 5 Conclusion 186 6 Outlook for Further Work 191 7 Bibliography 192 Appendix 207 7.1 Localization Method Reproducibility 207 7.2 DOE - Coefficient Lists 208 7.2.1 Trial 3.3.4 – Impact of Retention Aid (PAM) on Agglomeration Behavior and Sizing Performance 208 7.2.2 Trial 3.3.5 – Impact of Contact Curing on Agglomeration Behavior and Sizing Performance 208 7.2.3 Trial 3.3.6 – Impact of Accelerated Aging on Agglomeration Behavior and Sizing Performance 209