No abstract

SYNOPSISAn investigation was made of polymer-analogous reactions of the epoxide ring bound to the polymer chain with a number of agents such as amines, diamines, hydroxyamines, carboxylic acids, phosphoric acid, phosphorus pentoxide, thiourea, etc. The polymers used were homogeneous or slightly reticular gels. All reactions were considerably affected by the type and thermodynamic quality of the solvent. Reactions with the amino compounds were greatly dependent on their basicity and on the size of the alkyl groups. By using diamines one can obtain a material containing free amino groups capable of further reactions. A sufficiently high conversion of the reaction of the epoxide group with carboxylic and mineral acids could be achieved only in an anhydrous medium. In other media acid-catalyzed hydrolysis predominated, along with the required addition reaction. If the reaction mixture was treated with thiourea and then left to react with hydrogen sulphide, a polymer gel was formed containing two vicinal thio groups able to bind heavy metals.The reactions described show that the epoxide group bound in the copolymer allows a number of reactions which lead to products with properties markedly different from the starting material. I55

By the method of design of experiments it was investigated the effect of some components of polymerization feed as the content of inert components, crosslinking agent, initiator, thermodynamic quality of inert components and polymerization temperature on the specific surface area of the produced sorbents which were copolymers from glycidylmethacrylate and ethylenedimethacrylate. By varying the five parameters given above, it was possible to control the specific surface area within the range 0-460 m2 g-I. ZUSAMMENFASSUNG:Bei der Copolymerisation von Glycidylmethacrylat mit Ethylenglykoldimethacrylat wurden folgende Parameter variiert: Die Konzentration von Inertkomponente, Vernetzer, Initiator, die thermodynamische Qualitat der Inertkomponenten sowie die Polymerisationstemperatur. Hierdurch war es moglich, die spezifische Oberflache der Copolymeren in einem Bereich von 0 bis 460 m2g -' zu variieren.

The reaction of macroporous copolymers glycidyl methacrylateethylenedimethacrylate with ammonia, primary and secondary amines, diamines and hydroxyalkyl amines leading to products with wide applicability was investigated. The reaction can be carried out without or with solvent, water being quite sufficient as the latter. The effects of amine concentration, substituents, temperature and type of the solvent on the reaction course were examined. The reaction product with dimethyl amine and 2-hydroxyethyl amine was alkylated consecutively, and a strongly basic anion exchanger of second type was obtained. ZUSAMMENFASSUNG:Die Reaktion von makroporosen Copolymeren aus Glycidylmethacrylat und Athylendimethacrylat mit Ammoniak, primaren und sekundaren Aminen, Diaminen und Hydroxyalkylaminen wurde untersucht, die zu Produkten mit vielfaltiger Verwendbarkeit fiihrte. Die Reaktion kann ohne oder mit Losungsmittel durchgefuhrt werden. Die Einfliisse der Aminkonzentration, der Substituenten, Temperatur und Art des Losungsmittels auf den Reaktionsverlauf wurden untersucht. Die Reaktionsprodukte mit Dimethylamin und 2-Hydroxyathylamin ergaben nach anschlieoender Alkylierung stark basische Ionenaustauscher.* Part VII, Eur. Polym. J., in press.

By drying at 78 "C, the macroporous terpolymer 2,3-dihydroxypropyl methacrylate-co-sodium methacrylate-co-ethylene dimethacrylate with a water retention of 3.78 g H20/g loses porosity which is renewed by reswelling. Drying of this terpolymer at 0 -25 "C by which water or methyl alcohol is removed does not disturb its porosity. Less swelling copolymers such as 2,3-dihydroxypropyl methacrylate-co-ethylene dimethacrylate with a water retention of 1.71 g H20 /g do not lose its permanent porosity when dried. Inversion gas chromatography has made possible the determination of the glass transition temperature of these macroporous terpolymers (Tg = 45 "C) by using heptane and methyl alcohol as retention acids. With respect to this, and using scanning electron microscopy the loss of porosity due to drying was interpreted as sintering of macroporous copolymers whose polymer networks swell to a higher degree on heating above T, . ZUSAMMENFASSUNG:Das makroporose terpolymere Natriumsalz von 2,3-Dihydroxypropylmethacrylatco-methacrylsaure-co-ethylenglykoldimethacrylat (Wasseraufnahme: 3,78 g H,O/g) verliert an Porositat, wenn es bei 78 "C getrocknet wird. Durch erneute Quellung wird die Anfangsporositat wieder hergestellt. Wenn das gleiche Terpolymere bei 0 bis 25 "C getrocknet wird, kann Wasser oder Methanol ohne Porositatsverlust entfernt werden. Wenig quellende Copolymere wie Poly-2,3-dihydroxypropylmethacrylat-coethylenglykoldimethacrylat mit einer Wasseraufnahme von 1,71 g H 2 0 /g verlieren beim Trocknen ihre Porositat nicht. Durch inverse Gaschromatographie unter Verwendung von Heptan oder Methanol als Retentionsmittel wurde die Bestimmung der Glastemperatur der hier beschriebenen makroporosen Terpolymeren ermoglicht (T, = 45 "C).