Volker Steinert

SURFACE MODIFICATION WITH HYDROGELS VIA MACROINITIATORS FOR ENHANCED FRICTION PROPERTIES OF BIOMATERIALS

ABSTRACT A general method of surface modification is described which is based on dip-coating of a substrate with a macroinitiator and subsequent free radical polymerization of functional monomers. Using this method, it is possible to fix poly(acrylic acid) hydrogels on polymer surfaces, e.g. on catheters, which drastically reduces the friction of these materials. Similarly, other biological relevant properties, especially reduced protein or bacteria adsorption can be achieved by choosing appropriate monomers. The substrate was first homogeneously dip-coated with e.g. the water-insoluble macroinitiator poly(octadecene-co-maleic anhydride), partially reacted to the tert.-butyl perester. Homogeneity, thickness, and reactivity of the macroinitiator layer was characterized in detail. After a temper step, surface homo- and copolymerizations of ionic monomers were carried out in water directly from the modified surface. The consistency of the hydrogel coating could be well controlled by the reaction conditions a...

Kinetic Investigations of Reactions with Maleic Anhydride Copolymers and Model Compounds

Abstract Alternating copolymers that contain maleic anhydride (MAn) as a component occur in two different stereochemical configurations which are differentiated by their reactivity. Model compounds, 2, 3-dialkylsuccinic acids and their anhydrides, were investigated and it was demonstrated that there is a distinct difference between threo and erythro configurations in their chemical and physical behavior. Both configurations also occur in the alternating copolymers. Beside the model compounds, the alternating copolymers ethylene-MAn, propylene-MAn, and styrene-MAn were investigated in their reactions with amines, alcohols, and water (hydrolysis). The cis configurations showed the higher reaction rates. Reactions of the anhydride moieties with equimolar amounts of aniline, ethanol, and water demonstrated that reactions follow second-order rate laws. With excess reactant, the reaction follows a pseudo-first-order rate law. The rate constants depend on the degree of polymerization and on the comonomer. Increa...

Investigations on the dissociation behavior of hydrolyzed alternating copolymers of maleic anhydride and alkenes: 13C-NMR spectra and potentiometric titrations

The pKa values of the succinic acid moieties of hydrolyzed alternating ethene- and isobutene-maleic anhydride copolymers were determined in D2O. The pD-dependence on the 13C chemical shift of selected signals was analyzed for these copolymers. Four different pKas were determined for the copolymer with ethene due to the existence of both the erythro- and threo-configuration of the succinic acid moiety: pK01,erythro = 4.2, pK0.1,threo = 4.1, pK02,erythro = 6.1, pK02,threo = 6.8. The isobutene-maleic anhydride copolymer contains only threo-units. Therefore, only two dissociation steps with pK01 = 3.0 and pK02 = 8.7 were observed for the hydrolyzed form.

The influence of cations on the dissociation behaviour of copolymers of propene and maleic acid and their modified products with taurine in salt-free solution

Potentiometric and conductometric titrations were used to study the dissociation behaviour of poly(propene-co-maleic acid) and poly(propene-co-maleic acid) modified with various contents of taurine (2-aminoethanesulfonic acid) in salt-free solution. Copolymers of propene and maleic acid with different molecular weights were titrated with LiOH, NaOH, and KOH. The influence of molecular weight on pKa is ascertainable in both the first and second dissociation step. Of the various alkali metal cations studied, lithium had the most significant effect on the dissociation behaviour. The acidic strength decreased in the order lithium > sodium ≥ potassium. After insertion of sulfonic acid groups into poly(propene-co-maleic acid), the influence of strong acidic groups on the dissociation behaviour of carboxylic groups was studied. The contents of taurine were 10, 25, and 50 mol%. The second dissociation step was analyzed in this case. The pKa values increased with increasing content of taurine for titrations with LiOH and KOH, but not NaOH. When NaOH was used, the pKa decreases if the polymer was modified with 10% taurine. Higher taurine contents had no influence on the magnitude of pKa. The results demonstrate the strong influence of short-range electrostatic interactions on the dissociation behaviour of weak polyacids.

Investigations of the Mechanism of Alternating Copolymerization with Charge-Transfer Interaction of the Monomers

Abstract The applicability of the method of Giese to the measurement of the influence of monomer reactivity is examined. The reaction of alkyl mercuric salts with sodium borohydride permits the production of alkyl (cyclohexyl and butyl) radicals. Since hydrogen radicals are present in high concentration, the addition of alkenes to the reaction mixture leads to radicals from the alkenes. Further addition of alkene (polymerization) can be nearly completely excluded in this way. The composition of the reaction products is determined by gas chromatography. The addition rate of the alkenes relative to styrene allows correlation with the e value of the Q-e scheme of Alfrey and Price. The method answers the question of how far addition of the monomer complex occurs in one step or as separate addition of both monomers during copolymerization in the presence of charge-transfer (CT) complexes of the monomers. The investigations are performed by using the styrene/acrylonitrile/ZnCl2system, and it is demonstrated tha...