Soluble Polystyrenes Functionalized by Triorgano[(1‐oxoalkyl)oxy]stannanes (=Triorganotin Carboxylates): Synthesis,Structure, and Anion‐Recognition Characteristics

Polystyrene copolymers of the type ( P −H)_1−x( P −(CH₂)_n−COOSnR₃)_x containing [(1‐oxoalkyl)oxy]triphenylstannane or tributyl[(1‐oxoalkyl)oxy]stannanes as side chains ( P −H=styrene; P −(CH₂)_n−COOSnR₃ =para‐substituted styrene‐like monomeric unit with R=Ph (x=0.1), Bu (x=0.5); n=2–4) were investigated. The tributyl[(1‐oxoalkyl)oxy]stannane copolymer was prepared by direct conversion of the corresponding copolymeric methyl esters with hexabutyldistannoxane. By contrast, the [(1‐oxoalkyl)oxy]triphenylstannane copolymer could be prepared only by a procedure involving two reaction steps consisting of a preliminary hydrolysis of the related methyl ester ( P −H)_1‐x( P −(CH₂)_n−COOMe)_x followed by functionalization of the corresponding poly(carboxylic acid) ( P −H)_1‐x( P −(CH_2n−COOH)_x with hydroxytriphenylstannane. Attempts to directly convert the methyl ester with hydroxytriphenylstannane or hexaphenyldistannoxane led to the formation of uncompletely functionalized product. The structure of the stannane‐functionalized polymers was investigated in solution and solid state by NMR, IR, and thermal analysis. The tributylstannane and triphenylstannane copolymers were assessed as chloride‐selective anion carriers in polymeric‐liquid‐membrane potentiometric ion‐selective electrodes.     

Controlled stereochemistry of polyamides derived from cis/trans‐1,4‐cyclohexanedicarboxylic acid

A series of copolyamides 12.y was synthesized either with y = 6, or 1,4‐cyclohexanedicarboxylic acid (1,4‐CHDA) residue, or a mixture of both. The influence of the synthetic route of 1,4‐CHDA containing polyamides on the obtained cis–trans ratio of the incorporated 1,4‐CHDA was investigated. The use of acid chlorides provided a synthetic route with full control of the cis–trans ratio of the 1,4‐CHDA residue during synthesis, whereas synthesis at elevated pressure and temperature caused isomerization. The content and cis–trans ratio of 1,4‐CHDA in the copolyamides were determined by solution ¹³C NMR spectroscopy. Increasing the degree of partial substitution of the adipic acid by 1,4‐CHDA resulted in an increase in T_m, even for low molar precentages of 1,4‐CHDA. This phenomenon points to isomorphous crystallization of both the 12.6 and 12.CHDA repeating units. The mps of the synthesized polyamides were independent of the initial cis–trans ratio of 1,4‐CHDA, provided that the samples were annealed at 300 °C before DSC analysis. The polyamides exhibited a different melting pattern depending on the 1,4‐CHDA content. At a low a 1,4‐CHDA content a net exothermic recrystallization occurred during melting, whereas at higher contents of 1,4‐CHDA this recrystallization occurs to a lesser extent, and two separate melting areas are observed. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 833–840, 2001     

The reaction of di‐n‐butyltin oxide with hexafluoro‐2,2‐bis(4‐carboxyphenyl)propane

The reaction of hexafluoro‐2,2‐bis(4‐carboxyphenyl)propane with tetrabutyldipropoxydistannoxane, formed in situ from dibutyltin oxide and n‐propanol in benzene, yields a compound the structure of which is a strained macrocycle with a single dicarboxylate moiety. Copyright © 1999 John Wiley & Sons, Ltd.     

Coating systems for infra structural works

“Rijkswaterstaat” is a government organisation responsible for the construction, operation and maintenance of a large number of structures. The organisation consist of a general engineering division and a number of regional offices responsible for the Rijkswaterstaat objects in their particular region. Rijkswaterstaat spends between 40 to 50 K€ per year on coating and coating related activities. When the steel structures of the Eastern Scheldt barrier (± 200,000 m² of steel) were coated in the mid eighties the applied high solid epoxy system developed extensive cracking. This resulted in numerous locations with pit corrosion. Investigations were carried out and it was concluded that the cracking of this specific high-solids epoxy system was caused by restrained shrinkage. This resulted in the build up of high internal mechanical stresses in the coating system. Problems with stress build up were also encountered on other projects, although less severe and mainly concentrated at edges and welded joints. To prevent future problems, RWS has taken a number of initiatives such as the developed a procedure for the selection of coating systems. This selection procedure has proven to be useful for RWS in selecting coating systems for use on infra structural works. The basic principle of the selection procedure of the RWS selection procedure is different from most other procedures. The RWS selection procedure uses the object to be coated as a starting point instead of the coating system. This is done by first evaluating all relevant aspects of the object which may influence the selection of a system. These aspects are then translated into so called “Functional requirements”. Coating systems with properties that are in compliance with the performance requirements are gathered and through comparison of requirements and properties a selection is made. The objects that, until now, have been coated with systems selected with the selection procedure have performed adequately. Systems that have been selected with the procedure to replace or repair those that have developed cracking have until now not shown any new problems. At the present time more and more alternative tests and test procedures become available, most of them derived from ISO 12944. These will be studied closely and compared with the currently used methods on the level of functional requirements. RWS is already actively involved in the search for alternative test methods and will remain to do so in the future. In view of this the Rijkswaterstaat selection procedure will remain in function.     

Novel low‐loss waveguide delay lines using Vernier ring resonators for on‐chip multi‐λ microwave photonic signal processors

In this paper, novel photonic delay lines (DLs) using Vernier/non‐identical ring resonators (VRRs) are proposed and demonstrated, which are capable of simultaneous generation of multiple different delays at different wavelengths (frequencies). The simple device architectures and full reconfigurability allow the DLs to be integrated with other functional building blocks in photonic integrated circuits to realize on‐chip, complex multi‐λ microwave photonic signal processors with reduced system complexity. To prove the concept, DLs using VRRs in cascaded and coupled configurations have been fabricated in TriPleX^TM waveguide technology, which enables a very low delay‐induced loss of approximately 0.18 dB/100 ps. The fabricated DLs demonstrated simultaneous generation of four incremental delays, where a maximum incremental step of 550 ps and a corresponding top delay of 1650 ps were measured for a bandwidth up to 1 GHz. To our knowledge, this is the first report on VRRs for delay generation functionalities.