Solubility poly anhydrides

W. G. Kim and A. S. Hay. Synthesis of soluble poly(ether imides) from bis(ether anhydrides) containing bulky substituents. Macromolecules, 26 5275-5280,1993. 

Applications. Poly(ethylene oxides) are readily grafted with acrylic acid to give partially biodegradable detergent pol5miers (208-210). Grafts onto other substrates include poly(vinyl alcohol) (211), water-soluble maleic anhydride copolymers (212), polycaprolactone (213), and onto emnlsion polymers of acrylates and methacrylates (214). 

Soluble poly-DFCA can be acetylated with acetic anhydride and shows a broad NMR peak between 5.5 and 6 ppm indicative of the acetal proton which is bound to a carbon atom which has as the fourth valency a strongly electron withdrawing group attached. 

The cell distribution of 3-amino-4-hydroxymethyl acridine derivatives 70 (Scheme 25), which has the N3—C4—16 substitution pattern, was studied by real-time fluorescence microscopy and SIMS structured illumination microscopy). The latter method required the introduction of an iodine atom at position 6 of the acridine which influences the Upophihcity but does not modify significantly the biological properties such as IC50 and subcellular localization (2009EJMC4758). A co-polymer 71 consisting of water-soluble maleic anhydride-containing poly[maleic anhydride-u/i-acrylic acid] (poly(MA-alt-AA) or MAAA) copolymer was modified with acriflavine (AF) which displayed antibacterial activity on EHEC and Staphylococcus aureus (2014MI2903). 

Thianthrene-2,3,7,8-tetracarboxylic anhydride polymerized with aromatic diamines by the conventional low temperature technique to yield soluble poly(amic acid)s. Polyimides were obtained by thermal cyclization of poly(amic add) films. Rigid diamines gave brittle films whereas 4,4 -oxydianiline and 4,4-methylene dianiline gave films that were creasable. The polyimides had excellent thermal stability in nitrogen and air and a moderate increase in solubility over the more linear and rigid analogs obtained firom pyromellitic dianhydride. 

A selective two step transformation of the tBMA block into the water soluble poly(sodium methacrylate) was carried out. Firstly, anhydride, isobutene and water is formed at 200°C and then the cleavage of the anhydride is done in IN NaOH under reflux. This procedure does not influence the ester group with the perfluorobutane side chain. The reaction can be followed by FT-IR spectroscopy (30). 

Synthetic Polymers. Synthetic polymers are versatile and offer promise for both targeting and extracellular-intracellular drug delivery. Of the many soluble synthetic polymers known, the poly(amino acids) [poly(L-lysine), poly(L-aspartic acid), and poly(glutamic acid)], poly(hydroxypropylmethacrylamide) copolymers (polyHPMA), and maleic anhydride copolymers have been investigated extensively, particularly in the treatment of cancers. A brief discussion of these materials is presented. 

Catalysis in Transacylation Reactions. The principal objective of the study was to evaluate 4 as an effective organic soluble lipophilic catalyst for transacylation reactions of carboxylic and phosphoric acid derivatives in aqueous and two-phase aqueous-organic solvent media. Indeed 4 catalyzes the conversion of benzoyl chloride to benzoic anhydride in well-stirred suspensions of CH2CI2 and 1.0 M aqueous NaHCC>3 (Equations 1-3). The results are summarized in Table 1 where yields of isolated acid, anhydride and recovered acid chloride are reported. The reaction is believed to involve formation of the poly(benzoyloxypyridinium) ion intermediate (5) in the organic phase (Equation 1) and 5 then quickly reacts with bicarbonate ion and/or hydroxide ion at the interphase to form benzoate ion (Equation 2 and 3). Apparently most of the benzoate ion is trapped by additional 5 in the organic layer or at the interphase to produce benzoic anhydride (Equation 4), an example of normal phase-... 

Under similar UV irradiation conditions for the coatings obtained from the solution of model copolymers such as poly(tributylstannyl methacrylate) and maleic anhydride/styrene copolymer, no considerable change was observed in their IR spectra and solubility. 

The glyptals made from phthalic anhydride and glycerol were developed as compositions for use in paints and varnishes. If the reaction was carried out too long the product became intractible. But under milder conditions, other products could be obtained which could be used in making soluble products and then they could be set further after forming. It was learned that by modifying the reaction mixture with some monobasic acid to balance the hydroxyls and carboxyls in the reaction mixture, more soluble products could be obtained. Kienle of General Electric, was one of the early developers of these products. Later many other alkyd resins from other polyhydroxyl compounds and poly acids were produced for technical use. 

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