Preparation And Characterization Of Novel Polyimides Containing Calix[4]arenes In The Polymer Backbone And Study On Their Properties

Calixarenes, which are basket-shaped macrocyclic compounds with potentialinterest for host-guest complexation studies, represent the new type of receptors aftercyclodextrins and crown ethers, and have strong ability of selective extraction tometal ions, so calixarenes have been extensively focused by chemists from all overthe world. In this paper, the calixarene derivatives containing polymerisable groupswere chosen as the special molecular functional blocks. According to the principles ofthe molecular design and assembly, a series of novel functional polymeric materials,which have ability of molecular recognition to metal ions, were synthesized bycopolymerizations of some monomers with the calixarene derivatives.1. Three calixarene derivatives 6,10,13 with polymerisable groups on the upperrims, and a kind of new flexible diamine monomer with side-group, 3,3'-bimethyl-4,4'-diaminodiphenylmethane (DMDA) 14 were synthesized for the first timethrough multi-step reaction sequence and characterized by ~1H NMR, MS, EA and IR.2. One polyimide containing pendant calix[4]arene unit has been synthesized viaterminated reaction involving a 5-amino-25, 26, 27, 28-tetrahydroxycalix[4]arenemonomer 6 with 3,3',4,4'—oxydiphthalic anhydride (ODPA) and 4,4'-diaminodiphenyl ether(DAPE). The upper rim of the calix[4]arene monomer, whichhas the site group of polymerization, was linked into the chains of the polyimides. Thepolyimide can be blended with conventional ODPA-DAPE polyimide to modify theproperties of the polyimide.New polyimides containing calix[4]arene moieties on the polymer backbone weresuccessfully synthesized in DMF by polycondensations of 3,3',4,4'-oxydiphthalicanhydride (ODPA) with the diaminocalix[4]arene monomer10 or 13 using DMDA 14 as a comonomer and characterized by ~1H NMR and IR. The polyimides preparedare soluble in aprotic polar solvents, such as NMP, DMAc and DMF. Compared withconventional ODPA- DMDA polyimide, the polyimides obtained exhibit low thermalstability, low Tg, low mechanical properties and the excellent ability of recognition tometal ion in regard to bulky, cone-like calix[4]arene moieties and their effects on thechain conformation and morphological structure.3. Liquid membrane transport of K+ ion by means of bubbling pseudo-emulsionliquid membrane system with p-tert-butylcalix[4]arenas and its derivatives as carrierswas investigated. Seven kinds of calixarenes as carriers in three different conditionswere experimented, which is to say, the value of pH of the source phase and receivingphase were changed to look into the liquid membrane transport in the different pHgradient between the source phase and receiving phase. A comparison between theseven kinds of calixarenes about their transport ability of K+ ion was made and thereasons of different transport ability from their molecular structures were analyzed.Evidence shows:(1) The larger the△pH, the larger the net transport of K~+ ion, which shows the pHgradient between the source phase and receiving phase, namely△pH, is the criticalfactor of transport of K~+ ion for p-tert-butylcalix[4]arenes and its derivatives. Thedriving force for the transport is the pH gradient between the source phase andreceiving phase.(2) Preserving phenolic hydroxyl in the lower rim of calixarenes molecular couldenhance calixarenes' transport ability of K+ ion.(3) If the substituted functional group in the upper rim of calixarenes molecular hadelectron-withdrawing conjugative effect, the transport ability of K~+ ion would fall off;if it had electron-repulsive conjugative effect, the transport ability of K~+ ion would beenhanced.(4) The liquid membrane transport of K~+ ions by the two polyimides 2,4 wereinvestigated which testified that the polyimide containing calix[4]arene moieties hastransport ability to K+ ion as the carrier. The calix[4]arene incorporated in thepolyimide chain exhibits a receptor activity toward metal K~+ ion higher than a free calix[4]arene derivative.4. The extraction of calixarene with sulfur 13 to Ag+ ion on the condition of diffe-rent pH and concentration which affect on the extraction efficiency was investigated.The results indicate that calixarene with sulfur 13 has extraction ability to Ag~+ ion.The extraction of Ag~+ ion by polyimide 5 was performed, and the extraction resultwere analyzed and compared with that of the extractions by conventional ODPA-DMDA polyimide. All these analytical results confirmed the molecular recognitionabilities of the novel polyimide to Ag~+ ion, which was due to the introduction ofcalixarene with sulfur as a special functional block into the functional polymericmaterial.5. The Ag-type inorganic antimicrobial materials are becoming the research pointfor their special properties. Calixarene can be modified for host molecules withdefined structure and function. Specifically modified derivatives of calixarene asreceptor can form complex compound with silver cation. In this paper, three newcomplexes of calix[4]arene with silver were prepared, which have antimicrobialactivities against E.coli ATCC25922, Pseudomonas aeruginosa ATCC27853,Staphylococcus aureus ATCC29213 and Candidaalbicans ATCC 10231. After finishingby the three new complexes, the cotton fabrics have the excellent antimicrobial abilityto E.coli ATCC25922, Staphylococcus aureus ATCC29213 and CandidaalbicansATCC10231. At the same time, the antimicrobial activity of treated specimen stillremained at a high lever after 10 laundering cycles. The ultimate goal of the project isto find a new application for the well established binding properties of calix[4]arenein the textile chemistry.