Research Of Functionalization Macroporous Adsorption Resin LX1180and Heir Adsorptivity

Macroporous adsorption resins （MAR）, originated from1960s, and was a new kind oforganic polymers adsorbents. The MAR had the good adsorption capacity and low cost, whichextensively used in waste water treatment, clinical laboratory, extracted antibiotic andpurification of natural drugs etc. However, MAR was mostly preparation by suspensionpolymerization, structural parameters of MAR （the type of functional group, pore diameterand specific surface area etc） were hard to control, leading to the structure-activityrelationship between structural parameters and target molecule was not certain. Thus, thefurther development of MAR was restricted, and the relationship between them is worthfurther investigation.In this study, high crosslinking non-polar LX1180to realize chloromethylated andfunctional modification, because of the advantage of easy to control structural parameters ofhigh crosslinking non-polar MAR. Firstly, chloromethylation reaction was performed withmonochloromethyl ether （ME） which as chloromethylation reagent; in order to overcome thelack of low modify efficiency caused by high crosslinking degree, high chloromethylationdegree （CD） was obtained by optimized reaction conditions, and then conducted functionalmodification with high CD LX1180, which chosen SA and PAA as functional monomerrespectively. At last, adsorption and desorption experiment with different CD and functionaldegree （FD） were performed to rutin, gallic acid and anthocyanin. The research contents andresults in details were as follows:1. Chloromethylated modification was conducted to overcome the deficiency of low CDfor high crosslinking degree, the optimum conditions were followed:10.00g LX1180（preprocessed） was swollen with38.00mL CCl4in3-neck flask at65oC for36h, and thenreacted with0.02mol ME,14.000g NaCl and0.03mol ZnCl2in ultrasonic environment withthe power of75W at50oC for54h. In order to increase reaction rate, ZnCl2/Fe compositecatalysts were introduction in reaction system, in which the molar ratio of Fe to ZnCl2was12.5%, the reaction time related to the maximum chloromethylation degree reduced by24husing composite catalyst system. The sample prepared under optimal conditions possessed thechloromethylation degree of9.6%（WCl/WMAR）. The adsorption/desorption of three types offlavonoids （rutin, gallic acid and anthocyanin） using chloromethylized LX1180-Cl were tested.It was found that molecular size and polarity of adsorbate play important role to adsorptionand desorption of LX1180-Cl, the adsorption and desorption capacity increased with thesmaller molecular size and stronger polarity of adsorbate.2. On the basic of obtaining high CD of LX1180-Cl, the sulfonation modification wasconducted under alkaline conditions, which take sulfanilic acid （SA） as functional monomers.Optimal operating conditions were:20.00g LX1180-Cl was swollen with DMF/H2O （the ratio was VH2O/VDMF=0.33） at70oC for20h first,9g NaOH and30.00g NaCl were alsointroduced in the reaction system; and then reacted with0.02mol SA at70oC for18h, andfunctionalization degree （FD） of LX1180-SO₃^-in this condition was7.29%. Theadsorption/desorption of rutin, gallic acid and anthocyanin using different FD valueLX1180-SO₃^-were tested. It was found that the order of adsorption/desorption capacity tothree types of flavonoids was gallic acid> anthocyanin> rutin. The adsorption capacity ofallic acid and anthocyanin was increased with increasing of FD, while desorption capacity ofthat was decreased. Residual quantity of resin was increased with the increasing of FD.3. Using high CD of LX1180-Cl, carboxylation reaction was conducted with paraaminobenzoic acid （PAA）. Optimal operating conditions were:20.00g LX1180-Cl,8.00gNaOH and30.00g NaCl were added into threeneck flask, LX1180-Cl was swollen withDMF/H2O （the ratio was VH2O/VDMF=0.25） at70oC for36h first, and then reacted with0.03mol PAA at60oC for24h, and FD of LX1180-CO2-in this condition was6.03%. Theadsorption/desorption tests of rutin, gallic acid and anthocyanin to different FD valueLX1180-CO2-were shown that molecule-sized play a important role to adsorption/desorptioncapacity, in the same FD, adsorption capacity of LX1180-CO2-to three kind of flavonoidswere gallic acid> anthocyanin> rutin, while the desorption capacity of that were similar eachother.