The Synthesis Of Dioctyladipate Catalyzed By Lignin And Polyphenylene Ether Based Resin Carbon Sulfonic Acids

Dioctyl adipate(DOA),as a green cold-resistant plasticizer,can give good light resistance and flexibility,high plasticizing efficiency.So it is widely used in food preservation membrane,agricultural film and PVC etc.This thesis researches the preparation of new and highly-efficient carbon sulfonic acids and their catalysis performance in the synthesis of DO A,the obtained main works are described as follows:1.It is studied that the copper amine complex-catalyzed oxidation polymerization of 2,6-dimethylphenol in water to form the low molecular weight poly(2,6-dimethyl-1,4-phenylene)(PPO),followed by the sulfonation of PPO with fuming sulfuric acid in liquid phase to prepare sulfonated SPPO catalyst.The effect of molecular weight of PPO,type and amount of sulfonating agents,temperature and time of sulfonation on the SPPO's acid density has been checked and the higher acid density of SPPO catalyst(2.71 mmol·g-1)is obtained under the optimal conditions.The structure of SPPO is characterized by FT-IR,1H-NMR,13C-NMR,TG and other analysis methods.In catalytic synthesis of dioctyl adipate(DOA)reaction,the SPPO catalyst can keep 99.53%esterification rate and 97.24%recovery rate after it is repeatedly used for 7 times,which possesses an excellent catalytic activity and a good stability.2.A composite type of lignin phenolic resin carbon sulfonic acid(B-PRPC-SO3H)is prepared by using the black liquor as a raw material and the reagent B as an additive through a series of transformation prcoesess,including catalytic oxidation,phenolic reaction,acidification,carbonization and sulfonation.The effect of sulfonated method,amount of sulfonated reagent,temperature and time of sulfonation,amount of auxiliary B,heating rate,temperature and tiem of carbonization on the catalyst acidity has been checked and the B-PRPC-S03H catalyst with a higher acidity of 2.35mmol·g-1 is obtained under the optimized conditions.The above catalyst has an esterification rate and a good reusability in catalytic synthesis of DOA,it can be repeatedly used for 7 times,providing 99.73%esterification rate and 94.93%recovery rate.3.The macroporous sulfonic acid resin-continuously catalyzed esterification of adipic acid to DOA was carried out on self-assembly four tank reactors in series,With the mole ratio of acid to alcohol for 5:1,airspeed for 1.2 h-1,temperature for 135 ? and continuous operating time for 210h,the average rate of esterification can achieve in 92.28%,indicating that the device has a good operation stability.4.Finally,the separation and purification of DOA were studied using the crude ester obtained by an intermittent reaction.After the crude ester is treated by a series of steps including repeatedly washing with hot water,neutralization with aqueous Na2C03 solution,dealcoholization by vacuum distillation and decoloration with activated carbon.The high purity of DOA(99.95%),which meets the HG/T3 873-2006,can be obtained and is characterized by GC,IR,1H-NMR and 13C-NMR.