The New Synthetic Process Of Bisphenol F,the Preparation Of Hydroxamated Polymers And Neonicotinoid Insecticides

This thesis consists of three parts:firstly, the new synthetic process of Bisphenol F; secondly, the preparation and application of functional Hydroxamated polymers; the last one is the synthesis of Neonicotionoid insecticides.1. The new synthetic process of Bisphenol FBisphenol F is a new type chemical raw material developed in1980s, mainly used for the preparation of low-viscosity epoxy resin and polycarbonate, and the modification of phenolic resin, etc. It is composed of three isomers of the dihydroxy diphenyl methane, in which4,4-dihydroxy diphenyl methane has best performance. But so far there is no process for its single preparation.The application and market of Bisphenol F is widely developed, and even expected to replace Bisphenol A for its excellent performance and wide usage. However, the mainstream processes are difficult to realize scale production for its high ratio of phenol to formaldehyde and low yield (50%-60%, based on formaldehyde). Moreover, these processes are complicate, high cost and energy consumption for the use of vacuum distillation to recover phenol and purify product.In this thesis, most of the synthetic processes of Bisphenol F were reviewed and the processes with phosphoric acid as catalyst were in-depth studied. A new synthetic process was designed, in this process4,4-dihydroxy diphenyl methane was directly prepared and the yield was up to50%(based on formaldehyde). Moreover the by-products could be prepared to another product.Moreover, the scale-up production was studied for the coming industrial production. Innovative points are as follows:1. the ratio of phenol to formaldehyde is low, high utilization rate of phenolⅡ. the process is facile, without use of vacuum distillation and energy-savingⅢ.4,4-dihydroxy biphenyl methane was directly prepared, purity beyond ARⅣ. by-products can be recovered for use.2. The preparation and application of functional Hydroxamated polymers Hydroxamic acids have strong chelating ability with metal ions and their polymers have been widely used in metal processing, such as red mud flocculants, heavy metal ions fiocculants and mineral flotation.In this paper, the research progress of hydroxamated polymers and their application were reviewd. The study is focus on their application in red-mud flocculation, and their application in heavy metal ion flocculation was conducted a preliminary study.A variety of hydroxamic acid polymers were prepared using the copolymerization of hydroxamic acid monomers and the modification of polyacrylamide. The performance was texted in the Bayer Process, and the application was prospected.The preparation methods of hydroxamic acid monomers were also discussed and N-hydroxy acrylamide and N-hydroxy-methyl acrylamide were prepared using a novel system---triethylamine and chloroform. A new homopolymer of A’-hydroxyl-methyl acrylamide was prepared, which has not been reported in the literature yet.3. The synthesis of Neonicotionoid insecticidesNeonicotionoid insecticides comes from the botanical pesticide nicotine, they targeted on the insect nicotinic acetyl cholinesterase receptor. They are environmental friendly, high activity and low toxicity; they also have no cross resistance with conventional insecticides.A series of cyanide base amandine compounds were designed based on the’bioisosteres principle". We replace the pyridine ring of thiacloprid with substituted aryl ethyl and chloro-thiazole and (Z)-N-{3-[(2-Chloro-1,3-thiazol-5-y1)methyl]-1,3-thiazolidin-2-ylidene}cyanamide was prepared by the condensation of (Z)-2-(1,3-thiazolidin-2-ylidene) cyanamide and2-chloro-5-thiazolylmethyl chloride under alkaline conditions. Its structure was confirmed by melting point,1H NMR and X-ray diffraction.In addition, the preparation methods and application of new Neonicotinoid insecticides were studied and prospected.