Synthesis And Addition Polymerization Of Norbornene Derivatives Containing Alkoxymethylene

Interests in addition polymers of norbornene(NBE) (bicyclo-[2.2.1]hept-2-ene) have increased dramatically for the attractive properties, such as high chemical resistance, high glass transition temperature, excellent transparency, good UV resistance, low dielectric constant and so on. Most of the obtained polynorbornenes are insoluble in common solvents and show poor processability, which restrict its application. The introduction of functionalities to polynorbornene can enhance its properties.5-butoxymethyl-2-bicyclo[2.2.1]hept-2-ene and 5-hexaoxymethyl-2-bicyclo[2.2.1]hept are synthesized. The polymerization and copolymerization of norbornene derivatives was carried out by using bis-(β-ketoamino)nickel(Ⅱ)/B(C6F5)3 catalytic system, the structure and performance of the polymers have been characterized.5-butoxymethylenyl-2-norbornene (NBE-CH2OC4H9) was synthesized by bromobutane and 2-norbornene-5-methanol under the action of NaH, it consists of exo-and endo-isomers, the ratio of exo/endo is 32/68. Copolymerization of norbornene and 5-butoxymethylenyl-2-norbornene was carried out by using bis-(β-ketoamino)nickel(Ⅱ)/B(C6F5)3 catalytic system. The structure and performance of the obtained polymers were characterized by 1HNMR, FTIR, GPC, TGA. The catalyst shows high catalytic activity. The incorporation rate could reach 22.1-76.9mol% ether units at a content of 1/10-9/10 of the NBE-CH2OC4H9 in the monomer feeds ratios; the polymerizations are confirmed to be vinyl-addition mode. The polymer has good thermal stability, good mechanical properties and, excellent transparence and soluble in many common solvents, such as THF and CHCl3.5-hexaoxymethylenyl-2-norbornene (NBE-CH2OC6H13) was synthesized by bromohexane and 2-norbornene-5-methanol under the action of NaH, it consists of exo-and endo-isomers, the ratio of exo/endo is 30/70. Polymerization of 5-hexaoxymethylenyl-2-norbornene was carried out by using bis-(β-ketoamino) nickel(II)/B(C6F5)3 catalytic system. The influences of polymerization time were investigated.The polymer molecular weight and the conversions increase with the time increasing. The structure and performance of the obtained polymers were characterized by 1H NMR, FTIR, GPC, TGA. The catalyst shows high catalytic activity. The polymerizations are confirmed to be vinyl-addition mode. The polymer has good thermal stability, good mechanical properties and soluble in many common solvents, such as THF and CHCl3.Ⅲ...