Synthesis Of Aromatic Poly(Ether Ketone Amide)s And Conjugated Polymers By Heterogeneous Palladium-Catalyzed Carbonylative Polycondensation And Carbon-Carbon Coupling Polycondensation

In this dissertation,we investigated the synthesis of aromatic poly?ether ketone amide?s and conjugated polymers by heterogeneous palladium-catalyzed carbony-lative polycondensation and carbon-carbon coupling polycondensation.This disser-tation mainly consists of three parts:1.New aromatic poly?ether ketone amide?s containing cardo groups were prepared by the heterogeneous palladium-catalyzed polycondensation of aromatic diiodides with ether ketone units,aromatic diamines bearing cardo groups,and carbon monoxide.Polymerizations were carried out in N,N-dimethylacetamide?DMAc?at120oC in the presence of a magnetic nanoparticles-supported bidentate phosphine palladium complex[Fe₃O₄@SiO₂-2P-PdCl₂]and 1,8-diazabicyclo[5,4,0]-7-undecene?DBU?,and resulted in poly?ether ketone amide?s with inherent viscosities up to 0.77dL/g.All the polymers were quite soluble in various dipolar aprotic solvents at room temperature.These polymers showed glass transition temperatures between 223 and289°C and 5%weight loss temperatures ranging from 441°C to 464°C.These polyamides could be cast into transparent,flexible and strong films from DMAc solution with good tensile strength and tensile modulus.These polymers also exhibited lower dielectric constants,lower water uptakes,and higher optical transparency.Besides,the palladium catalyst can be recycled up to 8 times without loss of catalytic activity.2.New fluorinated aromatic poly?ether ketone amide?s containing cardo structures were prepared by heterogeneous palladium-catalyzed polycondensation of fluorinated aromatic diiodides with ether ketone units,aromatic diamines containing cardo groups,and CO.Polymerizations were conducted in N,N-dimethylacetamide?DMAc?at 120oC in the presence of a magnetic nanoparticles-supported bidentate phosphine palladium?II?complex[Fe₃O₄@SiO₂-2P-PdCl₂]and 1,8-diazabicyclo[5,4,0]-7-undecene?DBU?,and resulted in fluorinated cardo poly?ether ketone amide?s with inherent viscosities up to 0.75 dL/g.All the polymers were readily soluble in many organic solvents and could afford transparent,flexible and strong films by solution casting.These polymers exhibited good thermal stability with the glass transition temperature of 237-258°C,the temperature at 5%weight loss of 463-478°C in nitrogen.The poly?ether ketone amide?films also showed good mechanical properties,excellent electrical performance,and high optical transparency.The incorporation of fluorinated groups and cardo structures in the polymer backbone has played an important role in the improvement of dielectric performance and optical properties.Importantly,the palladium catalyst can be recycled up to 8 times without significant loss of catalytic activity.3.In the presence of Fe₃O₄@SiO₂-2P-PdCl₂,the Heck or Stille reaction of aromatic diiodides with 1,4-divinylbenzene or?E?-1,2-bis?tributylstannyl?ethene and Suzuki reaction of 2,7-dibromo-9,9-bis?6-bromohexyl?-9H-fluorene with 1,4-pheny-lenediboronic acid were investigated to synthesize three known conjugated polymers The resulting conjugated polymers were characterized by various techniques.The results indicated that this heterogeneous palladium catalyst exhibited the same catalytic activity as homogeneous one and could be recycled up to 8 times without significant loss of catalytic activity.In addition,compared with Pd content of conjugated polymers obtained by homogeneous palladium catalysis,the Pd residues in these conjugated polymers were less than 15 ppm,which was 100 times less than that in the former.