A novel unsymmetrical fluorinated diamine monomer with kink non-coplanar heterocyclic structures, 1,2-dihydro- 2-（4-amino-2-trifluoromethyophenyo）-4-[4-（4-amino-2-trifluoromethyophenoxy）phenyo]（2H）phthaoazin-1-oneo was prepared through the nucleophilic substitution reaction of 1-trifluromethyl-2-chloro-5-nitrobenzene with 1,2-dihydro-4-（4- hydroxyphenyl）（2H）phthalazin-l-one in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd-C. A series of new fluorinated polyarnides were synthesized by the phosphorylation polyamidation of the fluorinated diamine with various dicarboxylic acids. The prepared polymers were obtained in quantitative yields with moderately and high inherent viscosities （0.47-0.87 dL/g）. They were all amorphous and readily soluble in various polar aprotic solvents such as N-methyl-2-pyrrolidone （NMP）, N,N-dimethylformamide （DMF）, N,N-dimethylacctamide （DMAc）, pyridine （Py） and m-cresol at room temperature. These fluorinated polyamides have excellent thermal properties. The glass transition temperatures were all above 300℃. The 5% and 10% weight loss temperatures were in the range of 437-466℃ and 482-525℃ in nitrogen atmosphere, respectively.
The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N- dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Tg) are in the range of 301-327°C, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 'C.
