New bisphenyl-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphine oxide compound for use as monomer for preparing polyimide useful as material for e.g. electronic products, molding products, heat-resistant adhesives, and insulation

摘要

#CMT# #/CMT# A bisphenyl-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphine oxide compound is new. #CMT# : #/CMT# A bisphenyl-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphine oxide compound of formula (1), is new. X : H, nitro or amine. Independent claims are also included for: (A) a method for preparing the compound (1); and (B) a polymer obtainable by reaction comprising imide polymerization of the diamine monomer of formula (1c) with a dianhydride monomer. #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#USE : #/CMT# The compound (1) is used as a monomer for preparing polyimide (claimed) useful as material for electronic products, molding products, heat-resistant adhesives, and insulation. The polyimide is used as material for preparing inter-layer insulating films and protection films of semiconductor chips. The polyimide is used for manufacturing gigabyte level integration chips. #CMT#ADVANTAGE : #/CMT# The compound (1) prepares polyimides having a low dielectric constant and a superior adhesion while maintaining the superior thermal and mechanical properties of polyimides themselves. #CMT#DESCRIPTION OF DRAWINGS : #/CMT# The figure shows a result of analysis for 7FPPO, DN7FPPO and DA7FPPO. #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation (Claimed): Compound (1) is prepared by performing a Grignard reaction of the 2,3,5,6-tetrafluoro-4-trifluoromethylbromobenzene of formula (2) and the diphenylphosphonic chloride of formula (3) in the presence of an organic solvent and magnesium to obtain the 2,3,5,6-tetrafluoro-4-trifluoromethylphenyldiphenylphosphine oxide (7FPPO) of formula (la); nitrating the compound of formula (1a) (7FPPOO) with sulfuric acid and nitric acid to obtain the bis(3-nitrophenyl)-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphine oxide (DN7FPPO) of formula (1b); and hydrogenating the compound (1b) (DN7FPPO) in the presence of a palladium catalyst to obtain the bis(3-aminophenyl)-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphin e oxide (DA7FPPO) (1c). #CMT#EXAMPLE : #/CMT# 12 g Dinitro compound (DN7FPPO), 150 ml of absolute ethanol and 15 mg of 10% palladium catalyst (Pd/C) were put in a high pressure reactor. Reaction was performed under 100 psi of hydrogen pressure and at 50[deg]C for 24 hours. The Pd/C was separated from the reaction product using celite. The solvent was evaporated and the reaction product was purified by column chromatography to obtain a diamine compound (DA7FPPO; yield: 83%). Melting point of the diamine compound (DA7FPPO) was measured and showed 187.3-187.6[deg]C. The analysis revealed a primary amine stretching peak of 3500-3300 cm -> 1> and a primary amine bending peak at 1597 cm -> 1>. The 1>H-NMR analysis showed amine-substituted phenyl 1>H peaks at 7.22-7.15, 6.92 and 6.80-6.74 ppm and a single amine 1>H peak at 5.49 ppm. The 31P-NMR analysis showed a shift of 15.02-22.03 ppm, which confirmed production of amine. These analyses clearly demonstrated successful preparation of the target compound (DA7FPPO). 6.1 g Diamine compound (DA7FPPO) and 50 ml of distilled 1-methyl-2-pyrrolidone were added to a reactor. After DA7FPPO was completely dissolved, 0.16 g of phthalic anhydride and 5.82 g of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) were sequentially added to the reactor. Then, the reaction was then performed at room temperature for 24 hour. Imidization of poly(amic acid) was performed in a flask. First, 12.5 ml of o-dichlorobenzene was added and reaction was performed at 170-180[deg] C for 24 hours while under nitrogen atmosphere. After reaction was completed, the reaction product was cooled to room temperature, precipitated in water/methanol, and then washed. The obtained polyimide powder was dissolved in chloroform, re-precipitated in water/methanol and filtered. The obtained polyimide was dried for 2 hours at 100[deg]C, for 6 hours at 200[deg]C and then for 20 minutes at the glass transition temperature of 20[deg]C. The number average molecular weight of the obtained polyimides were controlled to 20000 g/mol.