Preparation method of diphenyl ether dianhydride and isomer thereof

[0032] Add trichlorotoluene 200ml, 4-chlorophthalic anhydride 35g in the reactor that 500ml has drying and distillation unit, in N 2 In the case of protection, heat up and reflux for 20min, add K 2 CO 3 13.5 g and 3.4 g of triphenoxyphosphine were refluxed for 6 hours, cooled and filtered to obtain 23.85 g of crude product with a yield of 80%.

[0033] Add 100ml of benzonitrile and the crude product prepared by the above reaction in a clean reactor with a drying and distillation unit, in N 2 Under protection, heat up and reflux for 1 hour, cool down to -10°C, filter, and dry to obtain 22.4 g of diphenyl ether dianhydride and its isomers. The yield was 75.1%.

[0035] Add o-dichlorobenzene 180ml, 4-chlorophthalic anhydride 30.5g in the reactor that has drying and distillation device in 500ml, in N 2 In the case of protection, heat up and reflux for 35min, add K 2 CO 3 12.7 g and 4.2 g of hexaethylguanidine chloride were reacted under reflux for 5.5 hours, cooled and filtered to obtain 21.5 g of crude product with a yield of 82.7%.

[0036] Add the mixed solution of 120ml benzonitrile and trichlorotoluene and the crude product prepared by the above-mentioned reaction in clean reactor with drying and distillation unit, in N 2 Under protection, heat up and reflux for 40 minutes, cool down to -12°C, filter, and dry to obtain 20.8 g of diphenyl ether dianhydride and its isomers. The yield was 80.1%.

[0038] Add o-dichlorobenzene 230ml, trichlorotoluene 190ml, 4-chlorophthalic anhydride 92g in 1000ml reactor that has drying and distillation device, in N 2 In the case of protection, heat up and reflux for 60min, add K 2 CO 3 36g, 5.2g of hexabutylguanidine chloride and 2.1g of triphenylphosphine bromide were refluxed for 7 hours, cooled and filtered to obtain 69.7g of crude product with a yield of 89%.

[0039] Add the crude product prepared by 190ml benzonitrile and above-mentioned reaction in clean reactor with drying and distillation unit, in N 2 Under the condition of protection, heat up and reflux for 35 minutes, cool down to -15°C, filter, and dry to obtain 68 g of diphenyl ether dianhydride and its isomers. The yield was 86.8%.