Process for producing 2, 3, 3′, 4′,-biphenyltetracarboxylic dianhydride
View Patent ↗2,3,3′,4′-biphenyltetracarboxylic acid is heat-dehydrated in a molten state at a temperature not lower than 200° C. in a flow of an inert gas in a reactor 10 having at least one reaction vessel 11 by stirring the molten material to produce 2,3,3′,4′-biphenyltetracarboxylic dianhydride. Thus obtained 2,3,3′,4′-biphenyltetracarboxylic dianhydride in the molten state is subsequently cooled and solidified in an inert gas or dry air, or cooled and solidified in the ambient air at a temperature of 40° C. or lower or 100° C. or higher.
1. A process for producing 2,3,3′,4′-biphenyltetracarboxylic dianhydride, comprising a dehydration step of:
heat-dehydrating 2,3,3′,4′-biphenyltetracarboxylic acid in a molten state at a temperature not lower than 200° C. in a flow of an inert gas in a reactor having at least one reaction vessel by (i) stirring the molten material, or (ii) in bubbling the molten material by passing the inert gas; thereby, producing 2,3,3′,4′-biphenyltetracarboxylic dianhydride.
2. A process according to claim 1 , wherein during the dehydration step, the 2,3,3′,4′-biphenyltetracarboxylic acid is continuously supplied to the reactor, and the resultant 2,3,3′,4′-biphenyltetracarboxylic dianhydride in a molten state is continuously taken out of the reactor.
3. A process according to claim 2 , wherein the reactor comprises a plurality of reaction vessels serially connected.
4. A process according to claim 1 , wherein an average reaction time of the dehydration step is not shorter than 2 hours.
5. A process according to claim 1 , wherein an average residence time in a single reaction vessel is not longer than 6 hours.
6. A process according to claim 1 , further comprising a solidification step wherein the molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride is received from the dehydration step; and is subsequently cooled and solidified in an inert gas or dry air, or cooled and solidified in the ambient air at a temperature of 40° C. or lower or 100° C. or higher, wherein the molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride is supplied to a solidifying apparatus comprising a cooling surface and cooled on the cooling surface to give a solid 2,3,3′,4′-biphenyltetracarboxylic dianhydride.
7. A process according to claim 6 , wherein the molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride is continuously received and continuously supplied to the solidifying apparatus.
8. A process according to claim 7 , wherein the solidifying apparatus comprises a cooling surface, and the molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride is cooled on the cooling surface.
9. A process according to claim 6 , wherein the cooled and solidified 2,3,3′,4′-biphenyltetracarboxylic dianhydride is pulverized to give a powder having a median size less than 100 μm.
10. A process according to claim 1 , wherein a water content of the 2,3,3′,4′-biphenyltetracarboxylic acid to be supplied to the dehydration step is not higher than 10%.
11. A process for producing 2,3,3′,4′-biphenyltetracarboxylic dianhydride, comprising:
cooling and solidifying a molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride in an inert gas or dry air; or
cooling and solidifying a molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride in the ambient air at a temperature of 40° C. or lower or 100° C. or higher,
wherein the molten 2,3,3′,4′-biphenyltetracarboxylic dianhydride is supplied to a solidifying apparatus comprising a cooling surface and cooled on the cooling surface to give solid 2,3,3′,4′-biphenyltetracarboxylic dianhydride.
12. A process according to claim 1 , wherein the obtained 2,3,3′,4′-biphenyltetracarboxylic dianhydride is polymerized with 4,4′-diaminodiphenyl ether at an equal molar amount in a solvent of N-methyl-2-pyrrolidone at a monomer concentration of 10% by mass at 25° C. for 4.5 hours, to give a polyamic acid having a logarithmic viscosity not less than 1.0, wherein the logarithmic viscosity is measured in a solution of N-methyl-2-pyrrolidone at a concentration of 0.5 g/100 ml at 30° C.
13. A process according to claim 6 , wherein the cooled and solidified 2,3,3′,4′-biphenyltetracarboxylic dianhydride is in flake form.
14. A process according to claim 6 , wherein the temperature of the cooling surface of the solidifying apparatus is 170° C. or lower.
15. A process according to claim 11 , wherein the cooled and solidified 2,3,3′,4′-biphenyltetracarboxylic dianhydride is in flake form.
16. A process according to claim 11 , wherein the temperature of the cooling surface of the solidifying apparatus is 170° C. or lower.