NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, NORBORNANE-2-SPIRO-a- CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC ACID AND ESTER THEREOF, METHOD FOR PRODUCING NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, POLYIMIDE OBTAINED BY USING THE SAME, AND METHOD FOR PRODUCING POLYIMIDE

A method for producing a norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, comprising:

• a step of reacting a 5-norbornene-2-spiro-α-cycloalkanone-α′-spiro-2″-5″-norbornene with an alcohol and carbon monoxide in the presence of a palladium catalyst and an oxidizing agent, to thereby obtain at least one compound of norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acids and esters thereof,
• the 5-norbornene-2-spiro-α-cycloalkanone-α′-spiro-2″-5″-norbornene being represented by the following general formula (3):
• wherein the formula (3), R2, R3, and R9s each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, and n represents an integer of 0 to 12,
• the norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acids and esters thereof is represented by the following general formula (2):
• wherein the formula (2), R2, R3, and R4s each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, R5, R6, R7, and R8 each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms, and n represents an integer of 0 to 12;
• and
• a step of obtaining a norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride from the compound by using formic acid, an acid catalyst, and acetic anhydride,
• the norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride is represented by the following general formula (1):
• wherein the formula (1), R1s, R2, and R3 each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, and n represents an integer of 0 to 12.

A method for producing a polyimide, comprising:

• a step of reacting a norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride with an aromatic diamine in the presence of an organic solvent, to thereby obtain a polyamic acid,
• the norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride being represented by the following general formula (1):
• wherein the formula (1), R1s, R2, and R3 each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, and n represents an integer of 0 to 12,
• the aromatic diamine being represented by the following general formula (10):
• H2N—R10—NH2 (10),
• [in the formula (10), R10 represents an aryl group having 6 to 40 carbon atoms,
• the polyamic acid having a repeating unit is represented by the following general formula (9):
• wherein the formula (9), R1s, R2, and R3 each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, R10 represents an aryl group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12;
• and
• a step of subjecting the polyamic acid to imidization, to thereby obtain a polyimide having a repeating unit represented by the following general formula (4):
• wherein the formula, R1s, R2, and R3 each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, and a fluorine atom, R10 represents an aryl group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12.