Process for isomerizing endo-form of aromatic group-containing norbornenes to exo-form thereof, isomer mixture of aromatic group-containing norbornenes and process for preparing same, and ethylene/aromatic group-containing norborne copolymer and process

• US 5,457,249 A
• Filed: 01/10/1994
• Issued: 10/10/1995
• Est. Priority Date: 02/12/1991
• Status: Expired due to Fees

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Petrochemical Industries, Ltd.
• Inventors: Tsuji, Yoichiro, Toda, Yoshihisa, Sagane, Toshihiro
• Primary Examiner(s): Pal, Asok
• Application Number:
  US08/180,811
• Time in Patent Office: 638 Days
• Field of Search: 585/11, 585/12, 585/24, 528/281, 528/282, 528/283
• US Class Current: 585/11
• CPC Class Codes: C07C 13/42 with a bicycloheptene ring structure
• CPC Class Codes: C07C 13/64 with a bridged ring system
• CPC Class Codes: C07C 2602/42 the bicyclo ring system containing seven carbon atoms
• CPC Class Codes: C07C 2603/86 containing four rings
• CPC Class Codes: C07C 5/2206 Catalytic processes not covered by C07C5/23 - C07C5/31

Abstract

A process for isomerization of an endo-form of aromatic group-containing norbornenes represented by the following formula (I) to an exo-form which comprises bringing the endo-form into contact with a solid acid catalyst. ##STR1## wherein p is 0 or an integer of 1 or more, q and r are each 0, 1 or 2, R¹ to R¹⁵ are each independently hydrogen or halogen atom, aliphatic hydrocarbon group, aromatic hydrocarbon group or alkoxy group, R⁵ (or R⁶) are R⁹ (or R⁷) may be linked together through an alkylene group of 1-3 carbons or may be directly linked together.

Claims

1. A cycloolefin random copolymer comprising structural units derived from ethylene and structural units derived from an aromatic group-containing norbornene wherein

(a) said aromatic group-containing norbornene is represented by the following formula (I) and is an isomer mixture having a molar ratio of an endo-form (I-A) to an exo-form (I-B) ((I-A/I-B)) of 80/20 to 0/100,

(b) said structural units derived from ethylene are present in an amount of from 10 to 95 mol %, and said structural units derived from the aromatic group-containing norbornene are present in an amount of from 90 to 5 mol %,

(c) the structural units derived from the aromatic group-containing norbornene are those represented by the following general formula (II), and

(d) said copolymer has an intrinsic viscosity (η

), as measured in decalin at 135°

C., of 0.05 to 10 dl/g, ##STR12## wherein p is 0 or an integer of 1 or more, q and r are each independently 0, 1 or 2, R¹ to R¹⁵ are each, independently hydrogen or halogen atom, aliphatic hydrocarbon group, aromatic hydrocarbon group or alkoxy group, or alternatively R⁵ (or R⁶) and R⁹ (when q is not

     0) or (R⁷) may be linked together through an alkylene group of 1-3 carbons or directly linked together, and X¹ represents the portion ##STR13## of the general formula (I), ##STR14## wherein p, q, r and R¹ -R¹⁵ are as defined above.

2. The cycloolefin random copolymer according to claim 1 wherein said copolymer comprises structural units derived from ethylene in an amount of 40 to 85 mol %, and structural units derived from the aromatic group-containing norbornene in an amount of 60 to 15 mol %.

3. The cycloolefin random copolymer according to claim 1 wherein the isomer mixture has a molar ratio of endo-form (I-A) to exo-form (I-B) ((I-A/(I-B)) of 70/30 to 5/95.

4. The cycloolefin random copolymer according to claim 1 wherein said copolymer contains structural units derived from ethylene in an amount from about 63 mol % to about 82 mol % and structural units derived from the aromatic group-containing norbornene in an amount from about 37 mol % to about 18 mol %.

5. A process for using an isomer mixture of an aromatic group-containing norbornene containing at least 20 mol % of exo-form isomer to prepare a cycloolefin random copolymer, which comprises

(a) copolymerizing ethylene and the aromatic-group-containing norbornene represented by the general formula (I) ##STR15## wherein p is 0 or an integer of 1 or more, q and r are each independently 0, 1 or 2, R¹ to R¹⁵ are each, independently hydrogen or halogen atom, aliphatic hydrocarbon group, aromatic hydrocarbon group or alkoxy group, or R⁵ (or R⁶) and R⁹ (when q is not 0) or (R⁷) are linked together through an alkylene group of 1-3 carbons or directly linked together, wherein the molar ration of endo-form (I-A) to exo-form (I-B) monomers ((I-A)/(I-B)) is from 80/20 to 0/100, ##STR16## wherein X¹ represents the portion ##STR17## wherein p, q, r and R¹ to R¹⁵ are defined above, in the presence or absence of a hydrocarbon solvent and in the presence of a catalyst comprising an organoaluminum compound and a vanadium compound soluble in said hydrocarbon solvent or in said aromatic group-containing norbornene, until the resulting copolymer contains structural units derived from ethylene in an amount of 10 to 95 mol % and structural units derived from the aromatic group-containing norbornene in an amount of 90 to 5 mol %, and wherein the copolymer has an intrinsic viscosity (η

), as measured in decalin at 135°

C., of 0.05 to 10 dl/g, and wherein the structural units derived from the aromatic group-containing norbornene are represented by the following general formula (II);

##STR18## wherein p, q and r and R¹ to R¹⁵ are defined above.

6. The process according to claim 5 further comprising the step of contacting a norbornene isomer mixture containing an amount of endo-form (I-A) of not less than 85 mol % with a solid acid catalyst until the molar ratio of the endo-form (I-A) to the exo-form (I-B) becomes 80/20 to 0/100.