Process for the production of cycloolefin random copolymer

• US 5,650,471 A
• Filed: 12/27/1995
• Issued: 07/22/1997
• Est. Priority Date: 12/28/1994
• Status: Expired due to Fees

• Current Assignee: Ticona GmbH (Celanese Corporation)
• Original Assignee: Mitsui Petrochemical Industries, Ltd., Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Abe, Yoshiharu, Sagane, Toshihiro
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/579,011
• Time in Patent Office: 573 Days
• Field of Search: 526/134, 526/160, 526/170, 526/133, 526/153, 526/127, 526/281, 526/943
• US Class Current: 526/160
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 232/08 having condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

There is provided a process for the production of a cycloolefin copolymer which comprises copolymerizing an α-olefin having 2 or more carbon atoms and a specific cycloolefin in the presence of a specific metallocene type catalyst in a solvent mixture of a hydrocarbon solvent having a solubility parameter (value of δ) of 7.7 [(cal/cm³)^1/2 ] or more and a hydrocarbon solvent having a solubility parameter (value of δ) of 7.5 [(cal/cm³)^1/2 ] or less as a polymerization solvent. A cycloolefin copolymer having a high molecular weight can be produced in a high concentration by this process at a high yield.

Claims

1. A process for the production of a cycloolefin copolymer which comprises

copolymerizing (1) an α

-olefin having 2 or more carbon atoms and (2) at least one cycloolefin selected from the group consisting of monomers represented by the following formula (I);

##STR11## wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R¹ to R¹⁸, R^a and R^b are independently selected from the group consisting of a hydrogen atom, halogen atom and hydrocarbon group, two out of R¹⁵ to R¹⁸ may jointly form a single hydrocarbon ring or multiple hydrocarbon rings including carbon atoms bonded thereto, and the single ring or multiple rings may have a double bond, and R¹⁵ and R¹⁶ or R¹⁷ and R¹⁸ may form an alkylidene group, and by the following formula (II);

##STR12## wherein p and q are each 0 or an integer of 1 or more, m and n are each 0, 1 or 2, R¹ to R¹⁹ are independently selected from the group consisting of a hydrogen atom, halogen atom, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and alkoxy group, the carbon atom bonded to R⁹ and R¹⁰ and the carbon atom bonded to R¹³ or R¹¹ may be bonded together directly or through an alkylene group having 1 to 3 carbon atoms, and R¹⁵ and R¹² or R¹⁵ and R¹⁹ may jointly form a monocyclic or polycyclic aromatic ring including carbon atoms bonded thereto when n=m=0,

in the presence of a catalyst formed from a transition metal compound catalyst component (a) represented by the following formula (III);

##STR13## wherein M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R¹ and R² are independently selected from the group consisting of a hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryl oxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, alkyl aryl group having 7 to 40 carbon atoms and aryl alkenyl group having 8 to 40 carbon atoms, R³ and R⁴ are independently a mononuclear or polynuclear hydrocarbon group having a cyclopentadienyl skeleton capable of forming a sandwich structure together with a central metal M¹, and R⁵ is one of the following divalent groups;

##STR14## in which R⁶, R⁷ and R⁸ are independently selected from the group consisting of a hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, alkyl aryl group having 7 to 40 carbon atoms and alkyl alkenyl group having 8 to 40 carbon atoms, R⁶ and R⁷ or R⁶ and R⁸ may jointly form a ring including an atom bonded thereto, and M² is silicon, germanium or tin, and at least one catalyst component (b) selected from the group consisting of organic aluminum oxy compounds and compounds capable of forming an ionic complex when they react with said transition metal compound,

in a solvent mixture containing a hydrocarbon solvent (i) having a solubility parameter of 7.7 (cal/cm³)^1/2 or more and a hydrocarbon solvent (ii) having a solubility parameter of 7.5 (cal/cm³)^1/2 or less in a volume ratio (i)/(ii) of 99/1 to 50/50, wherein a combination of the hydrocarbon solvent (i) and the hydrocarbon solvent (ii) is any one of combinations selected from the group consisting of cyclohexane and hexane, cyclohexane and heptane, cyclohexane and octane, cyclohexane and decane, methylcyclohexane and hexane, methylcyclohexane and heptane, methylcyclohexane and octane, and methylcyclohexane and decane.

2. The production process of claim 1, wherein an organic aluminum compound is further used as a catalyst component (c) to form the catalyst.

3. The production process of claim 1, wherein the volume ratio of the hydrocarbon solvent (i) to the hydrocarbon solvent (ii) is 90/10 to 50/50.

4. The production method of claim 1, wherein the α

-olefin to be copolymerized with the cycloolefin is ethylene.

5. The production method of claim 4, wherein the cycloolefin is norbornene.