Process for preparation and purification of material of a cycloolefin copolymer

• US 5,498,677 A
• Filed: 02/14/1994
• Issued: 03/12/1996
• Est. Priority Date: 02/12/1993
• Status: Expired due to Fees

• Current Assignee: Ticona GmbH (Celanese Corporation)
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Weller, Thomas, Osan, Frank, Brekner, Michael-Joachim
• Primary Examiner(s): Teskin, Fred
• Application Number:
  US08/195,076
• Time in Patent Office: 757 Days
• Field of Search: 526/281, 526/308, 526/160, 526/133, 526/170, 526/134, 526/139, 526/145, 528/493, 528/495, 528/481, 528/482, 528/491, 210/767, 210/769, 210/770, 264/331.17
• US Class Current: 526/133
• CPC Class Codes: C08F 232/08 having condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: G11B 7/2538 polycycloolefins [PCO]

Abstract

A material of a cycloolefin copolymer has a structure of alternating cycloolefin sequences, and has crystallinity in a temperature range from 210° to 320° C. The cycloolefin is prepared by polymerization of at least one polycyclic olefin, monocyclic and/or acyclic olefin with an open-chain olefin using a catalyst of a metallocene and an aluminoxane.

Claims

1. A process for the preparation of a cycloolefin copolymer comprising the step of polymerization, without ring opening, of 0.1 to 100% by weight, based on the total amount of monomers, of at least one cycloolefin monomer of the formulae I, II, III, IV, V, or VI ##STR6## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and are a hydrogen atom or a C₁ C₈ -alkyl radical, it being possible for the same radicals in the various formulae to have a different meaning,

0to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula VII ##STR7##

3. A process as claimed in claim 1, further comprising

adding said clear solution of said cycloolefin polymer to a liquid of a ketone, alcohol or ester, thereby precipitating said cycloolefin copolymer,

filtering, washing and drying said cycloolefin copolymer, and

pressing said cycloolefin copolymer into sheets thermoplastically at a temperature of 300°

C.

4. A process as claimed in claim 1, wherein the open-chain olefin comprises ethylene, and the cycloolefin ethylene incorporation ratio is adjusted to a value of 40 to 60 mol % of cycloolefin to 60 to 40 mol % of ethylene.

6. A process as claimed in claim 1, wherein the catalyst system comprises metallocene dissolved in a solution of the aluminoxane in an aliphatic or aromatic hydrocarbon.

8. A process as claimed in claim 6, wherein the metallocene is dissolved in an amount of 10^-4 to 1 mol per mole of aluminoxane.

9. A process as claimed in claim 1, wherein a salt-like compound of the formula

10. A process as claimed in claim 1, wherein a salt-like compound of the formula

11. A process as claimed in claim 1, wherein the open-chain olefin comprises an acyclic 1-olefin of the formula VIII ##STR8## in which R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are a hydrogen atom or a C₁ -C₈ -alkyl radical.

13. A process as claimed in claim 11, further comprising

adding said clear solution of said cycloolefin polymer to a liquid of a ketone, alcohol or ester, thereby precipitating said cycloolefin copolymer, and

filtering, washing and drying said cycloolefin copolymer.

2. in which n is an integer from 2 to 10, inclusive, and 0. 1 to 99.9% by weight, based on the total amount of monomers, of at least one open-chain olefin

at temperatures of -78°

to 150°

C. under a pressure of 0.01 to 64 bar in the presence of a catalyst system comprising a metallocene and one or both of an aluminoxane or salt-like compound, wherein a portion of the metallocene catalyst is preactivated with a salt-like compound,

in a cyclic olefin solution saturated with acyclic olefin by use of pressure, thereby forming a reaction solution comprising said cycloolefin copolymer and

wherein the reaction solution is purified by a process comprising

pouring the reaction solution into a liquid of a ketone, alcohol or ester,

filtering the resulting mixture to give a filter cake,

mixing the filter cake with decahydronaphthalene and diatomaceous earth to form a suspension,

heating the suspension to dissolve said cycloolefin polymer, and

filtering the resulting solution over a pressure filter with down to 0.3 μ

m pore width to give a clear solution of said cycloolefin polymer.

5. A process as claimed in claim 2, wherein the open-chain olefin comprises ethylene and the cycloolefin comprises norbornene, and the incorporation ratio is 50 mol % of norbornene to 50 mol % of ethylene.

7. A process as claimed in claim 5, wherein the concentration of the aluminoxane in the solution is from 1% by weight up to the saturation limit.

12. A method of purifying a reaction solution comprising a cycloolefin copolymer comprising repeating sequences, wherein each of said sequences comprises a cyclic olefin unit followed by an acyclic olefin unit, comprising

pouring the reaction solution into a liquid of a ketone, alcohol or ester,

filtering the resulting mixture to give a filter cake,

mixing the filter cake with decahydronaphthalene and diatomaceous earth to form a suspension,

heating the suspension to dissolve said cycloolefin polymer, and

filtering the resulting solution over a pressure filter with down to 0.3 μ

m pore width to give a clear solution of said cycloolefin polymer.