Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers

• US 5,629,398 A
• Filed: 06/05/1992
• Issued: 05/13/1997
• Est. Priority Date: 10/05/1990
• Status: Expired due to Term

• Current Assignee: Idemitsu Kosan Company Limited
• Original Assignee: Idemitsu Kosan Company Limited
• Inventors: Matsumoto, Junichi, Maezawa, Hiroshi, Watanabe, Masami, Okamoto, Takuji
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US07/867,227
• Time in Patent Office: 1,803 Days
• Field of Search: 526/132, 526/134, 526/170, 526/308, 526/281, 526/114, 526/115, 526/116, 526/118, 526/119, 526/147, 526/126, 526/127, 526/160, 526/161, 526/148, 526/151, 526/172, 526/113, 502/129, 502/152, 502/154, 502/155, 525/210, 525/211, 524/553, 524/554
• US Class Current: 526/281
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 32/00 Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 23/0815 Copolymers of ethene with aliphatic 1-olefins
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Abstract

A process for effectively producing a cyclic olefin polymer and a cyclic olefin/alpha-olefin copolymer without opening the cyclic olefin, is disclosed. Further, a novel cyclic olefin/alpha-olefin copolymer prepared by the above-mentioned process, compositions and molded articles comprising the novel copolymer, are also disclosed. In the process for producing a cylcic olefin based polymer according to the present invention, homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an alpha-olefin is effected in the presence of a catalyst comprising, as main ingredients, the following Compounds (A) and (B), and optionally Compound (C):

(A) a transition metal compound;

(B) a compound capable of forming an ionic complex when reacted with a transition metal compound; and

(C) an organoaluminum compound.

Claims

1. A process for producing a cyclic olefin based polymer wherein homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an alpha-olefin is carried out in the presence of a catalyst comprising as main components the following compounds (A) and (B):

(A) a transition metal compound; and

(B) a compound capable of forming an ionic complex when reacted with said transition metal compound,

wherein Compound (A) is a transition metal compound represented by the following formula;

space="preserve" listing-type="equation">M.sup.1 R.sup.1 R.sup.2 R.sup.3 R.sup.4

wherein M¹ is a transition metal selected from the IVB Group of the Periodic Table;

R¹, R², R³, and R⁴ may be the same as or different from each other, and are independently a ligand having a sigma bond, chelate ligand or Lewis base.

2. A process according to of claim 1, wherein Compound (B) is a compound comprising a cation and an anion wherein a plurality of functional groups are connected to an element.

3. A process according to claim 2, wherein Compound (B) is composed of a cation comprising an element selected from the groups of IIIB, IVB, VB, VIB, VIIB, VIII, IA, IB, IIA, IIB and VIIA of the Periodic Table;

and an anion wherein a plurality of functional groups are connected to an element selected from the groups of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA of the Periodic Table.

4. A process for producing a cyclic olefin based polymer wherein homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an alpha-olefin is carried out in the presence of a catalyst comprising as main components the following compounds (A) and (B):

(A) a transition metal compound;

(B) a compound capable of forming an ionic complex when reacted with said transition metal compound; and

(C) an organoaluminum compound, wherein Compound (A) is a transition metal compound represented by the following formula;

space="preserve" listing-type="equation">M.sup.1 R.sup.1 R.sup.2 R.sup.3 R.sup.4

wherein M¹ is a transition metal selected from the IVB Group of the Periodic Table;

R¹, R², R³, and R⁴ may be the same as or different from each other, and are independently a ligand having a sigma bond, chelate ligand or Lewis base.

5. A process according to claim 4, wherein compound (B) is a compound comprising a cation and an anion wherein a plurality of functional groups are connected to an element.

6. A process according to claim 5, wherein compound (B) is composed of a cation comprising an element selected from the group consisting of IIIB, IVB, VB, VIB, VIIB, VIII, IA, IB, IIA, IIB AND VIIA of the Periodic Table;

and an anion wherein a plurality of functional groups are connected to an element selected from the group consisting of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA of the Periodic Table.

7. A cyclic olefin copolymer having (1) 80 to 99.9 mol % of the repeating unit [X] ##STR7## wherein R^a is hydrogen or a C_1-20 hydrocarbon group and 0.1 to 20 mol % of the repeating unit [Y]:

##STR8## wherein R^b to R^m, which may be the same or different from each other, are each independently hydrogen, a C_1-20 hydrocarbon group or a substituent having a halogen atom, oxygen atom or nitrogen atom;

R^j or R^k and R^l or R^m may form a ring together, and n is 0 or an integer value;

(2) an intrinsic viscosity of 0.005 to 20 dl/g;

(3) a glass transition temperature of less than 20°

C.;

(4) a tensile modulus ranging from 300 to 2,000 kg/cm², determined by measurement at room temperature, and (5) a molecular weight distribution M_W /M_n of about 1.3 to 3.

8. A cyclic olefin copolymer according to claim 7, which has a melt peak measured by DSC (temperature decrease stage) of less than 90°

C.

9. A cyclic olefin copolymer according to claim 7 or 13, which has a crystallization peak measured by DSC (temperature decrease stage) such that the sub peak appears on the high temperature side of the main peak.

10. A molded article prepared from a cyclic olefin copolymer of claim 7, or 8.

11. A molded article according to claim 10, which is formed in the shape of film or sheet.

12. The molded article of claim 11, wherein said film or sheet has a haze of 9.4 or less.

13. A molded article according to claim 10, which is formed in the shape of wrapping film.

14. The molded article of claim 13, wherein said wrapping film has a haze of 9.4 or less.

15. A molded article according to claim 10, which is formed with a mold.

16. A cyclic olefin copolymer composition comprising (a) 100 parts by weight of a cyclic olefin copolymer of claim 7 or 8;

and (b) 0.01 to 10 parts by weight of an anti-blocking agent and/or a lubricant.

17. A cyclic olefin copolymer composition comprising (a) 100 parts by weight of a cyclic olefin copolymer of claim 7 or 8;

(b) 0.01 to 10 parts by weight of an anti-blocking agent and/or a lubricant; and

(c) 1 to 100 parts by weight of an alpha-olefin based polymer.

18. A film or sheet prepared from a cyclic olefin copolymer composition of claim 16.

19. A film or sheet prepared from a cyclic olefin copolymer composition of claim 17.