Cycloolefin copolymers and processes for their preparation

• US 5,756,623 A
• Filed: 10/30/1996
• Issued: 05/26/1998
• Est. Priority Date: 12/24/1993
• Status: Expired due to Term

• Current Assignee: Ticona GmbH (Celanese Corporation)
• Original Assignee: Mitsui Petrochemical Industries, Ltd., Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Kreuder, Willi, Osan, Frank
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US08/739,926
• Time in Patent Office: 573 Days
• Field of Search: 526/316, 526/297, 526/300, 526/309
• US Class Current: 526/308
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/02 Ethene
• 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 232/08 having condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/25 Cycloolefine

Abstract

Cycloolefin copolymer having a solution viscosity (eta)>=0.25 dl/g, A) comprising polymerized units of at least one polycyclic olefin, B) polymerized units of at least one olefin which comprise at least one double bond and, if desired, C) polymerized units of one or more acyclic monoolefins, wherein the equivalent weight with regard to olefinic double bonds is less than or equal to the number-average molecular weight, and which additionally contains at least one repeating unit which possesses at least two electron withdrawing groups. The cycloolefin copolymer is suitable as a coating composition and as an additive.

Claims

1. A cycloolefin copolymer having a solution viscosity>

0.25 dl/g in decalin at 60°

C., comprising components

A) 0.1-99.89% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least one cycloolefin the formula I, II, III, IV, V, VI or VII ##STR10## in which the radicals R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical and are a hydrogen atom, or a C₁ -C₂₀ hydrocarbon radical, or form a ring, it being possible for identical radicals to have different meanings in the various formulae I to VI, and n is a number from 2 to 10,

B) 0.1-99.89% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least one olefin containing at least one double bond, wherein the equivalent weight with regard to olefinic double bonds is less than or equal to the number-average molecular weight, and is a compound of the formula VIII, IX, X, XI, XII or XIII ##STR11## in which R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, C₁ -C₈ -alkyl, C₆ -C₁₄ -aryl or C₃ -C₁₅ -alkenyl, with it being possible for identical radicals to have different meanings in the various formulae VIII-XIII, and at least one of the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁵ in formula VIII and R⁸, R¹⁰, R¹¹ and R¹² in formula XII is a C₃ -C₁₅ -alkenyl radical, and m is a number from 0 to 10, and n and l are each a number from 0 to 10, with the proviso that n and l can not be 0 at the same time,

C) 0-80% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least alpha olefins of 2 to 20 carbon atoms, and

D) 0.01 to 50% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units which possess at least two electron-withdrawing groups which are carbonyl or nitrile

and said copolymer has a polydispersity (M_w /M_n) from 1.8 to 2.8.

6. The cycloolefin copolymer as claimed in claim 1, wherein component D is carbonyl.

7. The cycloolefin copolymer as claimed in claim 1, wherein said cycloolefin copolymer is prepared in the presence of a catalyst comprising an aluminoxane and at least one metallocene and said cycloolefin copolymer which contain double bonds react with at least one enophile selected from the group consisting of α

,β

-unsaturated carboxylic acids and α

,β

-unsaturated carboxylic acid derivatives.

8. The cycloolefin copolymer as claimed in claim 7, wherein said metallocene contains a metal selected from the group consisting of titanium, zirconium, hafnium, niobium and tantalum.

9. The cycloolefin copolymer as claimed in claim 8, wherein said enophile is maleic anhydride, maleic esters, maleimides, which are also may optionally be substituted, bromomaleic anhydride, sulfomaleic anhydride or azo azodicarboxylate.

10. A cycloolefin copolymer as claimed in claim 1, wherein the polymerized units B) contain at least 0.1% by weight, based on the total mass of the cycloolefin copolymer, of an acyclic C₄ -C₂₀ polyene.

11. A coating composition comprising at least one cycloolefin copolymer as claimed in claim 1.

12. A copolymer as claimed in claim 1, wherein the polycyclic olefin A) is norbornene.

13. A copolymer as claimed in claim 1, wherein the polycyclic olefin A) is tetracyclododecane.

14. A copolymer as claimed in claim 1, wherein the olefinic polymerized units B) are dienes of from 4-20 carbon atoms.

15. A copolymer as claimed in claim 1, wherein the alpha-olefins are ethylene and propylene.

16. A copolymer as claimed in claim 1, wherein the electron withdrawing unit is carbonyl.

17. A copolymer as claimed in claim 1, wherein

the units A) are present in an amount of 1-99% by weight;

the units B) are present in an amount of 1-50% by weight,

the units C) are present in an amount of 1-60% by weight, and

the units D) are present in an amount of 0.05-20% by weight.

18. A copolymer as claimed in claim 1, wherein

the units A) are present in an amount of 10-90% by weight;

the units B) are present in an amount of 2-30% by weight,

the units C) are present in an amount of 2-50% by weight, and

the units D) are present in an amount of 0.1-10% by weight.

19. The copolymer as claimed in claim 1, wherein

the polymerized units A) are norbornene or tetracyclodiodecane,

the polymerized units B) are dienes of from 4-20 carbon atoms, the polymerized units C) are ethylene or propylene and the polymerized units D) are carbonyl or nitrile and wherein the polydispersity (M_w /M_n) of the copolymer is less than 4.

20. The cycloolefin copolymer as claimed in claim 19, wherein the copolymer has a viscosity from 0.25 to 1.5 dl/g, a polydispersity from 1.8 to 2.8, a glass temperature from -20°

C. to 200°

C. and an iodine number from 0.5 to 200.

21. The copolymer as claimed in claim 20, wherein the glass temperature range is from 0°

to 200°

C. and the iodine number is from 0.5 to 50.

22. The copolymer as claimed in claim 19, wherein the polydispersity (M_w /M_n) of the copolymer is from 1.8 to 2.8 and the molecular weight M_w of the copolymer is from 11,200 g/mol to 38,000 g/mol.

2. A cycloolefin copolymer having a solution viscosity greater than or equal to 0.25 dl/g in decalin at 60°

C., consisting essentially of

A) 10 to 90% by weight norbornene or tetracyclodiodecane,

B) 2 to 30% by weight dienes of from 4-20 carbon atoms which contains at least one double bond wherein the equivalent weight with regard to olefinic double bonds is less than or equal to the number-average molecular weight and is at least one compound of the formula VIII, IX, X, XI, XII or XIII ##STR12## in which R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, C₁ -C₈ -alkyl, C₆ -C₁₄ -aryl or C₃ -C₁₅ -alkenyl, with it being possible for identical radicals to have different meanings in the various formulae VIII-XIII, and at least one of the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁶ in formulae VIII and R⁹, R¹⁰, R¹¹ and R¹² in formula XII is a C₃ -C₁₅ -alkenyl radical, and m is a number from 0 to 10, and n and l are each a number from 0 to 10, with the proviso that n and l can not be 0 at the same time.

C) 2 to 50% by weight ethylene or propylene and

D) 0.1 to 10% by weight carbonyl or nitrile, and said copolymer has

1) a polydispersity (M_w /M_n) from 1.8 to 2.8,

2) a glass transition temperature from 0°

C. to 200°

C.,

3) an iodine number from 0.5 to 50 and

4) a molecular weight M_w from 11,200 to 38,000 g/mol.

5. The cycloolefin copolymer as claimed in claim 2, wherein the copolymer contains from 0.1 to 10% by weight of carbonyl.

3. A cycloolefin copolymer having a solution viscosity greater than or equal to 0.25 dl/g in decalin at 60°

C., consisting essentially of

a copolymer which consists essentially of

A) 10 to 90% by weight norbornene or tetracyclodiodecane,

B) 2 to 30% by weight dienes of from 4-20 carbon atoms which contains at least one double bond wherein the equivalent weight with regard to olefinic double bonds is less than or equal to the number-average molecular weight and is at least one compound of the formula VIII, IX, X, XI, XII or XIII ##STR13## in which R₉, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, C₁ -C₆ -alkyl, C₆ -C₁₄ -aryl or C₃ -C₁₆ -alkenyl, with it being possible for identical radicals to have different meanings in the various formulae VIII-XIII, and at least one of the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁶ in formulae VIII and R⁹, R¹⁰, R¹¹ and R¹² in formula XII is a C₃ -C₁₅ -alkenyl radical, and m is a number from 0 to 10, and n and l are each a number from 0 to 10, with the proviso that n and l can not be 0 at the same time and

C) 2 to 50% by weight ethylene or propylene and

D) 0.1 to 10% by weight of carbonyl or nitrile and said copolymer has

1) a polydispersity (M_w /M_n) from 1.8 to 2.8,

2) a glass transition temperature from 0°

C. to 200°

C.,

3) an iodine number from 0.5 to 50 and

4) a molecular weight M_w from 11,200 to 38,000 g/mol.

4. A cycloolefin copolymer having a solution viscosity>

0.25 dl/g in decalin at 60°

C., comprising

a copolymer having the following components;

A) 0.1-99.89% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least one cycloolefin of the formula I, II, III, IV, V, VI or VII ##STR14## in which the radicals R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical and are a hydrogen atom, or a C₁ -C₂₀ hydrocarbon radical, or form a ring, it being possible for identical radicals to have different meanings in the various formulae I to VI, and n is a number from 2 to 10,

B) 0.1-99.89% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least one olefin containing at least one double bond, wherein the equivalent weight with regard to olefinic double bonds is less than or equal to the number-average molecular weight, and is at least one compound of the formula VIII, IX, X, XI, XII or XIII ##STR15## in which R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, C₁ -C₈ -alkyl, C₆ -C₁₄ -aryl or C₃ -C₁₅ -alkenyl, with it being possible for identical radicals to have different meanings in the various formulae VIII-XIII, and at least one of the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁶ in formula VIII and R⁹, R¹⁰, R¹¹ and R¹² in formula XII is a C₃ -C₁₅ -alkenyl radical, and m is a number from 0 to 10, and n and l are each a number from 0 to 10, with the proviso that n and l can not be 0 at the same time and

C) 0-80% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units of at least alpha olefins of 2 to 20 carbon atoms, and

D) at least two electron withdrawing groups to said copolymer wherein the cycloolefin copolymer contains 0.01 to 50% by weight, based on the total mass of the cycloolefin copolymer, of polymerized units which possess at least two electron-withdrawing groups which are carbonyl or nitrile and said copolymer has a polydispersity (M_w /M_n) from 1.8 to 2.8.