Cycloolefin copolymers having low melt viscosity and low optical attenuation

• US 5,637,400 A
• Filed: 08/10/1995
• Issued: 06/10/1997
• Est. Priority Date: 02/12/1993
• Status: Expired due to Term

• Current Assignee: Ticona GmbH (Celanese Corporation)
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Osan, Frank, Brekner, Michael-Joachim, Deckers, Hellmuth
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/492,106
• Time in Patent Office: 670 Days
• Field of Search: 526/127, 526/132, 526/160, 526/281, 526/308, 526/943, 528/482, 528/491, 528/503, 428/373, 428/375, 428/376, 428/394, 428/421, 428/516, 264/1.5, 350/96.29, 350/96.34, 350/1.24
• US Class Current: 428/373
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 232/08 having condensed rings coumarone-indene polymers C08F244/00
• 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: C08L 45/00 Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of cyclic anhydrides or imides C08L35/00; of cyclic esters of polyfunctional acids C08L31/00
• CPC Class Codes: D01F 8/06 with at least one polyolefin as constituent
• CPC Class Codes: G02B 1/046 characterised by the core material
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts
• CPC Class Codes: Y10T 428/2929 Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• CPC Class Codes: Y10T 428/2967 Synthetic resin or polymer
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer

Abstract

Thermoplastic cycloolefin copolymers (COCs) having low melt viscosity and low optical attenuation, a process for their preparation, and their use as optical waveguides (optical fibers).

Claims

1. A process for the preparation of a cycloolefin copolymer (COC) having low melt viscosity by copolymerization of from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one monomer of the formula I, II, III or IV ##STR16## 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 or aryl radical, where identical radicals in the various formulae can have different meanings,

from 0 to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formula V ##STR17## in which n is a number from 2 to 10, and from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VI ##STR18## in which R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are a hydrogen atom or a C₁ -C₈ -alkyl radical, in solution, in suspension, in the liquid cycloolefin monomer or cycloolefin monomer mixture or in the gas phase, at a temperature of from -78°

to 150°

C., at a pressure of from 0.5 to 64 bar, in the presence of a catalyst comprising a metallocene as transition-metal component and an aluminoxane of the formula VII ##STR19## for the linear type and/or of the formula VIII ##STR20## for the cyclic type, where, in the formulae VII and VIII, R¹³ is a C₁ -C₆ -alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, where the polymerization is carried out in the presence of a catalyst whose transition-metal component is at least one compound of the formula IX ##STR21## in which M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum,

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₅ -C₄₀ -arylalkenyl group, and

m may be one or two, depending on the valency of the central atom M¹,

R¹⁸ is ##STR22## ═

BR¹⁹, ═

AlR¹⁹, --Ge--, --Sn--, --O--, --S--, ═

SO, ═

SO₂, ═

NR¹⁹, ═

CO, ═

PR¹⁹ or ═

P(O)R¹⁹, where R¹⁹, R²⁰ and R²¹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₁ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkylaryl group, or R¹⁹ and R²⁰ or R¹⁹ and R²¹, in each case with the atoms connecting them, form a ring,

M² is silicon, germanium or tin,

R¹⁶ and R¹⁷ are different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M¹,

wherein the metallocene of the formula IX has C_S -symmetry with respect to the ligands R¹⁶ and R¹⁷ and with respect to the central atom M¹ connecting them, the copolymer being subjected, when the copolymerization is complete, to a purification process which results in an optical attenuation of the material of from 0.1 to 5 dB/m.

2. The process as claimed in claim 1, wherein the catalyst used is a metallocene of the formula XI in which R¹⁶ is fluorenyl and R¹⁷ is cyclopentadienyl.

3. The process as claimed in claim 2, wherein the metallocene used is diphenylmethylene(9-fluorenyl)-cyclopentadienylzirconium dichloride.

4. The process as claimed in claim 1, wherein the 1-olefin employed is ethylene.

5. The process as claimed in claim 1, wherein the 1-olefin employed is ethylene and the polycyclic olefin employed is norbornene.

6. The process as claimed in claim 2, wherein, in a first step of the purification process, the reaction mixture is suspended with a filtration aid and with a substance which precipitates the organometallic compounds in the reaction mixture, the heterogeneous components are filtered off in a second step, and, in a third step, the purified COC is precipitated from the COC filtrate with the aid of a precipitant or the solvent of the COC filtrate is evaporated off.

7. A cycloolefin copolymer (COC) prepared as claimed in claim 2.

8. A cycloolefin copolymer (COC) prepared as claimed in claim 5, wherein its glass transition temperature is above 100°

C.

9. An optical waveguide comprising a light-transmitting core or a light-transmitting layer and a cladding layer of a transparent polymer whose refractive index is lower than the refractive index of the light-transmitting medium, wherein the light-transmitting core or the light-transmitting and/or cladding layer comprises a COC as claimed in claim 8.

10. An optical waveguide as claimed in claim 9, wherein the cladding layer comprises a thermoplastic polymer having a refractive index of from 1.34 to 1.47 (at 589 nm).

11. An optical waveguide as claimed in claim 9, wherein the cladding layer comprises polymers or copolymers of 4-methylpentene and other olefins, copolymers of ethylene and vinylidene fluoride, with or without addition of other comonomers, copolymers of tetrafluoroethylene, hexafluoropropene and vinylidene fluoride, or copolymers of methyl methacrylate and methacrylates of fluorinated or partially fluorinated alcohols.

12. A cycloolefin copolymer prepared as claimed in claim 1, wherein less than 0.1% by weight of partially crystalline ethylene polymer, based on the total weight of the polymer, is formed during the polymerization.

14. An optical waveguide as claimed in claim 11, wherein the cladding layer contains other comonomers.

15. An optical waveguide as claimed in claim 14, wherein the other comonomers are hexafluoropropene, tetrafluoroethylene or mixtures thereof.

16. An optical waveguide as claimed in claim 11, wherein the copolymers of tetrafluoroethylene hexafluoropropene and vinylidene fluoride further contain ethylene.

17. An optical waveguide as claimed in claim 11, wherein the methacrylate of partially fluorinated alcohols is tetrafluoro-n-propyl methacrylate.

13. The process as claimed in 2, wherein the metallocene used is isopropylene (9-fluorenyl)cyclopentadienylzirconium dichloride.

18. A process for the preparation of a cycloolefin copolymer (COC) having low melt viscosity by copolymerization of from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one monomer of the formula I, II, III or IV ##STR23## 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 or aryl radical, where identical radicals in the various formulae can have different meanings,

from 0 to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formula V ##STR24## in which n is a number from 2 to 10, and from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VI ##STR25## in which R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are a hydrogen atom or a C₁ -C₈ -alkyl radical, in solution, in suspension, in the liquid cycloolefin monomer or cycloolefin monomer mixture or in the gas phase, at a temperature of from -78°

to 150°

C., at a pressure of from 0.5 to 64 bar, in the presence of a catalyst comprising a metallocene as transition-metal component and an aluminoxane of the formula VII ##STR26## for the linear type and/or of the formula VIII ##STR27## for the cyclic type, where, in the formulae VII and VIII, R¹³ is a C₁ -C₆ -alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, where the polymerization is carried out in the presence of a catalyst whose transition-metal component is at least one compound of the formula IX ##STR28## in which M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum,

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₈ -C₄₀ -arylalkenyl group, and

m may be one or two, depending on the valency of the central atom M¹,

R¹⁸ is ##STR29## ═

BR¹⁹, ═

AlR¹⁹ --Ge--, --Sn--, --O--, --S--, ═

SO, ═

SO₂,

═

NR¹⁹, ═

CO, ═

PR¹⁹ or ═

P(O)R¹⁹, where R¹⁹, R²⁰ and R²¹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₁ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -aryl alkenyl group or a C₇ -C₄₀ -alkylaryl group, or R¹⁹ and R²⁰ or R¹⁹ and R²¹, in each case with the atoms connecting them, form a ring,

M² is silicon, germanium or tin,

R¹⁶ and R¹⁷ are different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M¹,

wherein the metallocene of the formula IX has C_s --symmetry with respect to the ligands R¹⁶ and R¹⁷ and with respect to the central atom M¹ connecting them, the copolymer being subjected, when the copolymerization is complete, to a purification process which results in a polydispersity of from 1.9 to 3.5.

19. A process for the preparation of a cycloolefin copolymer (COC) having low melt viscosity by copolymerization of from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one monomer of the formula I, II, III or IV ##STR30## 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 or aryl radical, where identical radicals in the various formulae can have different meanings, from 0 to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formula V ##STR31## in which n is a number from 2 to 10, and from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VI ##STR32## in which R⁹, R¹⁰ , R¹¹ and R¹² are identical or different and are a hydrogen atom or a C₁ -C₈ -alkyl radical, in solutions in suspension, in the liquid cycloolefin monomer or cycloolefin monomer mixture or in the gas phase, at a temperature of from -78°

to 150°

C., at a pressure of from 0.5 to 64 bar, in the presence of a catalyst comprising a metallocene as transition-metal component and an aluminoxane of the formula VII ##STR33## for the linear type and/or of the formula VIII ##STR34## for the cyclic type, where, in the formulae VII and VIII, R¹³ is a C₁ -C₆ -alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, where the polymerization is carried out in the presence of a catalyst whose transition-metal component is at least one compound of the formula IX ##STR35## in which M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum,

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₅ -C₄₀ -arylalkenyl group, and

m may be one or two, depending on the valency of the central atom M¹,

R¹⁸ is ##STR36## ═

BR¹⁹, ═

AlR¹⁹, --Ge--, --Sn--, --O----S--, ═

SO, ═

SO₂ , ═

NR¹⁹, ═

CO, ═

PR¹⁹ or ═

P (O)R¹⁹, where R¹⁹, R²⁰ and R²¹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₁ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkylaryl group, or R¹⁹ and R²⁰ or R¹⁹ and R²¹, in each case with the atoms connecting them, form a ring,

M² is silicon, germanium or tin,

R¹⁶ and R¹⁷ are different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M¹, wherein the metallocene of the formula IX has C_s -symmetry with respect to the ligands R¹⁶ and R¹⁷ and with respect to the central atom M¹ connecting them, the copolymer being subjected, when the copolymerization is complete, to a purification process which results in a melt viscosity below 2000 Pa·

s.