Polymer blends of cycloolefin polymers and polyolefins

• US 5,359,001 A
• Filed: 04/20/1993
• Issued: 10/25/1994
• Est. Priority Date: 04/22/1992
• Status: Expired due to Fees

• Current Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Epple, Ulrich, Brekner, Michael-Joachim
• Primary Examiner(s): Seccuro, Jr., Carman J.
• Application Number:
  US08/049,980
• Time in Patent Office: 553 Days
• Field of Search: 525/97, 525/210
• US Class Current: 525/97
• CPC Class Codes: C08F 297/08 polymerising mono-olefins
• CPC Class Codes: C08L 23/00 Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• 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: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

For producing 100 parts by weight of a polymer blend 0 to 95 parts by weight of a finely divided polyolefin, 0 to 95 parts by weight of finely divided cycloolefin polymer and 0.1 to 99 parts by weight of a blockpolymer (which consists of monomeric units derived from norbornen and monomeric units derived from aliphatic monocycloolefins C_n H_2n and/or aliphatic 1-olefin, such as ethylene or propylene, are mixed and the mixture is processed under heat and shear forces. The block copolymer acts as phase mediator and contains in different blocks different proportions of the monomer units used.

Claims

1. A process for preparing a polymer blend comprising (i) combining at least one of (A) a finely particulate cycloolefin polymer, and (B) a finely particulate polyolefin, with (C) at least one block copolymer, to form a mixture;

and (ii) processing the mixture at an elevated temperature, under the action of shear forces, to form the polymer blend, wherein;

in the polymer blend, (A) is present in an amount of 0 to 95 parts by weight, (B) is present in an amount of 0 to 95 parts by weight, (C) is present in an amount of 0.1 to 99 parts by weight and, the sum of the amounts of (A), (B) and (C) present is 100 parts by weight;

the finely particulate cycloolefin polymer (A) comprises at least one monomer of formula I, II, III, IV, V and VI and at least one monomer of formula VII and VIII, but said cycloolefin polymer is not a block copolymer;

the block copolymer (C) is obtained by polymerizing;

a) 0.1 to 95% by weight, with respect to the total amount of monomers employed, of at least one monomer of the formula I, II, III, IV, V and VI,

b) 0 to 95% by weight, with respect to the total amount of monomers employed, of a cycloolefin of the formula VII, and

c) 0 to 99% by weight, with respect to the total amount of monomers employed, of at least one acyclic olefin of the formula VIII,

at a temperature of -78°

to 150°

C. and a pressure 0.01 to 64 bar, in the presence of a catalyst comprising a cocatalyst and a metallocene, and at a molecular weight distribution M_w /M_n of less than 2, always with respect to the polymer block forming, the reaction conditions are changed one or more times in such a way that the monomer/comonomer ratio changes by at least 10% or a further polymerizable monomer of the formulae I-VIII is metered into the monomer or the monomers; and

the monomers of the formula I, II, III, IV, V, VI, VII and VIII are;

##STR12## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are identical or different and are a hydrogen atom or a C₁ -C₈ -alkyl radical and n is a number from 2 to 10.

2. The process as claimed in claim 1, wherein component (B) of the blend includes aliphatic poly-1-olefin.

3. The process as claimed in claim 1 wherein component (B) of the blend includes polyethylene.

4. The process of claim 1, wherein additives are added to the mixture.

5. The process as claimed in claim 2, wherein from 1 to 55 parts by weight of at least one block polymer, from 10 to 80 parts by weight of polyolefin or polyolefins and from 10 to 80 parts by weight of cycloolefin polymer or polymers are combined and processed, with the proviso that the sum of the polymers totals 100 parts by weight.

6. The process as claimed in claim 2, wherein a weight ratio of polyolefin or polyolefins to block copolymer or block copolymers of at least 1:

1 is maintained.

7. The process as claimed in claim 3, wherein from 0 to 50 parts by weight of a finely particulate polyethylene or several finely particulate polyethylenes are used.

8. The process as claimed in claim 3, wherein the polyethylene is HDPE.

9. The process as claimed in claim 1, wherein in the polymerization a metallocene of the formula XI is used ##STR13## where M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum,

R¹⁴ and R¹⁵ are the same 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,

R¹⁶ and R¹⁷ are a mononuclear or polynuclear hydrocarbon radical which together with the central atom M¹ can form a sandwich structure,

R¹⁸ is ##STR14## ═

BR¹⁹, ═

A1R¹⁹ --Ge--, --Sn--, --O--, --S--, ═

SO, ═

SO₂, ═

NR¹⁹, ═

CO, ═

PR¹⁹, or ═

P(O)R¹⁹, where R¹⁹, R²⁰ and R²¹ are the same 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 form a ring with the atoms that connect them, and M² is silicon, germanium or tin.

10. A polymer blend produced by the process of claim 1.

11. A matrix material comprising the polymer blend of claim 10.

12. The process as claimed in claim 1 wherein component (B) of the blend includes polypropylene.

13. The process as claimed in claim 12, wherein the polypropylene is finely particulate isotactic polypropylene.

14. A composite comprising the matrix of claim 11.

15. A molding comprising the matrix of claim 11.

16. A process as recited in claim 1, wherein the catalyst comprises an aluminoxane of the formula (IX) ##STR15## for the linear type and/or of the formula (X) ##STR16## for the cyclic type, where, in the formulae (IX) and (X), the radicals R¹³ are identical different and are a C₁ -C₆ -alkyl group, a C₆ -C₁₈ -aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, and a metallocene of the formula XI ##STR17## in which M¹ is titanium, zirconium, hafnium, vanadium, nioblum or tantalum,

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₆ -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 -alkyl aryl group or a C₈ -C₄₀ -arylalkenyl group,

R¹⁶ and R¹⁷ are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M¹,

R¹⁸ is ##STR18## ═

BR¹⁹, ═

AIR¹⁹ --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 -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, form a ring, in each case together with the atoms linking them, and M² is silicon, germanium or tin.

17. The process of claim 1 wherein component (A) of the blend includes at least one acyclic olefin of formula VIII.