Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-06-16
2001-05-01
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
active
06225407
ABSTRACT:
The present invention relates to polymer blends made from cycloolefin copolymers (COC) and from impact modifiers. The novel polymer blends are impact-resistant and have high flexural strength and elongation at break, and improved processability.
Impact-modified polymers are well known and are suitable for a wide variety of applications (C. B. Bucknall, Toughened Plastics, Applied Science Publishers, London 1977; A. E. Platt, Rubber Modification of Plastics, Advances in Polymer Science, page 437).
It is also known that the impact resistance and the elongation at break of polymers can be improved by blending. For example, the impact resistance of brittle polymers can be improved by blending with polymer systems which are composed entirely or partially of rubbers with low glass transition temperatures, or by blending with core-shell particles, or by combining these modifiers. The morphologies obtained here, and therefore also the mechanical properties, are highly dependent on the processing conditions used (G. H. Michler, Kunststoff-Mikromechanik [Micromechanics of Plastics], Hanser, Munich 1992, page 281 et seq.; A. E. Platt, Rubber Modification of Plastics, Advances in Polymer Science, page 437; P. A. Lovell et al., Polymer, 34 (1993), page 61).
Polymer blends of cycloolefin copolymers are also known. EP-A-0 647 677 and EP-A-0 647 676 describe blends with core-shell particles. EP-A-0 661 345 combines core-shell particles with copolymers which are composed to some extent of rubbers with low glass transition temperatures.
PCT 97/46617 describes polymer blends of cycloolefin copolymers with copolymers which are composed to some extent of rubbers with low glass transition temperatures.
The materials obtained by blending the cycloolefin copolymers described do not have the impact resistance required for industrial applications.
The object of the present invention is to prepare a polymer with impact resistance sufficiently high for industrial applications.
It has been found that a novel polymer blend which comprises one or more cycloolefin copolymers and
a) one or more types of core-shell particles, or
b) one or more copolymers which are composed to some extent of rubbers with low glass transition temperatures, or
c) a combination of one or more types of core-shell particles and of one or more copolymers which are composed to some extent of rubbers with low glass transition temperatures
has impact resistance which is sufficiently high for industrial applications.
The novel polymer blend comprises at least one cycloolefin copolymer which is prepared by polymerizing from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one polycyclic olefin of the formula I, II, II′, III, IV or V
where R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are a hydrogen atom or a hydrocarbon radical, where the same radicals in the different formulae may have a different meaning, and from 0 to 99.9% by weight, based on the total amount of the monomers, of at least one monocyclic olefin of the formula VI
where n is a number from 2 to 10, and from 0.1 to 99% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VlI
where R
9
, R
10
, R
11
and R
12
are identical or different and are a hydrogen atom or a hydrocarbon radical, preferably a C
6
-C
10
-aryl radical or a C
1
-C
8
alkyl radical.
Preference is given to cycloolefins of the formulae I or III, where R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are a hydrogen atom or a hydrocarbon radical, in particular a (C
6
-C
10
)-aryl radical or a (C
1
-C
8
)-alkyl radical, where the same radicals in the different formulae may have a different meaning.
If desired, the polymerization may use one or more monocyclic olefins of the formula VI.
Preference is also given to an acyclic olefin of the formula VII, where R
9
, R
10
, R
11
and R
12
are identical or different and are a hydrogen atom or a hydrocarbon radical, preferably a C
6
-C
10
-aryl radical or a C
1
-C
8
-alkyl radical, for example ethylene or propylene.
The copolymers prepared are in particular those of polycyclic olefins, preferably of the formulae I and III, with ethylene.
Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, where these may have C
1
-C
6
-alkyl substitution. They are preferably copolymerized with ethylene. Very particular preference is given to ethylene-norbomene copolymers and ethylene-tetracyclododecene copolymers.
The novel polymer blend is characterized in that the cycloolefin copolymer(s) present are prepared by the process described below. The process for preparing the cycloolefin copolymers present in the novel polymer blend is described in detail in DE-A-196 52 340, which is expressly incorporated herein by way of reference.
The process according to the invention for preparing a cycloolefin copolymer encompasses the polymerization of from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one polycyclic olefin, and from 0 to 99.9% by weight, based on the total amount of the monomers, of at least one monocyclic olefin, and from 0.1 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin, in the presence of a catalyst system. The catalyst system to be used for preparing the cycloolefin copolymer present in the novel polymer blend comprises at least one transition metal compound. Preference is given to the use of one or more metallocenes as transition metal compound.
The polymerization is carried out in the liquid cycloolefin itself or in a cycloolefin solution. The pressure is usefully above 1 bar.
The catalyst system to be used in preparing the cycloolefin copolymer present in the novel polymer blend may moreover comprise one or more cocatalysts.
The catalyst system to be used for preparing the cycloolefin copolymer present in the novel polymer blend is a high-activity catalyst for olefin polymerization. Preference is given to using a metallocene and a cocatalyst. It is also possible to use mixtures of two or more metallocenes, particularly for preparing reactor blends or polyolefins with a broad or multimodal molar mass distribution.
The process for preparing the cycloolefin copolymer present in the novel polymer blend, and also the catalyst system to be used for this process, are described in detail in DE-A-1 96 52 340, which is expressly incorporated herein by way of reference.
The cocatalyst present in the catalyst system to be used for preparing the cycloolefin copolymer present in the novel polymer blend preferably comprises an aluminoxane.
Examples of the metallocenes to be used according to the invention are:
isopropylene(1-indenyl)(3-methylcyclopentadienyl)zirconium dichloride,
diphenylmethylene(1-indenyl)(3-methylcyclopentadienyl)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-methylcyclopentadienyl)zirconium dichloride,
isopropylene(1-indenyl)(3-isopropylcyclopentadienyl)zirconium dichloride,
diphenylmethylene(1-indenyl)(3-isopropylcyclopentadienyl)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-isopropylcyclopentadienyl)zirconium dichloride,
isopropylene(1-indenyl)(3-tert-butylcyclopentadienyl)zirconium dichloride,
diphenylmethylene(1-indenyl)(3-tert-butylcyclopentadienyl)zirconium dichloride
methylphenylmethylene(1-indenyl)(3-tert-butylcyclopentadienyl)zirconium dichloride,
isopropylene(1-indenyl)(3-trimethylsilylcyclopentadienyl)zirconium dichloride,
diphenylmethylene(1-indenyl)(3-trimethylsilylcyclopentadienyl)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-trimethylsilylcyclopentadienyl)-zirconium dichloride,
isopropylene(4,5,6,7-tetrahydro-1-indenyl)(3-trimethylsilylcyclopentadienyl)-zirconium dichloride,
diphenylmethylene(1-indenyl)(3-trimethylsilylcyclopentadienyl)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-trimethylsilylpentadienyl)zirconium dichloride,
isopropylene(4,5,6,7-tetrahydro-1-indenyl)(3-trimethylsilylcyclopentadienyl)-zirconium dichloride;
isopropylene
Berger Klaus
Hatke Wilfried
Jacobs Alexandra
Boykin Terressa M.
Connolly Bove & Lodge & Hutz LLP
Ticona GmbH
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