WO2012022409A1 - Cycloolefin polymer compositions, molded bodies, and use of said molded bodies - Google Patents

Cycloolefin polymer compositions, molded bodies, and use of said molded bodies Download PDF

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WO2012022409A1
WO2012022409A1 PCT/EP2011/003614 EP2011003614W WO2012022409A1 WO 2012022409 A1 WO2012022409 A1 WO 2012022409A1 EP 2011003614 W EP2011003614 W EP 2011003614W WO 2012022409 A1 WO2012022409 A1 WO 2012022409A1
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alpha
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ethylene
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Michael Grimm
Wilfried Hatke
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Topas Advanced Polymers Gmbh
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • C08L23/0823Copolymers of ethene with aliphatic cyclic olefins
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • C08L23/142Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene

Abstract

The invention relates to compositions containing A) cycloolefin polymer having a glass transition temperature of at least 140°C, B) polymer derived from one or more alpha-olefins, which possibly has further structural units derived from at least one alkane diene and/or from at least one vinyl aromatic monomer, and C) a selected polyolefin component as a phase mediator. Said compositions are characterized by excellent mechanical properties and in particular by high heat resistance. The compositions can be used to produce molded bodies that can be sterilized and that can be used in medical equipment.

Description

description

Cycloolefinpolymerzusammensetzungen, moldings and their use

The present invention relates Cycloolefinpolymerzusammensetzungen containing selected polyolefins. These compositions have high heat resistance and can be used in many fields. For example, in medicine and medical technology, food technology, electronics and electrical engineering, container and equipment, the

Vehicle, in the vulcanization of elastomer products, as well as

Packaging materials.

Cycloolefin (hereinafter referred to as "COP") have been known for years. Typical examples of these polymers are derived from norbornene. This may be ring-sustaining polymerization or ring-opening polymerization, optionally together with comonomers in the corresponding

(Co) polymers are placed. These polymers are characterized by an excellent transparency and all kinds are used for the production of films, optical components, as well as containers.

It has also been proposed to combine COP with other polyolefins, such as polyethylene or polypropylene.

1-olefins such as ethylene and propylene can be prepared by various

Catalysts for polyolefins, in particular polyethylenes and

be polymerized polypropylenes (see. for example, EP 0185918 A2 and EP 0387690 A1).

Polyethylene can also be produced by radical polymerization (see. Eg US 3,336,281 A). It then is a material of low density (LDPE) or copolymers of ethylene with 1-olefins, low density (LLDPE); There are also catalytically produced polyethylenes having high to medium-density (HDPE, MDPE).

It is generally known that important properties of polymers can be modified by alloying polymers with other polymers. Thus, in patents DD 214 137 and DD 214 623 thermoplastic materials of construction will be described on the basis of polyolefins

simultaneously have good heat resistance, chemical resistance, stiffness, toughness and very good dielectric properties. The

Described compositions comprise as essential constituents norbornene-ethylene copolymers and polyethylene or branched polyolefins, optionally with the addition of stabilizers, lubricants, elastomers, thermoplastics and reinforcing agents. To improve the impact strength and notched impact strength elastomers such as elastomeric ethylene co- and terpolymers or graft copolymers are added. The additions of

Polyethylene or branched polyolefins and ethylene-norbornene-copolymers according to these documents, an improvement effect of the chemical resistance and the toughness of the norbornene-ethylene copolymers. Conversely, the addition of norbornene-ethylene copolymer was as polyethylene or branched polyolefins to an increase in strength, modulus and hardness without a decrease in the Schlagzähigbiegefestigkeit carried out.

It is also known that polyolefin thermoplastic combinations of 40-98 wt .-% of crystalline polyolefin and 2-60 wt .-% random cyclic olefinic copolymer (T g of 70 to 210 ° C, crystallinity of 0 to 5%) good

Heat resistance and crack resistance, and have low shrinkage (see FIG. JP 01/318052 A). Combinations of COP and crystalline polyolefins have improved melt processability, according to patent application JP 03/122148 A.

A thermoplastic combination of 5 to 90 wt .-% linear polyolefin consisting of 8 to 40% ultra high molecular weight polyolefin selected viscosity and 60 to 92% low to high molecular weight polyolefin selected viscosity and 95 to 10 wt .-% of at least one Cycloolefinthermoplasten selected from ring-opening polymers and ring-opening copolymers thereof, 4990559 A is described in US.

Alloying of COP with other polyolefins is attractive because the latter are relatively inexpensive and the corresponding alloys thus offer cost advantages. EP 0566988 A1 discloses such polymer alloys of COP, polyolefins and additives. Suitable polyolefins polymers are known, which are derived from open-chain non-cyclic olefins, for example polypropylene and polyethylene or Polyolefinco- and terpolymers and / or graft copolymers. As additives cycloolefin block copolymers are known; they are made of hard and soft blocks, and have the function of compatibilizers between the phases of

Polymer blends. This document discloses a method in which can be reached starting from cheap combinations of cycloolefin polymers, polyolefins and additives to polymer alloys having a high level as possible in the material properties, in particular strength, hardness, heat resistance and toughness.

DE 195 36 043 A1 discloses a polyolefin with selected amorphous COP and further polyolefin, preferably polypropylene, such as isotactic propylene homopolymer, or mixtures of propylene homopolymer or

copolymers with other polyolefins, such as HDPE, LDPE and LLDPE. For the generation of homogeneous polymer mixtures, it is proposed in this document to choose the average molecular weight of the COP, within limits and a certain ratio of

observed molecular weight of the COP to the molecular weight of olefin polymers.

Finally, a method for manufacturing a package is known from WO 2004/026946 A1, wherein a thermoformable film with high heat resistance and water vapor barrier passes used. The film comprises a cycloolefin copolymer having a glass transition temperature of 65-200 ° C and may in addition include polyethylenes of various densities such as HDPE, LDPE and LLDPE, or other polymers such as ethylene-vinyl acetate copolymer or polypropylene.

From the prior art as well as our own experiments is also known that molding of combinations of COP with polypropylenes or polyethylenes, in general, by the addition of COP in its properties are modified. Thus, the COP additive usually leads to an increase of the E module, the resistance to deformation ( "creep resistance") and the

Heat distortion temperature ( "HDT"), as well as for lowering the tackiness at high temperatures ( "hot tack"), the water permeability and the

Wear resistance ( "warparge"). In addition, these moldings are characterized generally by high transparency and by good

Resistance to chemicals, in particular by a high water vapor resistance. For economic considerations, attempts to mix the comparatively high-priced COP with cheaper polymers; it should, if possible products are formed, which retain the good features of COP or even improved.

There have now been found on the basis of COP and other polyolefins selected blends which at to give moldings with a high level

Material properties can be processed. These moldings are characterized in particular by high strength, hardness, heat resistance and toughness. Therefore, an object of the present invention to provide compositions and COP of produced therefrom shaped articles with the above-called properties.

The present invention relates to a composition comprising

A) at least one Cyclolefinpolymer having a glass transition temperature of at least 140 ° C,

B) at least one derived from one or more alpha-olefins

Polymer having optionally further at least one alkadiene and / or derived from at least one vinyl aromatic monomer structural units, and

at least one improving the compatibility of the components A) and B) and different from component B)

Component selected from the group

- the block copolymers derived from at least two

different alpha-olefins,

- the random copolymers derived from ethylene and

at least one other alpha-olefin,

- the copolymers derived from at least one alpha-olefin and at least one alkadiene,

- the copolymers derived from at least one alpha-olefin and of at least one vinyl aromatic monomer,

- the homo- or copolymers derived from at least one alpha-olefin, which with ethylenically unsaturated carboxylic acids and / or their anhydrides and / or esters thereof, with

ethylenically unsaturated epoxides, with ethylenically unsaturated silicon compounds with ethylenically unsaturated amines, and combinations of two or more thereof are grafted,

- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated carboxylic acid and / or its anhydride and / or their esters,

- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated

epoxy compound,

- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated

Silicon compound

- the copolymers derived from at least one alpha-Olfein and at least one ethylenically unsaturated amine, and

- the copolymers derived from at least one alpha-olefin and of at least one of a saturated Vinylester

aliphatic carboxylic acid, optionally a

having hydroxyl group. polymers in accordance with the invention used as component A) cycloolefin is known per se polymers. These are prepared by ring-sustaining or by ring-opening polymerization. The COP derived from cyclic olefins. These are preferably copolymerized with non-cyclic olefins.

Preferably, for the preparation of the present invention used COP used cyclic olefins monomers of the following formulas I to VI are

Figure imgf000007_0001
Figure imgf000007_0002

Figure imgf000008_0001

Figure imgf000008_0002
wherein R ι, R 2) R3, R4, R5, R6. R7 and Rs are the same or different and are a hydrogen atom or a Ci-Ce alkyl radical, where identical radicals in the various formulas can have different meanings. Under Ci-Ce-alkyl straight or branched saturated aliphatic hydrocarbon radicals are to be understood with 1-8 carbon atoms in the context of this description, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl or n-octyl. The preferred cyclic olefin radicals of the formulas I to VI may be used singly or in combination, polymerized with one another or very particularly preferably together with the cyclic Olefinresten of the formula VII and / or with the non-cyclic Olefinresten of the formula VIII

Figure imgf000009_0001
wherein n is an integer from 2 to 10 and

R19, ​​Rio, RH and R12 are the same or different and are a hydrogen atom or a Ci-Cs-alkyl radical.

Preferred comonomers are propylene and especially Ethyien. in particular copolymers of polycyclic olefins of the formulas I or III and the acyclic olefins of the formula VIII are employed.

Particularly preferred cycloolefins are norbornene and tetracyclododecene, which can be substituted by Ci-C6-alkyl, wherein the ethylene-norbornene copolymers are of particular importance, in particular, the cycloolefin copolymer produced with retention of the ring structure.

Of the monocyclic olefins of the formula VII is cyclopentene, which may be substituted, preferred. Polycyclic olefins, monocyclic olefins and open chain olefins, mixtures second or more Oelfine of each type are to be understood. That is, as component A) can cyclolefin homopolymers and copolymers, such as bi-, ter- and

Multi polymers are used.

The extending opening of the double bond Cycloolefinpolymerisationen can be carried out, for example, using catalyst systems according to EP-A-0 407870 or EP-A-0203799 as well as with a conventional Ziegler catalyst system (see. For example, DD-A-222 317).

Cycloolefin and copolymers containing structural units derived from

Monomers of the formulas I to VI or VII contain are preferably prepared using a homogeneous catalyst. This is preferably a metallocene, the central atom is a metal from the group titanium, zirconium, hafnium, vanadium, niobium and tantalum, which is bridged to each other with two mono- or polynuclear ligands forming a sandwich structure, and an aluminoxane. This reaction is known and described for example in EP 0566988 A1 and the therein mentioned documents.

Preferably, as component A) a cycloolefin with

Viscosity of greater than 20 cm 3 / g (measured in decalin at 135 ° C in a concentration of 0.1 g / 100 ml) is used from 140 to 240 ° C and a glass transition temperature (T g).

For cycloolefin copolymers derived from ethylene and norbornene, it is known that the glass transition temperature can be adjusted by selecting the ratio of norbornene to ethylene. High proportions of norbornene units in the copolymer mean high glass transition temperatures. For copolymers derived from other cyclic olefins and non-cyclic olefins same applies. Under glass transition temperature method is to be understood in the context of the present specification according to ISO 11373 with the differential scanning calorimetry (DSC) certain size, wherein the heating rate is 10 K / minute. The compositions can contain, as component A) COP also polymerized with ring opening in the presence for example of tungsten, molybdenum, rhodium or rhenium containing catalysts. The cycloolefin polymers thereby obtained have double bonds by

Hydrogenation may be removed (see FIG. eg US-A-3,557,072 and US-A-4,178,424).

Preferably, cyclic olefin copolymers produced by metallocene catalysts are (referred to as "COC" called) is used as component A) by ring-sustaining copolymerization in the presence. Under these conditions, the cyclic structure is maintained and the Cyloolefinmonomeren incorporated into the resulting polymer chain.

Alternatively, or in addition to the above COC with preserved structure of the cyclic olefin monomers or types according to the invention prepared under ring-opening copolymerization derived from hydrogenated types can be used.

In addition to the substantially linear cycloolefin copolymers and the types produced by ring-opening copolymerization or the derived hydrogenated types and modified types can be used in addition, which have subsequently been grafted with ethylenically unsaturated, preferably functionalized monomers, such as unsaturated carboxylic acids.

As component B) in the inventive compositions can be one derived from one or more alpha-olefins polymer

optionally further comprising at least one alkadiene and / or derived from at least one vinyl aromatic monomer structural units used. In the case of alpha-olefins is non-cyclic monoethylenically unsaturated hydrocarbons with the

Double bond in alpha position. Examples of alpha-olefins are ethylene, propylene, butene-1, hexene-1, 4-methyl pentene-1, or isobutylene. It can be used on the basis of alpha-olefins homo- or copolymers. This may incur

Alkane dienes modified, for example with isoprene or butadiene and / or with vinylaromatics, for example styrene. and elastomeric terpolymers Polyolefinco- and beside it can be used.

Preferred polyolefins are derived from aliphatic 1-olefins having 2 to 8 carbon atoms, for example ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1 and octene-1 as well as combinations of two or more of these

Monomers.

The polyolefins of component B) is linear or branched types. The sequence of different monomer units in these polyolefins may be random or in the form of blocks. The individual monomer units may be sterically different,

For example, isotactic, syndiotactic or atactic. Preferably, component B) polyolefin homopolymers or copolymers derived from at least one alpha-olefin having 1-8 carbon atoms, which are optionally modified with isoprene, butadiene and / or styrene.

Particularly preferred components B) are polyolefin homopolymers derived from ethylene or propylene or polyolefin copolymers derived from ethylene and / or propylene present in an amount of up to 10.% Of higher alpha-olefins having 4-8 carbon atoms. Copolymers in this

Context to understand polymers, which are derived from three or more different monomers.

Component B) is very particularly preferably used are polyethylene (high (HDPE), medium density MDPE) and low density (LDPE). These polyethylenes are produced by the low or high pressure processes with corresponding catalysts and are characterized by low density in comparison with other plastics (<0.96 g / cm 3), high

Tenacity and elongation at break, very good electrical and dielectric properties, very good resistance to chemicals, and depending on the type of high resistance to stress cracking and good processability and machinability.

The polyethylene molecules contain branching. The degree of branching of the molecular chains and the length of the side chains influence the properties of the polyethylene material. The HDPE and MDPE types are slightly branched and only short side chains.

Polyethylene crystallized upon cooling from the melt. Here, the long chains of molecules arrange folded in some areas and form very small

Crystallites that are connected together with amorphous zones to structures, called spherulites. The crystallization is the better possible, the shorter the chains and the lower the degree of branching. The crystalline fraction has a higher density than the amorphous portion. Therefore, we obtain different densities, depending on the crystalline content. This

Degree of crystallization is, depending on polyethylene type between 35% and 80%.

60% high density polyethylene (HDPE) can be up to 80% degree of crystallization at densities between 0.940 g / cm 3 and 0.97 g / cm 3 achieved. 50% medium density polyethylene (MDPE) are up to 60% degree of crystallization at 0.930 g / cm 3 to 0.940 g / cm 3 density reached. 40% with low density polyethylene (LDPE) can be up to 50% degree of crystallization at densities between 0.915 cm reached 3 and 0.935 g / cm 3 g / cc. In this type is highly branched polymer chains which have a low density.

Moreover, one still knows linear low density polyethylene (LLDPE). Its polymer molecule has only short branches. These branches are prepared by copolymerization of ethylene and higher a- olefins, such as butene, hexene or octene. The degree of crystallization of this type is 10 to 50% and the density is in the range of 0.87 g / cm 3 to 0.940 g / cm 3. Other types of polyethylene are characterized by their high molecular weight. These are high molecular weight polyethylene (HMW PE) or ultra high molecular weight polyethylene (UHMWPE). The polymer chains of this type are longer than those of HDPE, MDPE, LDPE or LLDPE. The average molecular weight of HMWPE is 500 - 1000 kg / mol. The average molecular weight of UHMWPE is about and can reach values ​​up to 6000 kg / mol.

The properties of polyethylene are predominantly determined by density, molecular weight and molecular weight distribution. Thus, increases. As the impact and

Impact strength, tensile strength, the elongation at break and resistance to stress cracking with the molecular weight about. HDPE narrowly distributed with little low molecular component is more impact resistant, even at low temperature, as a broadly distributed within the same ranges for melt index and

Viscosity. Widely distributed types in turn are easier to process.

The higher the molecular weight of polyethylene, the more difficult the production of compositions by means of extruder. while a

Polyethylene 10 5 g / mol up can be used as a single polyethylene component with an average mass of about 4.9 x still are, for example

Polyethylene types between 0.5 to 8 x 10 6 g / mol only in alloyed form, that is to be processed according to the invention with composition according to increasing content of component A) and C) by means of extrusion or injection molding. In order to optimize the processability of such compositions in substantial retention of the mechanical properties, also HMWPE and / or UHMWPE, in addition to the high molecular weight polyethylene as part of component B) in the invention

Compositions are incorporated.

Polypropylene is a product manufactured by means of stereospecific catalysts acting isotactic, syndiotactic or atactic polypropylene. the isotactic polypropylene, in which all methyl groups are arranged on one side of the zigzag imaginary molecular chain, used in the inventive compositions as the component B) is particularly preferred. In cooling from the melt, the regular structure of the isotactic polypropylene favors the formation of crystalline regions. The

Chain molecules are seldom incorporated into full-length into a crystallite since they also contain non-isotactic and therefore not crystallizable shares. In addition, amorphous regions resulting from the

Entanglement of the chains in the melt, particularly at high

Polymerization. The crystalline fraction is dependent on the fabrication conditions of the moldings and is 50% to 70%. The semi-crystalline structure makes a difference strength and stiffness due to the high secondary forces in the crystallite; arise during the disordered regions having the higher mobility of their chains above the glass transition segments flexibility and toughness. The density of polypropylene is very low and ranges from 0.895 g / cm 3 and 0.92 g / cm 3. Molded articles of polypropylene are characterized, in comparison with moldings of polyethylenes with higher rigidity, hardness and strength. Polypropylene has a glass transition temperature of 0 to -10 ° C. The crystallite melting range is from 160 to 165 ° C. These temperatures can be modified by copolymerization; to those skilled in the

Measures known.

Preferred components B) are present with 1-10 HDPE, MDPE, LDPE, LLDPE, HMWPE, UHMWPE, propylene homopolymers, propylene copolymers.% Of structural units derived from 1-alkenes with 4-8 C atoms and / or styrene and / or butadiene propylene-ethylene copolymers containing 10 to 90 are derived, wt.% of propylene-derived structural units, as well as combinations of two or more thereof. The compositions of the invention are characterized by the presence of a selected component C). It may be block copolymers derived from at least two different alpha-olefins. Examples include block copolymers having polypropylene and polyethylene blocks. The block copolymers may comprise two blocks or of more than two blocks which in turn are derived from two or more alpha-olefins. The ratio of the blocks may vary within wide ranges, for example, a block may comprise a proportion of 20 to 80.% Having in the total mass of the block copolymer and a second block contains a proportion of 80 to 20.%.

Component C) may be random copolymers, which are derived from ethylene and at least one other alpha-olefin.

Examples of copolymers of this type are of ethylene and one or more 1-alkenes with 3-8 C atoms, copolymers derived, particularly ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1- octene-derived random copolymers. When preparing the mixtures according to the invention is to ensure that components B) and C) are different.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and at least one alkadiene. These may be random copolymers or block copolymers. Examples of copolymers of this type are of ethylene and butadiene, propylene and butadiene, ethylene, propylene and butadiene, ethylene and isoprene, propylene and isoprene, or of ethylene, propylene, and isoprene copolymers derived.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and of at least one vinyl aromatic monomer. These may be random copolymers or block copolymers. Examples of copolymers of this type are of ethylene and styrene, propylene and styrene, or of ethylene, propylene and styrene copolymers derived.

Component C) may also be homo- or copolymers, which are derived from at least one alpha-olefin and with ethylenically unsaturated carboxylic acids and / or their anhydrides and / or their esters, with ethylenically unsaturated epoxides, with ethylenically unsaturated silicon compounds , with ethylenically unsaturated amines, and with

Combinations of two or more thereof are grafted. In the derived alpha-olefins polymer backbone may be in the case of

Copolymers random copolymers or block copolymers. Examples of polymers forming the backbone of these graft polymers are polyethylene, polypropylene or polyethylene-polypropylene. These homo- or copolymers grafted with selected ethylenically unsaturated monomers or with combinations thereof. Examples of ethylenically unsaturated carboxylic acids are itaconic acid, fumaric acid, acrylic acid, methacrylic acid, and in particular maleic acid; Examples of anhydrides of ethylenically

unsaturated carboxylic acids are the anhydrides of the above-mentioned

Carboxylic acids; Examples of esters of ethylenically unsaturated carboxylic acids are the alkyl esters, for example, derived from CiC ö alkanols, the aforementioned carboxylic acids; Examples of ethylenically unsaturated epoxides are Gyicidylester of ethylenically unsaturated carboxylic acids, such as glycidyl methacrylate;

Examples of ethylenically unsaturated silicon compounds are esters of ethylenically unsaturated carboxylic acids with Trialkoxysilylalkanolen,

Dialkoxyalkylsilylalkanolen or Alkoxysilyldialkylsilylalkanolen, eg

Trialkoxysilylpropyl- (meth) acrylate; Examples of ethylenically unsaturated amines are vinylamine or allylamine.

Particularly preferred graft copolymers of this type are ethylene polymers, propylene homopolymers or ethylene-propylene copolymers, each with maleic acid, with acrylic acid, methacrylic acid, or with

Combinations of two or more thereof have been grafted.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and of at least one ethylenically unsaturated carboxylic acid and / or its anhydride and / or esters thereof. Examples of alpha-olefins for the preparation of these copolymers

are used, ethylene, propylene or mixtures thereof. Examples of ethylenically unsaturated carboxylic acids are itaconic acid, fumaric acid,

Acrylic acid, methacrylic acid, and in particular maleic acid; Examples of anhydrides of ethylenically unsaturated carboxylic acids are the anhydrides of the aforementioned carboxylic acids; Examples of esters of ethylenically

unsaturated carboxylic acids are the alkyl esters, for example, derived from C1 to C6 alkanols, the above-mentioned carboxylic acids. The copolymers may be random copolymers or block copolymers.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and of at least one ethylenically unsaturated epoxy compound. Examples of alpha-olefins to

Preparation of these copolymers are used, ethylene, propylene or mixtures thereof. Examples of ethylenically unsaturated

Epoxy compounds are glycidyl esters of ethylenically unsaturated

Carboxylic acids, such as glycidyl methacrylate. The copolymers may be random copolymers or block copolymers.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and of at least one ethylenically unsaturated epoxy compound. Examples of alpha-olefins to

Preparation of these copolymers are used, ethylene, propylene or mixtures thereof. Examples of ethylenically unsaturated

Epoxy compounds are glycidyl esters of ethylenically unsaturated

Carboxylic acids, such as glycidyl methacrylate. The copolymers may be random copolymers or block copolymers.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and of at least one ethylenically unsaturated silicon compound. Examples of alpha-olefins which are used for preparing these copolymers, ethylene, propylene or mixtures thereof. Examples of ethylenically unsaturated silicon compounds are esters of ethylenically unsaturated carboxylic acids dialkylsilylalkanolen with Trialkoxysilylalkanolen, Dialkoxyalkylsilylalkanolen or alkoxysilyl, eg Trialkoxysilylpropyl- (meth) acrylate. Both

Copolymers may be random copolymers or

acting block copolymers. Component C) can also be copolymers, which are derived from at least one alpha-olefin and at least one ethylenically unsaturated amine. Examples of alpha-olefins which are used for preparing these copolymers, ethylene, propylene or mixtures thereof. Examples of ethylenically unsaturated amines are vinyl amine and allyl. The copolymers may be random copolymers or

acting block copolymers.

Component C) can also be copolymers, which are derived from at least one alpha-olefin and at least one Vinylester a saturated aliphatic carboxylic acid, optionally having a hydroxyl group. Examples of alpha-olefins which are used for preparing these copolymers, ethylene, propylene or mixtures thereof. Examples of Vinylester a saturated aliphatic carboxylic acid are Vinylester of Ci-Cis-alkanecarboxylic acids, especially vinyl acetate. The copolymers may be random copolymers or block copolymers.

When to be selected as components B) and C) in each individual case the polymer is different compounds. Compound C) is used as phase mediators between the group consisting of components A) and B) phases. It is advisable to consider when choosing the component C) that it has a certain similarity to components A) and B). For example, if used as component B) a polyethylene or a polypropylene, or a copolymer of ethylene and propylene-derived units, so are included in component C) is also advantageously of ethylene or propylene derived units. For example, if used as component A) a COC with ethylene or propylene as co-component, as derived units are present in component C) is also advantageously of ethylene or of propylene.

The copolymers of component C) may be referred to as phase mediators according to the present invention, since they at the

Interface the group consisting of components A) and B) polymer phases can be arranged so that the interfacial tension diminish, increase the adhesion between the phases and controlling the size of the particles (disperse phase) in the composition. A phase of mediation

Polymers is usually the more successful, the greater the structural similarities of the molecules of the phase mediator with the to-promoting polymers. As applied to the phase switching of COP and polyolefins, should be preferred components C) are used which contain built-in as predominantly monomer component or components, those are also included as a monomer component or components in the polymer to compatibilizer.

The compositions according to the invention with component C) as phase mediators generally have dramatically better mechanical properties than compositions without component C). They can also stabilize the phase structures by preventing coalescence.

The proportion of component A) in the inventive compositions is preferably 4.5 to 95 wt .-%, particularly preferably 19 to 80% by weight and most preferably 23-75 wt.%.

The proportion of component B) in the inventive compositions is preferably 4.5 to 95 wt .-%, particularly preferably 19 to 80% by weight and very particularly preferably 23 to 75 wt.%. The proportion of component C) in the inventive compositions is preferably 0.5 to 20 wt .-%, particularly preferably 1 to 10 wt.% And very particularly preferably 2 to 6% by weight.

In this case, the proportions of components A), B) and C) add up to 100% by weight.

The erfind ungsgemässen compositions may contain one or more component A), one or more component B), and one or more components C). Said compositions are prepared by known for thermoplastics standard methods and processes such. example by

Kneading, molding, extrusion or injection molding.

The compositions of this invention may contain additives, for example thermal stabilizers, UV stabilizers, antistatic agents,

Flame retardants, plasticizers, lubricants, lubricants, pigments,

Dyes, optical brighteners, processing aids, inorganic and organic fillers, that is to say in particular also reinforcing materials such as glass, carbon or high modulus fibers, or combinations of two or more of these additives.

The proportion of additives in the composition of the invention amounts commonly to between 0 and 25 wt.%, Preferably of between 0.1 and 20.% And particularly preferably of between 0.5 and 10.%, Based on the total mass of Composition.

The compositions of this invention can particularly advantageously suitable for the production of moldings after pressing, injection molding or

Extrusion processes are processed. Examples of shaped articles are plates, fibers, rods, films and tubes.

These moldings are also an object of the present invention.

These moldings are characterized by the above-mentioned advantageous

Properties, in particular by the high heat resistance, so that they are suitable for sterilization or for use at temperatures up to 180 ° C, for example. The invention also relates to the use of the above-described

Shaped body or the shaped bodies produced from the compositions described above in medicine, medical, food, electronics, electrical engineering, container and apparatus engineering, vehicle construction, in the vulcanization of elastomer products, as well as packaging materials. The shaped bodies described above come thereof, for example, as a temperature-resistant film, a deep-drawn films, as temperature and chemical-resistant containers or parts, such for example as bottles or caps, used. These parts are characterized by the ability to steam sterilization and therefore can be preferably used in the field of medicine, medical devices and food technology.

The molded articles described above are, for example, as

Insulation films, as capacitor films and as release films in battery technology used and thus be in the field of electronics and

Using electrical engineering.

The molded articles described above are characterized by a high

Temperature resistance, good insulation properties and high

Water vapor barrier effect and are, for example, as films for applications in solar technology used.

In the apparatus and container are shaped bodies according to the invention for the production of blank temperature and use of chemical resistant container as well as parts and fillings for apparatus, such as inserts for scrubbers or columns (column bottoms).

In vehicle are shaped bodies according to the invention for the manufacture of temperature-resistant films or heat-resistant parts can be used for the vehicle interior. These sheets or parts are distinguished by their niederiges specific weight and are suitable for weight loss. During vulcanization of elastomer products are shaped bodies of the invention can, for example, as cores in the vulcanization of elastomer moldings such as hoses, use. The following examples illustrate the invention. A limitation is intended thereby.

General Procedure

The polymeric components described in Table 1 below were first dried (100 ° C, 24 h, vacuum) and then in the specified weight ratios as below in a 30 mm

Twin-screw extruder (Fa. Leistritz) under protective gas (N 2) extruded. The obtained granulated polymer compositions were dried then injection molded (100 ° C, 24 h, vacuum) and to give moldings. The specimens obtained were examined for their physical properties. Details can be found in Table 2. Table 1: Composition of the investigated polymer compositions

Figure imgf000023_0001

'Component A is TOPAS 6013, a ring produced under maintaining copolymerization of norbornene-ethylene copolymer having an ethylene unit content of 50 mol%; T g (DSC) 140 ° C

2) Component B is HOSTACOM ® PPR 1042 12, a polypropylene copolymer

3) Component C is ENGAGE ® 8452; a random polyolefin elastomer derived from ethylene and 1-octene having a density of 0.875 g / cm 3 Table 2: Prüfunqsergebnisse

Figure imgf000024_0001

) Determined according to ISO 1133 at 230 ° C with 2.16 kg

2) determined according to ISO 75-1 / 2

3) Charpy impact strength, notched; determined according to ISO 179 / 1eA at 23 ° C) Charpy impact strength, notched; determined according to ISO 179 / 1eA at -30 ° C

5) Charpy impact strength, unnotched; determined according to ISO 179 / 1eA at 23 ° C

6) Charpy impact strength, unnotched; determined according to ISO 179 / 1eA at -30 ° C

7) determined according to ISO 527

8) determined according to ISO 527

Claims

claims
1. A composition comprising
A) at least one Cyclolefinpolymer having a glass transition temperature of at least 140 ° C,
B) at least one derived from one or more alpha-olefins polymer having optionally further at least one alkadiene and / or structural units derived from at least one vinylaromatic monomer, and
C) at least one compatibility of the components A) and B)
improving and differing from component B) component selected from the group
- the block copolymers derived from at least two different alpha-olefins,
- the random copolymers derived from ethylene and at least one other alpha-olefin,
- the copolymers derived from at least one alpha-olefin and at least one alkadiene,
- the copolymers derived from at least one alpha-olefin and of at least one vinyl aromatic monomer,
- the homo- or copolymers derived from at least one alpha-olefin, which with ethylenically unsaturated carboxylic acids and / or their anhydrides and / or esters thereof, with
ethylenically unsaturated epoxides, with ethylenically unsaturated silicon compounds with ethylenically unsaturated amines, and combinations of two or more thereof are grafted,
- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated carboxylic acid and / or its anhydride and / or their esters,
- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated epoxy compound,
- the copolymers derived from at least one alpha-olefin and of at least one ethylenically unsaturated silicon compound,
- the copolymers derived from at least one alpha-Olfein and at least one ethylenically unsaturated amine, and
- the copolymers derived from at least one alpha-olefin and of at least one of a saturated Vinylester
aliphatic carboxylic acid, optionally a
having hydroxyl group.
2. Composition according to claim 1, characterized in that
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003
wherein R2, R3, R4, R5, Re, R7 and Re are the same or different and are a hydrogen atom or a d-Cs-alkyl radical, where identical radicals in the various formulas can have different meanings.
3. Composition according to claim 2, characterized in that component A) is derived from monomers of the formulas I to VI as well as cyclic Olefinresten of the formula VII and / or of non-cyclic Olefinresten of the formula VIII
Figure imgf000028_0001
wherein n is an integer from 2 to 10 and
R-19, Rio. R11 and R12 are identical or different and
represent hydrogen atom or a d-Ca-alkyl.
4. A composition according to claim 3, characterized in that component A) from polycyclic olefins of the formulas I or III and from acyclic olefins of the formula VIII, in particular of
Norbornene or tetracyclododecene and ethylene or propylene derived.
5. A composition according to any one of claims 1 to 4, characterized
in that component A) a cycloolefin polymer having a viscosity number of greater than 20 cm 3 / g, measured in decalin at 135 ° C in a concentration of 0.1 g / 100 ml, and having a glass transition temperature T g of 140-240 ° C.
6. The composition according to any one of claims 1 to 5, characterized
in that component B) is a polyolefin, derived from aliphatic 1-olefins having 2 to 8 C-atoms, in particular of ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1 and Okten- 1, as well as combinations of two or more of these monomers.
A composition according to claim 6, characterized in that component B) is selected from the group HDPE, MDPE, LDPE, LLDPE, HMWPE, UHMWPE, propylene homopolymers, propylene copolymers polymeric weight of 1-10.% Of structural units derived from 1-alkenes with 4-8 C-atoms and / or styrene and / or butadiene are derived, propylene ethylene copolymers having 10 to 90 wt.% of propylene-derived structural units, as well as combinations of two or more thereof.
Composition according to one of claims 1 to 7, characterized
in that component C) is an ethylene homopolymer,
Propylene homopolymer or ethylene-propylene copolymer containing each with maleic acid, with acrylic acid, with methacrylic acid or with
is combinations of two or more thereof has been grafted, or in that component C) is a random copolymer derived from ethylene and another alpha-olefin.
Composition according to one of claims 1 to 8, characterized
in that the proportion of component A) is 4.5 to 95 wt .-%, the proportion of component B) wt .-% is 4.5 to 95 and the proportion of component C) 0.5 to 20th - is%, and the proportions of components A), B) and C) add up to 100 wt .-%.
Composition according to one of claims 1 to 9, characterized
in that it contains additives, preferably thermal stabilizers, UV stabilizers, antistatic agents, flame retardants,
Plasticizers, glidants and lubricants, pigments, dyes, optical brighteners, processing aids, inorganic and organic
Fillers, and reinforcing materials such as glass, carbon or
based which are preferably present in a total amount of 0.1 to 20 high-modulus fibers, and combinations of two or more thereof.%, based on the total weight of the composition, are present.
11. moldings made of a composition according to any one of claims 1 to 10 degrees.
12. Use of the compositions according to one of the
Claims 1 to 10 in moldings produced medicine, medical, food, electronics, electrical engineering, container and
Apparatus engineering, vehicle construction, in the vulcanization of elastomeric articles as well as packaging materials.
13. Use according to claim 12, characterized in that the at the shaped body to a temperature-resistant film, a deep-drawing film to a temperature and chemical resistant container or a part thereof to form an insulating film, a capacitor film to a release film in the battery technology, a film for applications in solar technology to an insert for scrubbers or for columns to be a part of a vehicle interior or a nuclei for the
Vulcanization of the elastomer moldings is.
PCT/EP2011/003614 2010-08-17 2011-07-19 Cycloolefin polymer compositions, molded bodies, and use of said molded bodies WO2012022409A1 (en)

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