CA2094558A1 - Polymer blends of cycloolefin polymers and polyolefins - Google Patents

Abstract

Abstract Polymer blends of cycloolefin polymers and polyolefins 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 CnH2n 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.

Description

209~

HOECHST AR~IENGESELLS E~FT ~OE 92/F lllX Dr. SP/PL/wo Description Polymer blends o~ cycloolefin polymer~ and polyolefin~

Cycloolefin polymers are a clas~ of polymer~ with an outstanding property spectrum, having in ~ome ca~es, inter alia, good heat re i6tance, transparency, hydro-lytic ~tability, low water uptake, good weathering resistance and high rigidi~y. They are hard, brittle thermoplastics.

It i~ known that cycloolefins can be pol~merîzed by means of various cataly~t~. Dependinq on the catalyst, the polymerization proceeds via ring opening (US-A-3 557 072, US-A-4 178 424) or with 6cisæion of the double bond (EP-A-156 464, EP-A-283 164, EP-A-291 208, EP-A-291 970, DE-A-3 922 546).

Cycloolefin polymers are insu~ficien~ly resi6ta~t to impact and shock stress. It i8 generally known that the resistance to shock and impact stress is good in the case ; of polyolefins ~uch as polyethylene, polypropylene and 1-polybutene. ~owever, these polyolefins have a limited heat resistance, low strength, a low modulu~ and low hardness.

It is known that 1-olefin~ such as ethylene and propylene can be polymerized by mean3 of variou~ catalyst~ to form polyolefins, in particular polyethylenes and poly-propylenes (DE 3 620 a~o, ~P 399 348, EP 086 644, EP 185 918, EP 387 690).

Polyethylene can al~o be prepared by free-radi~al poly-merization (US 3 336 281). ~he resultant product i5 a low denRity material ~LDPE), compared to the material that has been catalytically prepared, which is of high to `~ 2~ 3~8 medium density (HDPE, NDPE). The same i~ true of co-polymers of ethylene with 1-olefin~ (LLDPE).

It is generally known that important properties of polymers, ~uch as the aforementioned properties, can be modified if polymer6 are blended with other polymer~. For instance, the patent specification~ DD 214 137 and DD 21~ 623 describe thermoplastic ~tructural ~aterial~
based on p41yolefins that ~imultaneously have a good heat resistance, re6i~tance to chemical~, rigidity, ~oughne~æ
and very good dielectric properties. They con~ain as essential constituen~s norbornene-ethylene copolymer~ and polyethylene or branched polyolefin~, if necessary with the addition of stabilizers, lubricant~, elastomer~, thermoplastics and reinforcing agents. Elastomers such as ela~tomeric ethylene copolymers and t~rpolymer~ or graft copolymers are added to improve the impact ~trength and notched impact streng~h. Howevar, block-type copolymers or terpolymers of ethylene or 1-ole~ins and cycloolefins are not mentioned as ela~tomer6.

According to the above documents additions of poly-ethylene or branched polyolefins to ethylene-norbornene copolymer~ lead to an i~provement in the re~i~tance to chemicals and toughness of the norbornene-ethylene copolymers. Conversely, the addition of norbornene-ethylene copolymers to polyethylene or branched poly-olefins led to an increase in ~he strength~ modulus and hardness, without resulting in any decrease in the impact flexural strength.

Furthermore, it i~ known that polyolefin thermopla~tic combinations of 40 to 98 ~ by weight of crys~alline polyolefîn and 2 to 60 % by weight of a random cyclic olefinic copolymer (glass tran~ition temperature 70 to 210~C, cryatallinity 0 to 5 %) have a good heat resi~-tance and crack resi~tance combined with low ~hrinkage (JP 1 318 052). According to Japanese Patent Application 2 ~ 9 ~ 8 JP 3 122 148 cycloolefin polymer com~inations of polymers of the cyclic olefin and crystalline polyolefins have an improved melt processability.

US-A 4 990 559 describes a thermoplastic co~bination of 5 to 90 % by weight of linear poly41e~in (comprising 8 to 40 % of ultrahigh molecular weight polyolefin (~ 10 to 40 dl/g) and 60 to 92 ~ by weight of low to high molecu-lar weight polyolefin (~ 0.1 to 5.0 dl/g)) and 95 to 10 %
by weiqht of at least one cyclool2fin thermopla~tic selected from ring-opening polymer~ and ring-opening copolymers.

A blending of cycloolefin copolymers with polyolefins such as polyethylene, polypropylene, l-polybutene, 1-polyhexene, poly(4-methyl-1-pentene), inter alia, i~
attractive BinCe such polyolefins are relatively cheap and the corresponding blends then also offer co~t advantages. It is then important to achieve as favorable a property combination as possible in the blend, utilizing the C08t advantages. Such blends are mainly suitable for applications where good material properties are required.

It is an object of the present invention to provid~ a process in which, ~tarting from favorable combinations of cycloolefin polymers, polyol~fin~ and additive~, polymer blends are obtained having a~ broad a range of material propertie as possible, in particular strength, hardness, heat resistance and toughness.

It is also ~n object of the pre~ent invention to obtain, starting from the individual components, i.e. polyole~ins 3Q or cycloolefin polymer~ (including cycloolefin ~o-polymers), by means of additions blends having good material properties.

This object i~ achieved by the process claimed in claim 1.

-- ,a --The polyolefins used are derived from open-chain non cyclic olefins, for example from ~thylene, propylene, l-butene, 1-hexene, 4-methyl-1-pentene, i~obutylene, isoprene or butadiene. In addition to polyi80prene and polybutadiene, there may also be used elastomeric buta-diene copolymers and terpolymers and/or their graft copolymers, and also elastomeric polyolefin copolymer~
and terpolymer~ and/or their graft copolymers. ~he polyolefins are preferably derived from l-olefin6, styrenes and/or their copolymer~ and terpolymers and al~o graft copolymers al60 falling under this cla6sification.
Preferred polyolefins compri~e aliphatic l-olefins, in particular those having 2 to 8 carbon atoms, for example ethylene, propylene, l-butene, 1-hexena, 4-methyl-1~
pentene and 1-octene. Particularly preferred are 1-olefins having 2 to 6 carb~n atoms, such a~ ethylene, propylene, 1-butene, l~hexene and 4-methyl 1-pentene.
Polyolefins that can be ~Red include in particular al~o copolymers and terpolymers of variou~ l-olefins, which may also comprise cyclic olefins, for example o ethy-lene, propylene, hexadiene, dicyclopentadiene and ethyli-dene norbornene. Particularly preferred polyolefins are polyethylene and polypropylene.

A process for the preparation of a suitable ~inely particulate block copolymer is the subject of the non-prior-published German Patent Application P 42 05 41~.8, incorporated herein by reference. ~he block copolymer~
described there, which are included as additive6 in the blends prepared according to the invention, comprise at least two blocks with different amounts of olefins, one olefin being derived from norbornene and at lea~t one olefin being a cycloolefin CnH~2 where n ~ 4 to 13 ox an acyclic olefin. Corresponding homopolymere may also occur as impurities in ths block copolymers. In general, different blocks of a block copolymer also have different glass transition temperature~ In the case of two-block copolymers the block with the low gla~s transition temperature is termed the ~soft block", and the block with the higher glass transition temp~rature i~ termed the "hard block".

Surprisingly, the polymer blends with the~e block co-5 polymers prepared by thr process according to the inven-tion have outstanding mechanical properties. Their toughness is in all cases bet~er than that of pure cycloolefin polymers, and their strength, hardnes3 and modulus are in some case~ higher than those of pure polyolefins. Compared to the blends without these block copolymers described in DD 214 137 and DD 214 623, the blends prepared according to the inv~ntion have an improved melt vi~cosity~ higher elongation at break, and improved impact strength.

The polymer blends obtained by the process according to the invention comprise from 0.1 to 99 part~ by weight of at least one block copolymer (C)~ from 0 to 95 parts by weight of cycloolefin polymer or polymers (A) and from 0 to 95 parts by weight of polyolefin or olefins ~B), the ~um of (A) ~ (B) ~ (C) being 100 part6 by weight. Fur-thermore, additives known per se, for example fillers or dyes, can be incorporated.

For the blends according to the invention ~uitable cycloolefin polymers (A) compri~e structural units that are derived from at least one monomer of the formulae I
to VII

HC/¦ \CH/
¦IR3 C R4 ~ ( I ), H C~¦ ~C H~p~ 2 C H

6 ~ J
H C/ ¦ C H
¦¦R~-C R ¦ C~2 ( I I ) .
HC\I /CH

H C/ I \C H~ I \C H/
¦¦R3--C--R ¦R5--~--R~ ¦ ( I I I ) .
~lH/ ~CH/ \ 2 / F H \ /C H \ /C H \ / R

¦¦R3--C R~ ¦ R5 C R6 ¦ R7- C R~ ¦ ( I V ) \ I / ~C H/C H\ I /C H

/ I \ / \ /
¦¦R --C--R ¦ I (V) .
\I H/ `T H/ \ R 2 / ¦ \CH/ ~CH~¦ ~CH/
¦¦R --C--R ¦ ¦ R7- C_R~ ¦ (V I ) .
\C H ~C H C H \ R 2 _ 7 _ 2~

CH CH
( Y l 1 ) .
( C H2 ) n h R' R2 R3 R4 R5, R6, R7 and R~ are the same or different and are a hydrogen a~om or a Cl-C8-alkyl radi-cal, the ~ame radicals in the variou~ formulae being able to be different, and n i8 an integer from 2 to 10.

The cycloolefin polymer6 (A) may comprise, in addition to the structural units that are derived from at least one monomer o~ the formulae I to VII, further structural units that are derived from at least one acyclic l olefin of the formula (VIII) R \ C - C ~ (Ylll), R~l / \ Rl2 where R~, Rl, Rll and Rl2 are the same or different and are a hydroyen atom or a Cl-C~-alkyl radical.

Preferred comonomers are ethylene or propylene. In particular copolymer5 of polycyclic olefins of the formulae I or III, and the acyclic olefins of the for-mula VIII, are u~ed. Particularly preferred cycloolefinsare norbornene and tetracyclododecene, whi~h may be ~ubstituted by C1-C6-alkyl, ethylene-nQrbornene copolymers being particularly important. Of the monocyclia olefins of the formula VII, preference i~ given to Gyclopentene, which may be ~ubstituted. Polycyclic olefins, monocyclic olefins and open-chain olefin~ are understood to include `; also mixtures of two or mor~ olefin~ of the re~pective -~ type. ~his means that cycloolefin homopolymers and copolymers ~uch a3 bipolymer~, terpol~mer~ and multi-polym~rs can be used.

209~3a8 The cycloolefin polymerizations proceeding with scission of the double bond may be catalyzed u~ing more novel catalyst systems (EP-A-0 407 870, EP-A-0 203 799), and also with a conventional Ziegler catalyst ~ystem (DD-A-222 317~.

Cycloolefin homopolymer~ and copolymer~ that compri~e structural units derived from monomers of the formulae I
to VI or VII are preferably prepared using a homogeneous catalyst. The latter comprises a metallocene, ~ho8e central atom is a metal from the group titanium, zir-conium, hafnium, vanadium, niobium and tantalum, which forms a sandwich structure with two bridged mononuclear or polynuclear ligands, and an aluminoxane. The bridged metallocenes are prepared according to a known reaction scheme (c~. J. Organomet. Chem. 288 (1985) 63-S7, EP-A-387 690). The aluminoxane acting a~ ao-catalyst can be obtained by various methods ~cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-302 424). ~he structure and also the polymerization of the6e cycloolefins i8 described in detail in EP-A-0 407 870, EP-A-0 485 893, EP-A-0 501 370 and EP-A-0 503 422. The3e compounds are cycloolefin copolymers that differ as regards their chemical uniformity and their polydi~per~ity.

Prefera~ly cycloolefin polymers are used having a Vi8-cosity number greater than 20 cm3/g (measured in decalin at 135C in a concenkration of 0.1 g/100 ml) and a glass transition temperature (Tg) of from 100 to 240C.

The blends may al50 compri~e cycloolefin polymer~ ~-hat have been polymerized with ring opening in the pre~ence of, for example, tung~ten-, molybdenum-, rhodium- or rhenium-containing catalys~ fi . ~he re6ultant cycloolefin polymers have double bonds that can be removed by hydro-genation ~US-A-3 557 072 and US-~-4 178 424).

9 ~ 5 ;~
The cycloolefin block eopolymer~ (C) contained in the blends prepared according to the invention are form~d from a monomer mixture compri~ing one or more cyclo-olefins of the formulae I to VI, in particular formulae I
or III, and at least one olefin ~elected from th~ group of cycloolefins of th~ formula VII and the acyclic olefins of the fonmula VIII.

Preference is giv~n to those compounds of the formulae I
and III in which the radicals R1 to R6 are hydrogen or a Cl-C6-alkyl radical, and ~ompounds of the formula VIII in which R9, Rl and R11 are hydrogen (in particular ethylene and propylene).

According to the process of German Patent Application P 42 05 416.8, to prepare the cycloolefin block co-polymer, from 0.1 to 95 % by weight, based on the totalamount of the monomers used, of at least one monomer of the formulae I, II, III, IV, V or VI

I I R 3 C - R~ ¦

~ l / R

HC / ¦ \ CH /
¦IR3 - C - R ¦ ~2 (Il).
HC\I /CH

H j/ ¦ \ jll/ ¦ \ /

HC \ ! / CH ¦ / CH

- 10~

H C/ ¦ \ ~ H/ ¦ \C H/ ¦ \C H
¦¦R3-C R~ ¦ RS--C ~t ¦ R7- C-Ra ¦ ( IV) -R S
/ j \ / \C H /
¦¦R -C--R~ ¦ (V~.
\I H/ ~C H/ \ R 2 R
R~
--F \CH/ \CN~¦ \CH ( V I ) .
¦¦R -C--R~ ¦ ¦ R7-C--RI' ¦
HC\I /CR~ / `!H/ \~2 h Rl R2 R3 R4 R5, R6, R7 and RB are the ~ame or different and are a hydrogen atom or a Cl-C8-alkyl radi~
cal, the same radicals in the VariOUB formulae being able to be different, from O to 95 % by weight, based on the total amount of the monomer~ used, of a cycloolefin of the formula VII

CH _ (Vl l ) ( ~ H 2 ) ~

where n i6 a num~er from 2 to lO, and from 0 to 99 ~ by weight, based on the to~al amount of the monomers used, of at lea~t one acyclic olefin of the formula VIII

\ C _ C ~ (V111).

where R9, Rl, Rll and Rl2 are the same or di~erent and are a hydrogen atom or a C1-C8 alkyl radical, are polymerized at temperatures of from -78 to 150C and at a pres~ure of from O.Ol to 64 bar, in the pre~ence of a cataly~t comprising a cocatalyst and a metallocene of the formula XI

R~6 R ~ ~1 / (Xl) \ \ R
R
where M1 is titanium, zirconium, hafnium, vanadiu~, niobium or tantalum, R14 and Rl5 are the same or different and are a hydrogen atom, a halogen atom, a C~-ClO-alkyl group, a C~-C~0-alkoxy group, a C6-C10-aryl group, a C6-C~0-aryloxy group, a C2 C10-alkenyl group, a C~-C40-arylalkyl group, a C~-C~0-alkylaryl group or a CB-C40-arylalkenyl group, 0 Rl6 and Rl7 are a mononuclear or polynuclear hydro~arbon radical which together with the central atom M1 can form a ~andwich ~tructure - 12 ~ S~

Rl8 i~s ~1~ Rl~ Rl~ R~ t9 Rl~ Rl9 _ 1 2_ _ l 2~ 2_ --U ~--C R z ~ C-- --o _ U 2-- --C--C--R20 R20 1 20 12~ 420 ~ R~ l~c = BR19, - A~R18, -Ge , -Sn-, ~O-, -S-, = SO, ~- SO2, = NRl5, = CO, - PR19, or ~ p(o)~l9, where R1a, R20 and R21, are the same or different and a hydrogen atom, a halogen atom, a Cl C10-alkyl group, a Cl-C10-fluoroalkyl group, a C6~C10-fluoroaryl group, a C6-C10-aryl group, a c1-c1O-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 ca~P f orm a ring with the atoms that connect them, and M2 is silicon, germanium or tin.
The reaction conditions are changed alway~ at a molecular weight di~tribution MW/N~ of le88 than 2, always based on the polymer block that is bein~
formed - in ~uch a way that the monomer-comonomer ratio changes by at least 10 %, or a further polymerizable monomer of the formulae I - VIII i~
metered into the monomer or monomers.

The polymerization is carried out in such a way that a two-stage or multistage polym~rization take~ place accordin~ to the number of changes in the parameters that are made or according to the monomer composition, a homopolymer ~equence of one of the monomers of the formulae I to YIII also being able to be polymerized in the first polymerization stage. Alkyl is ~traight-chain or branched alkyl. Th~ monocyclic olefin VI~ may al30 be substituted (e.g. by alkyl or aryl radical ).

The polymerization take~ place in dilute ~olutio~ (~ 80 %
by vol. of cycloolefin), in concentrated solution (~ 80 by vol. of cycloolefin), or directly in the liquid, - 13 - 2~9~3~
undiluted cycloolefin monomer.

The temperature and reaction time mu~t be suitably matched depending on the activi~y of the cataly~t, the desired molecular weight and desir~d molecular weight S distribution of the re~pective polymer block. ~l~o, the concentration of th~ monomer~ and al~o ~he n~ture o~ the solvent must be taken into account, especially a~ these parameters basically determine the relative incorporation rates of the monomers and are thus decisive for the glasc transition tempera~ure and heat resi~tance of the polymers~

: The lower the polymerization temperature is chosen within ~he range from -78 to 150C, preferably from 78 to 80C
and particularly preferably from 20 to 80DC, the longer the polymerization duration can be, with almost the same breadth of molecular weight distribution N~ for the respective polymer blocks.

If the sudden change in the reaction conditions is effected at a point in tLme in which the molecular weight distribution MW~M~ of the forming polymex block is equal to 1, then it can be assumed with certai~ty that all polymer blocks formed in this polymerizatinn stage have a catalyst-active chain end (i.e. are living polymer chains), and thus a further block can be polymerized onto these chain ends by changing the polymerization conditions. The coupling i~ 100 ~ for thi extreme case.
~he more the molecular weight distribution M~ of the polymer blocXs formed in a polymerization ~tage deviates from 1, i.e. M~ > 1, the greater the increase in the number of catalyst-inactive chain ends (i.e. dead chain ends or terminated chains), which are no longer capable of a coupling of a further block.

For the process for preparin~ block copolymers this means that ~he more the value N~/N~ of the polymer block prepared in the polymerization stage X i# in the region of 1 at the point in time at which the change in the reaction parameters takes place, the greater the proportion of block polymer chains become~ in the end product in which a chemical coupling between block X and block X + 1 has been effected.

Based on the structural uniformity and purity of the cycloolefin block copolymexs, thi6 means that the time windows for the individual polymerization stages shall as far as possible be chosen 80 that they oorrespond to a M~/M~ of the corresponding polymer blocks of almost 1, in order to obtain cycloolefin block copolymers of high purity and high structural uniformity.

If it is also desired to achieve a specific molecular weight for a polymer block, then the reaction duration must also be adjusted to the desired molecular weight.

During a polymerization stage or the formation of a polymer block, the monomer ratios in the reaction space are generally maintained constant 8Q that chemically uniform polymer blocks are formed. It i6 however then also possible to change the monomer ratios continuously during a polymerization stage, which then leads to polymer blocks that exhibit a structural gradient along the polymer chain, i.e. the incorporation ratio (for example the ratio of the number of norbornene building blocks to that of the ethylene building blocks in a part of the polymer block) changes continuously along the corresponding polymer block. In the case of polymer blocks that are built up from more than two type~ of monomers, this gradient can be achieved by continuoucly changing the concentration of a single monomer component.

Blocks with structural gradients can also be produced in those polymerization ~tages in which the concentration of several monomer component~ i~ simultaneously oontinuou~ly - 15 - 2~ 8 changed.

The change~ ~o be made in the monomer ratios can be achieved for example by changing the pre~ure of the acyclic olefin, by changing the tQmperature and thus the ~olubility of gaseous ~lefin~, by dilution with 801vent5 at constant pressure o the acyclic olefin or also by metering in a liquid monomer. Furthenmore, several of the aforementioned parameters can be simul~aneously altered.

Such sudden and al~o continuous change~ in the monomer ratio - and thus the preparation of blo~k copolymer~ -can be effected not only under bakchwifie control of the reaction but also under continuou control of the reaction.

Continuous and also multistage polymerization proces~es are particularly advantageous ~ince they permit an economically favorable u~e of the cycloolefin. Also, in continuous proces~es the cyclic olefin, which may occur as residual monomer together with the polymer, can be recovered and returned to the reaction mixture.

With such a polymerization procedure the block length can be controlled ~ia the throughput and reaction volume of the different reaction ve~sels (i.e. these two guantities determin~ the residence time at th~ differsnt reaction location~).

Preferred cycloolefin block copolymer~ tha~ may be mentioned for the blends are norbornene/ethylene block copolymers, norbornene/ethylene/propylene block co-polymers, dimethanooctahydronaphthalene (tetra~yclo-dodecene)/ethylene blocX copolymer~, dimethanooctahydro naphthalene/ethylene/propylene block copol~mer~ and block copolymers in which each polymer ~equence or polymer block is built up from a copolymsr, i.e. a bipolymer, terpol~mer or multipolymer, and also norbornene or 2 ~

dimethanooctahydronaphthalene has been incorporated in at least one polymerization 8tage. ~he particularly preferr~d norbornene/ethylene block copolymers/
norbornene/ethylene/propylene block copolymers and corresponding dimethanooctahydronaphthal~ne block copolymers are buil~ up from norbornene/e~hylene, norbornene/ethylene/propylene Gopolymer s~quences or corresponding dimethanooctahydronaphthalene copolymer 6equences of different composition, i.e they compri~e blocks (polymer ~egment~) that in sach case are norbornene/ethylene copolymers, norbornene/ethylene/
propylene terpolymers or corre~ponding dLmethan~-octahydronaphthalene copolymers or terpolymers.

The cycloolefin block copolymers prepared according to the described process can for ~he purpo~es of the present inYention be termed compatibilizers since they can arrange themselves at the interface of the polymer phases and hence reduce the interfacial tension, increase the adhesion between the phases, and control the ~ize of the particles (disperse phase) in the blend.
Compatibilization polymers i~ generally more successful the greater the ~tructural ~imilaritie~ between the blocks of the compatibilizer mediator and those of the polymers to be compatibilized. Complete miscibility of at least one type of block in at least one polymer is also advantageous in this connection. Applied to the compatibilization of cycloolefin polymers and polyolefins, there should preferably be used cycloole~in block copolymers that comprise, as predominantly incorporated monomer component or componen~ in the blocks, those that are al~o contai~ed as monomer component or components in the polymer6 to be compatibilized. If the polyolefin (B) i~ polyethylene, then preferably ~he block copolymer (C) should comprise at least one block predominantly of ethylene unit~ and at lea~t one block predominantly of cycloolefin units, in particular those that are present in the cycloolefin ~:2 1~ 5 ~ `~

copolymer (A). The ~ame al50 applies to polypropylene.
The blends containing phase mediators generally have dramatically improved mechanical propertie%. Also, they can stabilize ~he phase ~ructures by preventing coalescence.

The polyolefins (B) used in the blends are derived from open-chain noncy~lic olefin~, for example from eth~lene, propylene, 1 butene, l-hexene, 4-me~hyl-1-pentene, isobutylene, isoprene or butsdiene. In addition to polyisoprene and polybutaliene, there may al80 be used elastomeric butadiene copolymers and terpolymers and/or their graft copolymers, and al~o elastomeric polyolefin copolymers and terpolymer6 and/or their qraft copolymers.
The polyolefins are preferably derived from l-olefins, styrenes and/or their copolymers and terpolymers and also graft copolymers being included in this classificatîon.
Preferred polyolefins comprise aliphatic 1-olefins, in particular those havîng 2 to 8 carbon atoms, for example ethylene, propylene, l-butene, l-hexene, 4-methyl-1-pentene and l-octene.

Polyolefins that can be u~ed include in particular al~o copolymers and terpolymers of various l-olefin~, which may also comprise cyclic olefins, for example of ethylene, propylene, hexadiene, dicyclopentadiene and ethylidene norbornene.

The polyethylenes (B) preferably used in the blends ~re high density ~HDPE) polyethylene and medium density (MDPE3 polyethylene. Such polyethylenes are prepared by the low-pressure process using ~uitable catalysts~
Characterizing properties are: low density compared to other plastics (~ 0.36 g/cm3), high toughness and elon-gation at break, very good electrical and dielectric properties, ~ery good re istance to chemical~, and, dspending on the type, good resistance to strecs crack formation and good processability and machinabllity~

Polye~hylene molecules contain branc ~ n ~ degree of branching of the molecular chain6 and the length o~ the side chains ~ubstan~ially in~luence the properties of the polyethylene. The HDPE and NDPE type~ are sli~htly branched and have only ~hort ~ide chains.

Polyethylene crystallizes from the melt on cooling: the long molecular chains arrange themselYes in a folded manner in domains and form very ~mall cry~tallites, which are joined together with amorphous zones to form ~uper-lattices, i~e. spherulite~. The crystallization i8increa~in~ly possible the ~horter the chains and the less the degree of branching. The cry~talline fraction has a higher density than ~he amorphous fraction. Different densities are ~herefore obtained, depending on the crystalline fraction. This degree of c~y6tallization i~
between 35 and 80 %, depending on the type of polyethylene.

High density polyethylene (HDPE) reaches a degree of crystallization of 60 to 80 ~ at densities of from 0.940 g/cm3 to O.965 g/cm3; medium density polyethylene ~MDPE) reaches a degree of crystallization of 50 to 60 at a density of from 0-930 ~/cm3 to O . 940 g/cm3.

The properties of polyethylene are largely determined by density, molecular ~eight and molecular weight distribution. ~or example, the impact ~trength and notched impact ~trength, teax ~trength, elangation a~
break and resistance to strecs crack formation increase with the molecular weight. HDPE with a narrow molecular wei~ht di6tribution and having a ~mall low molecu~ar weight fraction i8 more impact re~istant, even at low temperatures, than HDPE having a broad molecular weight distribution, within the same ranges for the melt flow index and vi~c08ity number. Type~ having a broad molecu-lar weight distribution are in tur~ more easily processable.

- 19 -` 2~
The higher the molecular weight of polyethylene, the more difficult it becomes to prepare blend~ by means of extruders. Whereas a polyethylene wi~h a mean molecular weight of about 4.9 x 10t5 g/mol can ~ust b~ used as a single polyethylene component, polyethylene types having for example molecular weights of between 0.5 and 8 x 106 g/mol can be processed by means of extrusion or in~ection molding only in blended form, i.e. a~ a blend according ~o the invention with correspondingly increas-ing contents of component~ A and C. In order to optLmizethe processability of such blends while largely retaining the mechanical properties, in addition to high molecular weight polyethylene HDPE (0.1 - 0.5 x 106 g/mol) may al60 be incorporated as part of the component B into the blends according to ths invention. These ultrahigh molecular weight low-pressure polyethylenes (UHNMPE) may specifically also be constituen~s of ~he polymer blends.

Polypropylene is an isotactic, syndiotactic or atactic polypropylene prepared using stereospecifically ~cting catalysts. Only isotactic polypropylene, in which all methyl groups are arranged on one side of the molecular chain, imagined to be in the form of a zigzag, ha~ the properties of a technically usable ma~erial.

On cooling from the melt, this regular structure promotes the formation of crystalline regions. However, the chain molecules are seldom incorporated over their whole length into a crystallite since they also compri~e non-isotactic fractions and thus do not comprise cryskalli~able fractions. Furthermore, amorphous regions are formed due to the convolutions of the chains in the melt, particularly at a high degree of pol~merization. The crystalline fraction depends on the production conditions of the molded parts and is from 50 ~ to 70 ~. ~he paxtly crystalline structure imparts a certain ~trength and rigidity on account of the strong ~econdary forces in the crystallite, whereas the unordered regions with the 2 0 ~ 8 higher mobility impar~ flexibility and toughness to their chain ~egment6 above the glass transitlon temperature.

The proportion of cycloolefin polymer~ (A) in the blends according to the invention is preferably from 0 ~o 90 %
by weight and par~icularly preferably from 0 to 85 ~ by weight, and the propor~ion of polyolefin~ lB) in the blends prepared according to the $nvention is preferably at most 90 ~ by weight and particularly preferably at most 85 ~ by weight. ~he proportion of the cycloolefin : 10 blocX copolymers i5 preferably from 1 to 60 % by weight and particularly preferably from 1 to 55 % by weight, the proportions of the components A, B and C totalling 100 ~
by weight. The blends prepared according to th~ in~ention may comprise one or more cycloolefin polymers, one or more polyolefins, in particular polyethylenes or poly-propylenes, and one or more cycloolefin block copolymers.

The aforementioned polymer blends are prepared and processed by known standard methods for thermoplastics, for example by kneading, compression molding, extrusion or injection molding.

The blends prepared according to the invention may comprise additives, for example thermal stabilizer~, W
stabilizers, anti~tats, flameproofing ayents, pla~ti-cizers, lubricant~, pi~ments, dye~, optical brightener~, processing auxiliarie~, inorganic and organic fillers, i.e. in particular also reinforcing materials ~uch as glass fibers, carbon fiber~ or high-modulu~ fibers. ~he blends may be used paxticularly advantageou~ly for the production of moldings by the compre~ion molding, injection molding or eætru~ion proces~es. Example~ of moldings include sheet~, fibers, films ~nd hoses.

The following polymers were prepared by ~tandard methods:
cycloolefin copolymer~ A1 [COC Al], A2 [COC A2J, A3 tCOC A3J and A4 [COC A4]

2 ~ 9 ~

Pxeparation of COC Al A clean and dry 75 dm3 capacity polymerization reactor equipped with a stirrer was flushed with nitrogen and then with ~thylene. 20550 g of norbornene melt (~b) were then placed in the polymeriæation reactor. ~he reactor contents were heated to 70C while s~irring and ethylene was injected to a pre~sure of 6 bar.

250 cm3 of a solution of methylaluminoxane in toluene (10.1 ~ by weight of me~hylaluminoxane having a molecular weight of 1300 g/mol according to cryoscopic mea~urement) were then metered into the reactor and the mixture wa~
stirred for 15 mi~utes at 70C, the ethylene pressure being maintained at 6 bar by in~ecting in further ethylene. In parallel to this 500 mg of diphenyl-methylene~9-fluorenyl)cyclopentadienyl zirconium di-chloride were dissolved in 250 cm3 of a solu~ion of methylaluminoxane in toluene (concentration and quality see above) and preactivated by standing for lS minutes.
The soluti~n of the complex (cataly~t solution) was then metered into the reactor. In order to ~top the molecular weight increasin~, hydrogen can be added di~continuously or continuously through a lock to the reaction vessel immediately after the catalyst has been metered in (see COC A2 and COC A3). Polymerization was then carried out 2~ at 70C for 305 minutes while stirring, the ethylene pressure being maintained at 6 bar by in~ecting in further ethylene. The reactor contents were then quickly discharged into a stirred vessel containing 40 1 of liquid ~aturated aliphatic hydrocarbons l~Exxsol 100/110), 1000 g of ~elite J 100 and al~o 200 cm3 of deionized water at 70-C. The mixture was filtered 80 that the filter aid (Celite J 100) was retained and a clear pol~mer eolution wa~ obtained as filtrate. The clear solution was precipitated in a~etone, stirred for 10 minute~, and the su~pended polymer olid was then filtered off.

2 ~ 9 ~

In order to remove residual solYent from the polymer, the latter was stirred twice more with acetone and filtered off. Drying was carried out at 80 n C under reduced pressure within 15 hours.

S Yield: 4~00 g Preparation of COC A2 The preparation of COC A2 wa& performed in a ~imilar manner to COC Al, 1350 ml of hydrogen being added im-mediately after the catalyst had been metered in. The other altered reaction conditions are summarized in Table 1.

Preparation of COC A3 The preparation of COC A3 was performed in a similar manner to COC A1, 1875 ml of hydrogen bein~ continuously added after the catalyst had been metered in. ~he other altered reaction conditions are summarized in Table 1.

Preparation of COC A4 The preparation of COC A4 was performed in a ~imilar manner to COC A1. The altered reaction conditions are summarized in Table 1.

2 ~
_ 23 --8 8 ,, `~' o ~

.1 u~ ~

~J R O O
~ ~0 _ C ~ ~ O O o ~_ ¢C¢

Q ~ ~ N

U~ O o ~0 R ~ R

- 24 ~ 3 Metallocene A: Diphenylmethylene(9-fluorenyl) pentadienyl zirconium dichloride Cycloolefin copol~mer A5 [COC A5]

A clean and dry 75 dm3 capacity polymerization reactor equipped with a stirrer wa~ flushed with nitrogen and then with ethylene. 27 1 of Exx~ol and 10700 g of norbornene melt were then placed in the polymerization reactor. The reactor was heated to 70C while ~tirring and ethylene was in~ected to a presæure of 2.5 barO

500 cm3 of a solution of methylaluminoxane in toluene (10.1 ~ by weight of methylaluminoxane having a molecular weight of 1300 g/mol according to cryo~copic measurement) were then metered in~o the reactor and the mixture was stirred for lS minutes at 70C, the ethylene pressure being maintained at 2.5 bar by injecting in further ethylene. Parallel to this 37 mg of i-propylene(9-fluorenyl)cyclopentadienyl ~irconium dichloride were dissolved in 300 cm3 of a ~olution of methylaluminoxane in toluene tconcentration and quality ~ee above) and preactivated by ~tanding for lS minutes. The 601ution of the metallocene (catalyst ~olution) was then metered into the reactor. Polymerization was carried out for 90 minutes at 70C while stirring, the ethylene pres ure being maintained at 2.5 bar by injecting in further ethylene. The reactor content6 were then quickly dis-charged into a stirred ves~el containing 40 1 of Exxsol 100/110, 1000 g of Celite J 100 and also 200 cm3 of deionized water at 70C. The mixture was filtered ~o that the filtsr aid (Celite J 100) was retained and a clear polymer solution was obtained as fîltrate. The clear solution was precipitated 1~ acetone, ~tirred ~or 10 minutes, and the suspended polymer solid was filtered off.

- 2~
In order ~o remove re~idual solven~ from th2 polym~r, the latter was stirred twice more with acetone and filtered off. Drying was carried out at 80C under reduced pressure within 15 hours.

Yield: 5100 g The physical characteristic6 of the five cycloolefin copolymers COC Al, COC A2, COC A3, COC A4 and COC AS are chown in Table 2.

~9~

_~

~1 A ~ ~ o ~
vlv ~
_ _ A C~ ~ ~ t~
V X ~) I` ~ N u~ N
_ _ A o O ~ CO 1~ ~ O
~ CD ~ O
V X ~C~ ~1 ~ N o N

._ q) In tll CO ID D ~ N p~ i5 S~ ~ OOt`O~ U~
N ~~
a ~ _- ~ ~
O ~ '~ U
O Z--' Y'~ Lr) ~ It) ~ 0~
. _ E3 :1 D~ dP ~

~ ~ CD 11-~ ~ ~ N 8 ~ ~ ~ ~ U7 _ ~ a ~, ~ ~ ~

O ~ ~ O
0~ ~ .
C~ .
E~ 11 2 ~

GPC: <Nw~, <Nn>; 150-C ALC Nillipore Water~ Chromatograph Column ~e~: 4 Schodex column~ AT~B0 ~/S
Solvent: o dichlorobenzene at 135C
Flow rate: 0.5 ml/min., concentration 0.1 g/dl RI detec~or, calibration: polyethylene (9~1 PE) Further characteristics of the cycloolefin copolymers A1, A2, A3, A4 and AS can be found in the example~.

Preparation of cycloolefin block copolymers COC Cl, COC C2, COC C3 and COC C4 Preparation of COC Cl A clean and dry 1.5 1 capacity autoclave equipped with a stirrer was flushed with nitrogen and then with ethylene.

375 ml of toluene and 107 g (1.14 mol) of norbornene and also 20 ml of a 10 % strength solution of met~yl-aluminoxane in toluene were then placed in the autoclave.
The autoclave was heated to 20C while stirring and ethylene was in~ected in to a pressure of 1.0 bar.

Pasallel to this 90.7 mg ~0.2 mmol) of rac-dimethylsilyl-bis(l-indenyl) zirconium dichloride were di~olved in 20 ml of methylaluminoxane solution (see above) and preactivated by standing for 15 minutes. The metallocene methylaluminoxane solution was then metered into ~he autoclave. Polymerization was then carried out for 45 minutes at 20C while stirring, the ethylene pressure being maintained at 1.0 bar by in~ecting in further ethylene.

After 45 minutes a solution of 520 ml of toluene and 20 ml of a 20 ~ strenyth 801ution of trimeth~laluminum in XExxsol was then met~red into the autoclave to~ether with , - ~8 -ethylene at a pressure of 15.0 bar and polymerized for 2 minutes at this pressure. The ~topp~r ~olution of 30 ml of isopropanol and 20 ml of Exxsol was then metered into the autoclave under exce~s pressure. ~he pressure of the polymer ~olution was relea~ed while ~tirring constantly, and the solution was then dischargedO

The solution was precipi~a~ed in acetone and washed twice with acetone. The polymer obtained was then stirred into a concentrated hydrochloric acid-water ~olution, in which it stood for about 2 hour6. The polymer was then wa~hed until it gave a neutral reaction and was stirred twice more with acetone. Drying was carried out at 50~C under a reduced pre3sure within 15 hours.

Yield: 36.6 g Preparation of COC C2 ~he preparation of COC C2 wa~ performed in a similar manner to COC Cl, 85 mg (0.19 mmol~ of rac-dimethylsilyl-bistl-indenyl) zirconium ~ichloride being used and the solution of 520 ml of toluene and 20 ml of a 20 %
strength solution of trimethylaluminum in ~Exxsol being metered in and ethylene being injected to a pressure of 15.0 bar after 30 minutes.

Yield: 9~.4 g Preparation of COC C3 A clean and dry 75 dm3 capacity polymerization reactor equipped with a ~tirrer wa~ flushed ~ith nitrogen and then with ethylene. 50 1 of Exxsol and 2.4 kg of norbor-nene melt were then placed in the polymerization reactor.
The reactor was heated to 40C while ~tirring and ethy-lene was in~ected in to a pressure of 1 bar.

2 ~ a 8 ~ 2~
500 cm3 of a solution o~ methylaluminoxane in toluene(10.1 % by weight of methylaluminoxane having a molecular weight of 1300 g/mol according to cryoscopic measurement) were th~n metered into the reactor and ~he mixture was stirred for 15 minute~ at 40C, the e~hylene pressure being maintained at 1 bar by in~ecting in further ethylene. Parallel to this 2000 mg of rac-dimethyl~ilyl-bistl-indenyl) zirconium dichloride were dissolved in 500 cm3 of a solution of methylaluminoxane in ~oluene (concentration and quality see above) and preactivated by standing for 15 minutes. The prepared catalyst ~olution was then metered into the reactor. Polymerization was then carried out for 45 minutes at 40C while ~tirring, the ethylene pressure being maintained at l bar by injecting further ethylene.

1 1 of propylene (liquid) wa~ then metered into the polymerization reactor, the reaction pressure was raised to 3.3 bar with ethylene, and was maintained at 3.3 bar by injecting in further ethylene. The resctor contents were then guickly discharged into a stirred vessel containing 40 1 of Exxsol 100/110, 1000 g of ~Celite J 100 and also 200 cm3 of deionized water at 70C. The mixture was filtered BO that the filter aid (Celite J 100) was retained and a clear polymer solution was obtained as filtrate. The clear solution was precipitated in acetone, stirred for 10 minutes, and the suspended polymer solid was then filtered off.

In order to remove residual solvent from the polymer the latter was stirred twice more with acetone and filtered off. Drying was carried out at B0C under r~duoed pressure within 15 hours.

Yield: 3200 g _ 3~ _ 2~
Preparation of COC C4 A clean and dry 75 dm3 capacity pol~meri~ation reactor equipped with a ~tirrer was ~lushed with ni~rogen and then with e~hylene. 16.5 1 of toluene and 3.5 1 of norbornene melt were then placed in ~he polymerization reactor. The reactor was hea~ed to 40C while ~tirring and ethylene was in~ected ~o a prefi~ure of 1 bar.

500 cm3 of a ~olution of methylaluminoxane ~n toluene (10.1 % by weight of methylaluminoxane having a molecular weight of 1300 g/mol according to cryoscopic measurement) were then metered into ~he reactor and tha mixture wa~
stirred for 15 minute6 at 40C, the ethylene pressure being maintained at 1 bar by in~ectin~ in further ethylene. Parallel to this B00 mg of rac-dimethylsilyl-bis(l-indenyl) zirconium dichloride were dissolved in 500 cm3 of a solution of methylaluminoxane in toluene (concentration and quality ee above) and preactivated by standing for 15 minutes. 14 1 of toluene together with 2000 cm3 of a solution of methylalumino~ane in toluene (concentration and quality see above~ were placed in a pressure lock and ~aturated with propylene at 5 bar. The pressure was then raised to 15 bar with ethylene and further ethylene was in~ected until the solution was saturated. Following this the olution of the ~etallocene (catalyst solution) was metered into the reactor.
Polymerization was then carried out for 30 minute~ at 40C while stirring, the ethylen~ pxes6ure bein~
maintained at 1 bar by in~ecting in further ethylene. The contents of khe pressure lock were then abruptly metered into the polymeri~ation reactor ~nd the reac~ion pres~ure was maintained at 13.5 bar with ethylene. Aft~r 5 minute~
the reactor contents were quickly di~charged into a ~tirred vessel containing 40 1 of ~xxsol 100/110, 1000 g of ~Celite J 100 and al~o 200 cm3 of deionized water at 70C. The mixture was filtered ~o that the filter aid (Celite J 100) was retained and a clear polymer solution - 31 - 2~
was obtained a6 filtrate. The clear olution was precipitated in acetone, ~tirred for 10 minutes, and the suspended polymer solid was then filtered off.

In order to remove residual solvent from the polymer the latter was stirred twice more with acetone and filtered off. Drying was carried ou~ at 50~C under reduced pressure within lS hours.

Yield: 5727 g The physical characteristic~ of the cycloolefin block copolymers are given in Table 3 and in the examples:

2 ~ a 8 Table 3:

. _ - _ __ Cycloolefin- VN ~Mw> ~Mn> cMw> T9 1 Tg 2 block- lc:m3/~] x 10~ x 104 ~Mn~ ~C] ['3C]
copolymer ~g/mol] [g/mol]
_ . _ _ , . _ __ . .
C 1 148,8 11,5 ~,8 ~0 27~8 120,0 C 2 110,9 8.4 4.5 199 25,1 15~8 C 3 122.6 11~2 ~,9 1~9 29,5 107.8 C 4 129,0 ~9 1,9 4~7 ~11.5 15~8 , _ ~ _ --__ VN: Viscosity number determined according to DIN 53728 2~ 3 GPC: <Mw>, ~Mn~; 150-C ALC Millipore Waters Chromatograph Column se~: 4 Scho~ex columns AT-80 M/S
Solven~- o-dichlorobenzene at 135C
Flow xate: 0.5 ml/~in., concentration 0.1 g/dl RI detector, calibration: polyethylene (809 PE) Tg: Glass transition temperature ~tages measured with a dif~erential scanning calorLmeter (DSC-7) from Perkin-Elmer (~berlingen) - heating-up and cooling rate 20 R/minute - and with an automatic torsion pendulum from Brabender (Duisburg) Polyethylene (Bl/B2/B3/B4) The high-density polyethylenes B1, B2, B3 and B4 u~ed can be obtain~d commercially. Bl i5 marketed for example as ~Hostalen GF 476D by Hoech~t AG, Frankfurt am Main. B~ is ~Hostalen GD 4760, B3 i8 ~Hostalen ~M 9240 ~ and B4 is ~Hostalen GURX106 (UHNMPE).

Polypropylene (B5) The isotactic polypropylene B5 used can be obtained commercially and is marketed as ~Hostalen PPH 1050 by Hoechst AG, Frankfurt am Main.

Preparation of the blends The aforede~cribed polymers were fir~t of all dried (115C, 24 hours, reduced pres~ure) and were hen kneaded and extruded in variou~ w~ight ratios in a laboratory compounder (HAAXE ~Karl~ruhe)l 0Rheocord Syxtem 40/
Rheomix 600)) and laboratory extruder (HAAKE (~arlsruhe) Rheocord Sy~tem 90/Rheomox TW 100~) under a shielding gas (Ar). The ground and granulated blends obtained were dried (115C, 24 hours, reduced pres~ure) and were then , . .

- 34 - 2~
either prass molded into ~heets (i20 x 1 mm) (vacuum press: 0Polystat 200 S, 5chwabenthan (Berlin)) or in-~ection molded into moldings ~larg2 dumbbell-shaped test pieces according to ISO/DIS 3167, ~mall ~tandard te~t piece according to DIN 53451) tin~ection molding machine:
~N 90-210 B with ~Microcontrole MC 3, Rraus~ N~ffei (Munich)). ~he resulkant pre~s-molded s~eetfi, dumbbell-shaped test pieces and ~mall ~tandard ~e~t piece~ were investigated as regards their physical propertie~.

The following apparatu~ wa~ used for thi~ purpose:

A differential scanning calorimeter (DSC-7) from Perkin-Elmer (~berlingen) for measuring for ~xample glass transition ~emperature ~tages, melting point6 and heats of fusion.

An automatic torsion pendulum from Brabender (Duisburg) for measuring the shear modulus, damping and linear expansion.

A tensile test machine (type: ~Instron 4302) from Instron (Offenbach).

~ melt flow index test apparatus (MPS-D) fxom Goe~tfert (Buchen) for measuring flowabilities. Melt flow index according to DIN 53735-MVI-B (dead weight/variable temperature; cylider. internal dimension 9.55 ~ 0.01) mm, length at lea~t 115 mm, outlet ~oz~le 2.095 (+/- 0.005) mm, a melting time of 5 minutes being selected.

A hardnes~ tester (type: Zwick 3106) from Zwick (Ulm) for measuring the ball indentation hardne~ses according to DIN ISO 2039.

A pendulum impact tester (type: Zwick 5102) from Zwick (Ulm) for measuring the impact strengths according to 2 ~

DIN 53453.

The hea~ distor~ion temperature (HDT~ was measured according to DIN 53461.

The I~od notched impac~ streng~h wa5 measured according to ISO 180/lA.

Example 1:

The cycloolefin copolymer Al, the polye~hylene Bl and, in some cases, the cycloolefin block copolymer Cl (pha~e mediator) were thoroughly dried and then kneaded together in various weight ratios under an argon atmosphere usin~
the laboratory compounder. ~he following table ~hows the measured thermal properties of the blends.

2~ 3 , _ _ _ _ . _ 5 _ _ _ O ~ _ ~ _ _ ~ O æ t, ~ O_ + _ ' + CU N . N

I ~) o ~ ~ tD ~ ~D CD . . . tD
~ ~ _ __ LL _ C~ C~l ~ ~ r~ _ O ~
~ ~ . ~ c~ c~ . a:~ . c~ ~ o _ __ ~ _ . _ ~ . r~ ~ c~ . 03 . ~ 0 ~ ~ _ _ . _ __ '~ '~
~ o . - ~ ~ . ~ . C~ ~ o _ . ~
O ~ . o . . co a~ ~ . c~ ~ ~ ~

o _ _ ~ ID B -- co _ 8 u~ C ~ ~
_, _ _ . . C~

O ~ g __ 't O ~O __ =__ 5 0,~
+ o .~

- 37 - 2~ 8 Example 2 ~he cycloolefin copolymer A1, the polye~hylene B1 and, in some cases, the cycloolefin block copol~mer Cl (phase mediator) were thorou~hly dried and then kneaded together in various weigh~ ratio~ under an argon atmo~phere using the laboratory compounder, and were then ground. The ground products were used, after having been thoroughly dried, to measure ~he flowabili~ie~, the relevant values being shown in the following table.
~ _ _ _ _ .
COC Al HDPE B1 COC C1 MVI
[% by weight] ~% by weight] [% by weight] 21,6 kg/250C
[cm3/10 min]
¦ 100 _ __ ._ 1,5 10/~ 30,0 34,~
38,4 81,8 18,2/e 23,2 180108 _ 18, Z/e 81 5 30/e 31 ,6 The tests identified with an "e~' are according to the invention, the remainder being comparative tests.

Example 3:

The cycloolefin copolymer A1, the polyethylene B1 and, in some caces, the cycloolefin block copolymer C1 (pha~e mediator) were thoroughly dried and then kneaded together in various weight ratio~ under an argon atmosphere usins the laboratory compounder, and were then ground. ~he 209~a8 ground products were thorougly dried ~nd press-molded into sheets. The following table ~hows the mechanical data of the blend6 that were measured in the tensile test.
_ _ _ _ _ ¦ COC A1 HDPE B1 COC C1 E-Modul Yi~ld S~r~ss elongation at ¦ [wt.-%] [w~.-%] ~ %~ [GPa] [MPa]break [%]
I _ _ .
I1~0 3,5 62 6 ¦45 45 10/e 2,6 52 88 145 55 2,~ 52 21 ¦50 S0 2,6 5~ 11 ¦81,8 1~,2/0 3,4 60 10 I 81,8 18,2/e 1,4 33 550 ¦ 100 1,2 27 660 I . ~ _ 30/e 2,4 46 138 .
E-Modul = Modulus of elasticity The tests identified with an "e" are according to the invention, the xemainder being comparative te~ts.

Example 4:

The cycloolefin copolymer A2, the polyethylene ~1 and, in some cases ~ the cycloolefin block copolymer C2 (phase mediator) were thoroughly dried and then kneaded together in various weight ratios under an argon atmosphere using the laboratory compounder. The following table ~hows the measured thermal properties of the blend~.

- 39 ~ 'a~

__ _... ... _ . =
COC A2 HDPE B1 COC C2 Cooling 2nd Hea~ing [~ %] [u~.-%] [~--%] Tm ¦ dHm Tm ¦ dHm T~ r~ l ¦
HDF 'E B1 HDPE 91 COCA2 COC C2 C] [J/g] ~G] [J/9] [C] l~] [C~
. .. . . 11 100 . . 183 . . ~
42,9 47,1 10 115 99,1* 13491,5 181 + + ¦
42,9 57,1 113 120,3* 136117,4 183 . .
81,1 18,9 182 13 154 82,5 17,5 116 179,4* 136175,1 + +
. ., . _ 11 35,8 44,2 20 115 93,5* 13583,4 181 23 +
35,8 64,2 112 138,8* 140131,3 185 64,2 35,8 180 20 153 . _ ~ ~ _ .
28,7 41,3 30 116 87,8* 134 77,0 182 23 +
28,7 71,3 114 157,5* 136 150,3 182 .
. . . . _ _ _ 100 116 213,1 135 205,3 Heating-up and collingrate: 20 K/min~e Tm and Tg notseparate~
+ not measurable (equipment sensitivity too low) 2~ )58 ~ 40 -Example 5 The cyclo~lefin copolymer A2, the polyethylene Bl and, in some ca~e~, the cycloolefin block copolymer C2 (pha~e media~or) were thoroughly dried and then kneaded togethar in variou6 weight ratios under an argon atmosphere u~ing the l~boratory compounder, and were ~hen ground. ~he ground products were thoroughly dried and used to mea~ure the flowabili~ies, the values of which are given in ~he following table.
. _ _---- e _ _ _ ~ _ [% by w~ight] [% by weight] [% by weight] 21,6 kg/250C
[cm3/10 min]
¦ 100 _ _ _ 11,5 42,9 47,1 10/e 43,5 42,9 57,1 4~,5 81,1 18~9/e 23,5 82,5 17,5/e 57,3 I . _ 35,8 44,? 20/e 42,3 35,~ 64,2 44,6 64,2 35,8/e 38,3 . . _ _ 28,7 41,3 30/e 41,4 28,7 71,3 55,0 _ __ 100 I B1,5 100 98,1 I _ -- _ __ The tests identified with an "e" are acoording to the invention, the remainder being comparative tests.

Example 6:

The cycloolefin copolymer A2, the pole~hylene Bl and, in some cases, the cycloolefin block copolymer C2 (phase - 41 - ~ 8 mediator) were thoroughly dried and ~hen kneaded together in various weight ratios under an argon atmo~p~re u~ing the laboratory compounder, and were then ground. The ground products were thoroughly dried and ~hen pres 8 -molded into sheet~. The following table ~hows the mechanical data o~ the blend~ mea~ured in the tensile test.
. _ - - _ _ .
COC A2 HDPE B1 C;OC C2 E-Modul Yield Stress 010ngation a~
[w~.-%] [wt.-%] [wt.-%] [GPa~ [MPa] break [/O]
. ~
100 . 3,3 58 5 42,947,1 10/e 2,6 52 40 42,957,1 . 2,6 51 9 81,1 18,9/e 3,1 56 7 82,5 17,5/e 0,9 28 448 I _ _ 35,844,2 20/e 2,5 47 101 35,864,2 2,6 48 13 64,2 35,8/e 2,8 53 27 _ . . .
28,741,3 30/e 1,1 31 146 28,771,3 1,5 40 24 _ _ 100 . 1,2 27 658 100 0,4 31 401 _ _ - _ The tests identified with an "e" are according to the invention, the remainder being comparative tests.

2 ~ 5 8 Ex~mple 7:

The cycloolefin oopolymer A2, the polye~hylene Bl and, in some cases, the cycloolefin block copolymer C2 (phase mediator) were thorou~hly dried a~d then kneaded ~oge~her in various weight ratios under an argon atmosphere using the laboratory compounder, and were then ground. The ground products were ~horoughly dried and ~hen press-molded into sheets. The following ~able ~hows the mechanical data of ~he blend measured in the torsion pendulum test.

2 ~ 9 ~- -- . ..
o ; . .
O ~ ~ ~D ~ W
E, æ u~ D I
_ ~) N tD æ ~
_ ~ ~E, O u7 ' (~ z --~

~ --_ ~ _ _ ~
o ~ ~ 3 ~ ~ 0 O ~ N O ~ ~ I~ E

o ~ co I F;
~D tDæ~ o) I c l ~ ~ ~ ~ ~ ~ I O
_ _ .a) ._ , o I 0 U~) ~ o G

_ . ~ O

I ~, ~ I` t~ 8 -"

~ ~ _ _ ,G
, _ .æ E

s ~ ~

Example 80 The cycloolefin copolymer A3, the polyethylene B2 and, in some cases, the cycloolefin block copolymer C3 (phase mediator) were thoroughly dri~d and then extruded together in various weigh~ ratios under an argon atmosphere using a twin-screw extruder, and were ~hen granulated. The following table ~hows the mea~ured thermal properties of the blend~.

2~9~

. _ = _ _ _ 5 l ~) ~ ~. l + . + . O
~ ~o~o ___ _ _ _ I
o ~ V . U~ ., ~_ ~ ~ I
fi ~ m c . N lo I_ N ~

E I ~ ~ c~ l c~ . i~
_ g I N -- ~ N ~- . æ
.~ ~ . ,~ ~
a o , O O , ~r l o c l - - - - - - ~ c ~

IL ~ . ~O . O . C ~ ~ ~
1~ _ __ _ _ lo ~ ~ L ~ L _L æ ~ ~C ~

..

- 46 - 2~ 9 ~5~ 8 Example 9:

The cycloolefin copolymer ~3, the polyethylene B2 and, in some ca~es, the cycloolefin block copolymer C3 (phase mediator) were throughly dried and then extruded together in various weight ratio~ under an ar~on atmosphere UBing a twin-screw extruder, and were then granulated. The granulated material wa~ thoroughly dried and u~ed to measure the flowabilities, the value~ of which are given in the following table.

[wt.-%] [~--%] [wt.-%] 5 k~/270C
~cm3/10 min]
100-- -- - -1,4---10/e 8 7 875 L~L ~s The tests identified witn an "e" are according to the invention, the remainder being comparative tests.

Example 10:

The cycloolefin cop~lymer A3, ~he polye~hylene B2 and, in some cases, the cycloolefin block copolymer C3 ~phase mediator) were thoroughly dried and then extruded in various weight ratios under an argon atmo~phere u~ing a twin-screw extruder, and were then granulated. The granulated material was thoroughly dried and in~ection-molded into large dumbbell-~haped te~t pieces. The following table shows the measured ball indentation 3 ~ ~
hardnesses .

¦ COC A3HDPF B2 COC C3 =
~ %~ [wt.-%] [~-%~ hardness 1~ .[Nl/8Zm~ q ~ 0/e 1 22b 112b 00 l2,5/ ~Sn2~

The tests identified with an "e" ~re according to the invention, the remainder being comparative ~ests. ~est force: ~ 961 N
b 358 N
c 132 N

Example ll:

~he cycloolefin copolymer A3, the polyethylene B~ and, in some cases, the cycloolefin block copolymer C3 (pha e mediator) were thoroughly dried and ~hen extruded together in various weight ratios under an argon atmosphere using a twin-screw extrudert and were then granulated. The granulated material was thoroughly dried and then in~ection-molded into small ~tandard test pieces. ~he following table shows the measured Lmpact ~trengths.

- 48 - `2a~3~
_ COC A3 HDPE ~2 COC C3 impac~ Str0n0ht ~ %] [wt.-%] [~-/~] _._ I
[Jl m] ~kJ~ m2] ¦
25C 60C 25(~ 6~C~
_ _ 100 35,2 35,0 5,9 5,8 10/e 128,4 153,2 21,0 25,2 36,3 33,8 6,0 ~,6 87,5 1 2,5/e78,6 123,3 12,9 20,2 100 o.Br. o.Br. o.Br. o.Br.
. _ _ The tests identified wi~h ~n ~e" are according ~o the invention, the remainder being comparative tests.

Example 12:

The cycloolefin copolymer A5, ~he polyethylene B3, the polyethylene B4 (GUR) and, in some cases, the cycloolefin block copolymer C4 ~phase mediator) were thoroughly dried and then extruded together in ~arious weight ratios under an argon atmosphere using a twin-~crew extruder, and were then granulated. The following table ~hows the measured thermal properties o~ the blends.

_ 49 _ 2~9~

. - 5 - _ C~ O ~ C~~ ~ O- l ~) ~ ~_ ~ ~ _ _ ~ O_~ ~ +,~ U~ ~ ~

O)- _ _ ~
~ ~6 ~ ~ N O~
I o a~ ~. , , ~ _B u~ ~' _ N 1~
I O , u) ~ ~ , ~ N
E ''~ ~ - - ~ "~

.c ~ ", ~ , ~ ~ -- l O O

~ , ~ ~ oo _ n N _~

118 ~ l lo `~ l ~
. _ ___ _ _ ,c~ c i~ _ ~PB ~ g ~ o~
m O . o u, ~ l , o ._ ~

_ _ __ ~ E

0 3~ g _-- T +

Example 13:

~he cycloolefin copolymer ~5, the polyethylene B3, the polyethylene B4 (GUR) and, in some cases, the cycloolefin block copolymer C4 tphase mediator) were thoroughly dried and then extruded in variou~ w igh~ ratios under an argon atmo~phere using a twin-~crew extruder, and were then granulated. The granulated material was thoroughly dried and then in~ection-molded into large dumbbell-shaped test pieces. The following ~able shows ~he measured heat distortion temperatures.
_ _ _ _ - _~
COC A5 HDPE B3 HDPE B4 GUR COC C4 HDT-(A/B) I [wt--%] [wt.-Yo] 1Wt--%] ~ /O] [~] i 100 1S3(A) l - . , _ _ _ I
10/e 159 (B) 157 (B) 33,3 33,3 33,3/e 40 (~) ,.......... l __ ._ 100 tooso~
'- 100 ' I -' ~ ~'--_ _ _ _ ; -~ -100 59 (B) I = _ _ The tests identified with an "e" are according to the invention, the remainder being comparative te~ts.
Example 14:

The cycloolefin copolymer A5, the polyethylene B3, the polyethylene B4 and, in some cases, the cycloolefin block copolymer C4 (pha~e mediator) were thoroughly dried and then extruded together in various weight ratios under an 2 ~ 3~ ~
argon atmosphere using a twin-screw e~truder, and were then granulated. The granulated material wa~ ~horoughly dried and then injec~ion-molded into large dumbbell-~haped test piece~. The followiny table ~hows the measured notched impact ~rength _ _ 7 _ _ _-COC A5 HDPE B3HDPE B4 GUR C;OC C4 Izod-notched impact [W~.-/C~] ~ _G/o] [% by weight] ~ %~ Strength [~3/m]
_ _ . . _ _ ¦ 100 _ 18 10/e 36 33,3 33,3 33,3/e 480 I _ _ . ~ _ I
100o.Br.
I .
1 Oû o.Br.
I _~ .

~ . _ _, = _ _ OBr.: without fracture The tests identi~ied with an "e~' are according to the invention, the remainder being comparative tests.

Example 15:
The cycloolefin copolymer A4, the polypropylene B5 and, in some cases, the cycloolefin block copolymer C4 (phase mediator) were thoroughly dried and then extruded together in various weight ratios under an argon atmosphere using a twin-~crew extruder, and were then granulated. The following table shows the measured thermal properties of the blend6.

~ ~ ~J ~ ~ ~

__ _ 5 5 _- _ ~ ~ . o~ a, o, O~D . ~,, o, .~, o, o. . _ O O . +, . +, +, +. n . o) , ~D +

o) _ - _ _ _ __ _ :~c: ~0 _ ~ 0,0,~,O, . ~ 0,0, ,~0-O, C~l _ 9 -o - o _.o o o o ~ ~D 1~ ~ C~
--~ l N , ~ ~ . O
I m ~ N C~ '~ ~
'. .~ --o o o o U~ U~
~ O . ~ Q) ' O 0~ l ~t) ~
_ . _ ~1 ~ 0 0 O~ 't U~ CO ~
O~ . I~ ~ ~ . u~ - ~ -._ _ a, $ ~C ~ m o .~ ~ ~ o~ ~ u~ 0 o ~ ~ ~ m ~, E l o . o u~ l ~a~ ~ ~ ~ -- ~' E E
_ ~ Cl- C
~; ~ . o,")-~o 8 . o,~-~o ~CD,u,D, _ _. ,, .
m ~ . O O ~ æ o o o ~- , o ~ E
~ ~ C~
_ _ _ _ ~ ~:
~ ' lo I~ o~ E ~ ~tci+l o~

- 53 - ~ 3`~

~xample 16:

~he cycloolefin copolymer A4, the pol~propylene B5 and, in some ca~e~, the cycloolef~n block ~opolymer C4 (pha~e mediator) were thoroughly dried and then extruded toge~her in variou~ weight ratios under an argon atmosphere using a twin-screw extruder and were then granulated. The gr~nulated materisl was thoroughly dried and used to mea~ure the ~lowabili~ie~, the ~alues of 1~ which are given in the following table.
_ _ . __ COC A4 iPP B5 COC C4MVI
[wt.-%] [wt.-%] [wt.-%] [ccm/10 min]
¦ 100 1,B
__ ~

~ ~10 10/e . . _ I _ _ _ _ _ e ¦~ 75 14,3 e 1 13 I . _ _ _ 10/85,6 ~0 ~ ~-_ . ___ _ 10/e 11 14,3/e 4 5 I _ _ 10/e 12 l _ -- .__ ~ 5 4 ~

Tempera~ure and loading weight: 230~C/lO kg The tests identified with an ~e" ~re according to khe invention, the remainder being compaxative te~ts.

Example 17:

The cycloolefin copolymer A4, the polypropylene ~5 and, in some cases, the cycloolefin block copolymer C4 (phase mediator) were thoroughly dried and then extruded together in various weight ratios in an argon atmo~phere using a twin-screw extruder and were then granulated. The granulated material was thoroughly dxied and then pres~-molded into sheets. The following ~able shows the mechanical data of the blends measured in the torsion pendulum tes~.

The tests identified with an "e" are according to the invention~ the remainder being comparative tests~

.

_ 55_ 2~

_ _ = _ = = - 5 _ _ ~t tt) N , a~ t~ O) _ 1-) U7 ~ ~ O) C
O o r` ~ N ~_ ~ _ .- N N N 1~3 ID

E N tD N1~ 't C'~ _ N N ~; ~ ~ N

CL _ C~ C~ a)~; ,_ ~;t , t~ c~ tD __ CD ~

E ~ N O) O _ ~ N _ .~ O tO O ~g O
_ E N N ~O ~ ~ O . ~ ~!; O ~ ~ O
~ co _ _ æ O O _ N æ N ~ ~ _ _ O _ _ _ _ ~D O O N _ N _ _ _ o o a) 8 _ N _ N N 6 8 N _ N

I _ _ ~. . O _ ~ N O _ _ ~ -- N O
_ r-m :~ . o o . ~ ~ . 8 CD c, . o ._ _. I~ - - ---1~ ~L~

- 56 - 2 ~ fi~ 4'3 a -~

~xample 18J

The cycloolefin copo~ymer ~4, the polypropylene BS and, in some cases, the cycloolefin block copolymer C4 (pha~e mediator) were ~horoughly dried and then e~truded together in various weight ratios under an argon atmosphere using a twin-~crew extxuder and w~re then granulated. ~he granulated mat~rial was thoroughly ~ried and then injection-molded into lar~e dumbbell-shaped test 1o pieces. The following table show~ the mea~ured I~od notched impact ~trengths and elongations at break.
_ _ . _ _ ¦ COC A4iPP B5 COC C4 Izod no~ched elonga~ion mpaGt ~trength at break ¦ [w~.-%][wt.-%] ~ %] [J/m] [IJ/m2] 1%]
! __ ¦ 100 17 2,1 3,6 l _. _ _ ¦ 60 30 10/e 30 3,8 24 _ . _ ~. _ ~,9 3,~
l _ ¦ 85,7 14,3/e 35 4,4 31 l _ -_ ._ _ I 75 25/e n.g. n.g. 362 l _ _. __ _ 10/e 19 2,4 4,6 I __ ~ _ _ 100 o.Br. o.Br. >75 l _ _ .
100 65 8,1 500 I _ _ 10/e 26 3,2 20 I _ _ _ _._ _ ._ .
23 2,9 8,8 I _ _ _, 85,7 14,3/e 41~ 52 52 . I ._ _ . 75 25/e 48 6,0 ~1 _ _ __ 10/e 49 6,2 51 _ ___ ==_, ~

~ 57 ~ '3,~
*

measured on press-molded sheets n.g. not measured o.Br. wit~out fracture The tests identified wit~ an "e" are according to the invention, t~e remainder being comparatlve tests.

Claims (12)

1. A process for preparing a polymer blend by combining finely particulate cycloolefin polymers and finely particulate polyolefins and processing the mixture at elevated temperature and under the action of shear forces into a polymer blend, wherein in order to prepare the block copolymers from 0.1 to 95 % by weight, based on the total amount of the monomers, of at least one monomer of the formulae I, II, III, IV, V or VI

(I), (II), (III).

(IV), (V), (VI), where R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different and are a hydrogen atom or a C1-C8-alkyl radical, the same radicals in the various formulae being able to be different, and from 0 to 95 % by weight based on the total amount of the monomers, of a cycloolefin of the formula VII

(VII) where n is a number from 2 to 10, and from 0 to 99 % by weight, based on the total amount of the monomers, of at least one acyclic olefin of the formula VIII

(VIII), where R9, R10, R11 and R12 are the same or different and are a hydrogen atom or a C1-C8-alkyl radical, are polymerized at temperatures of from -78 to 150°C and at a pressure of from 0.01 to 64 bar, in the pres-ence of a catalyst comprising a cocatalyst and a metallocene, and the reaction conditions are changed one or more times at a molecular weight distribution MwMn of less than 2, of the block polymer that is being formed, in such a way that the monomer-co-monomer ratio changes by at least 10 %, or a further polymerizable monomer of the formulae I - VIII is metered into the monomer or monomers, the block polymer obtained is separated, from 0.1 to 99 parts by weight of at least one block copolymer, from 0 to 95 parts by weight of finely particulate polyolefin or polyolefins and from 0 to 95 parts by weight of a finely particulate cycloolefin polymer or polymers which comprises or comprise at least one of the monomers I, II, III, IV, V, VI or VII and also at least one acyclic olefin VIII but is or are not a block copolymer, are combined, the sum of the polymers totalling 100 parts by weight, additives are incorporated if desired, the components are mixed together, and the mixture is processed at elevated temperature under the action of shear forces into a polymer blend.

2. The process as claimed in claim 1, wherein at least one finely particulate aliphatic poly-1-olefin is used as polyolefin.

3. The process as claimed in claim 2, wherein at least one finely particulate polyethylene is used as polyolefin.

4. 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.

5. The process as claimed in claim 2, wherein a weight ratio of polyolefin or polyol fins to block co-polymer or block copolymers of at least 1:1 is maintained.

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

7. The process as claimed in claim 3, wherein HDPE is used as polyethylene.

8. The process as claimed in claim 1, wherein in the polymerization a metallocene of the formula XI is used (XI) 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-axylalkenyl 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 = BR19, = A1R19, -Ge-, -Sn-, -O-, -S-, = SO, = SO2, = NR19, = CO, = PR19, or = P(O)R19, where R10, 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-axylalkyl 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.

9. A polymer blend obtainable according to the process as claimed in claim 1.

10. The use of the polymer blend according to claim 9 as a matrix material for composites or for the produc-tion of moldings.

11. The process as claimed in claim 2, wherein at least one finely particulate polypropylene is used as finely particulate polyolefin.

12. The process as claimed in claim 11, wherein finely particulate isotactic polypropylene is used as finely particulate polypropylene.