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 C.sub.n H.sub.2n and/or aliphatic 1-olefin, such as ethylene or propylene, are mixed and the mixture is processed under heat and shear forces. The block copolymer acts as phase mediator and contains in different blocks different proportions of the monomer units used.

Cycloolefin polymers are a class of polymers with an outstanding property 
spectrum, having in some cases, inter alia, good heat resistance, 
transparency, hydrolytic stability, low water uptake, good weathering 
resistance and high rigidity. They are hard, brittle thermoplastics. 
It is known that cycloolefins can be polymerized by means of various 
catalysts. Depending on the catalyst, the polymerization proceeds via ring 
opening (U.S. Pat. No. 3,557,072, U.S. Pat. No. 4,178,424) or with 
scission 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 insufficiently resistant to impact and shock 
stress. It is generally known that the resistance to shock and impact 
stress is good in the case of polyolefins such as polyethylene, 
polypropylene and 1-polybutene. However, these polyolefins have a limited 
heat resistance, low strength, a low modulus and low hardness. 
It is known that 1-olefins such as ethylene and propylene can be 
polymerized by means of various catalysts to form polyolefins, in 
particular polyethylenes and polypropylenes (DE 3 620 060, EP 399 348, EP 
086 644, EP 185 918, EP 387 690). 
Polyethylene can also be prepared by free-radical polymerization (U.S. Pat. 
No. 3,336,281). The resultant product is a low density material (LDPE), 
compared to the material that has been catalytically prepared, which is of 
high to medium density (HDPE, MDPE). The same is true of copolymers of 
ethylene with 1-olefins (LLDPE). 
It is generally known that important properties of polymers, such as the 
aforementioned properties, can be modified if polymers are blended with 
other polymers. For instance, the patent specifications DD 214 137 and DD 
214 623 describe thermoplastic structural materials based on polyolefins 
that simultaneously have a good heat resistance, resistance to chemicals, 
rigidity, toughness and very good dielectric properties. They contain as 
essential constituents norbornene-ethylene copolymers and polyethylene or 
branched polyolefins, if necessary with the addition of stabilizers, 
lubricants, elastomers, thermoplastics and reinforcing agents. Elastomers 
such as elastomeric ethylene copolymers and terpolymers or graft 
copolymers are added to improve the impact strength and notched impact 
strength. However, block-type copolymers or terpolymers of ethylene or 
1-olefins and cycloolefins are not mentioned as elastomers. 
According to the above documents additions of polyethylene or branched 
polyolefins to ethylene-norbornene copolymers lead to an improvement in 
the resistance to chemicals and toughness of the norbornene-ethylene 
copolymers. Conversely, the addition of norbornene-ethylene copolymers to 
polyethylene or branched polyolefins led to an increase in the strength, 
modulus and hardness, without resulting in any decrease in the impact 
flexural strength. 
Furthermore, it is known that polyolefin thermoplastic combinations of 40 
to 98% by weight of crystalline polyolefin and 2 to 60% by weight of a 
random cyclic olefinic copolymer (glass transition temperature 70.degree. 
to 210.degree. C., crystallinity 0 to 5%) have a good heat resistance and 
crack resistance combined with low shrinkage (JP 1 318 052). According to 
Japanese Patent Application JP 3 122 148 cycloolefin polymer combinations 
of polymers of the cyclic olefin and crystalline polyolefins have an 
improved melt processability. 
U.S. Pat. No. 4,990,559 describes a thermoplastic combination of 5 to 90% 
by weight of linear polyolefin (comprising 8 to 40% of ultrahigh molecular 
weight polyolefin (.eta. 10 to 40 dl/g) and 60 to 92% by weight of low to 
high molecular weight polyolefin (.eta. 0.1 to 5.0 dl/g)) and 95 to 10% by 
weight of at least one cycloolefin thermoplastic selected from 
ring-opening polymers and ring-opening copolymers. 
A blending of cycloolefin copolymers with polyolefins such as polyethylene, 
polypropylene, 1-polybutene, 1-polyhexene, poly(4-methyl-1-pentene), inter 
alia, is attractive since such polyolefins are relatively cheap and the 
corresponding blends then also offer cost advantages. It is then important 
to achieve as favorable a property combination as possible in the blend, 
utilizing the cost advantages. Such blends are mainly suitable for 
applications where good material properties are required. 
It is an object of the present invention to provide a process in which, 
starting from favorable combinations of cycloolefin polymers, polyolefins 
and additives, polymer blends are obtained having as broad a range of 
material properties as possible, in particular strength, hardness, heat 
resistance and toughness. 
It is also an object of the present invention to obtain, starting from the 
individual components, i.e. polyolefins or cycloolefin polymers (including 
cycloolefin copolymers), by means of additions blends having good material 
properties. 
This invention provides a process for preparing a polymer blend comprising 
(i) combining at least one of (A) a finely particulate cycloolefin 
polymer, and (B) a finely particulate polyolefin, with (C) at least one 
block copolymer, to form a mixture; and (ii) processing the mixture at an 
elevated temperature, under the action of shear forces, to form the 
polymer blend, wherein: 
in the polymer blend, (A) is present in an amount of 0 to 95 parts by 
weight, (B) is present in an amount of 0 to 95 parts by weight, (C) is 
present in an amount of 0.1 to 99 parts by weight and, the sum of the 
amounts of (A), (B) and (C) present is 100 parts by weight; 
the finely particulate cycloolefin polymer (A) comprises at least one 
monomer of formula I, II, III, IV, V and VI and at least one monomer of 
formula VII and VIII, but said cycloolefin polymer is not a block 
copolymer; 
the block copolymer (C) is obtained by polymerizing: 
a) 0.1 to 95% by weight, with respect to the total amount of monomers 
employed, of at least one monomer of the formula I, II, III, IV, V and VI, 
b) 0 to 95% by weight, with respect to the total amount of monomers 
employed, of a cycloolefin of the formula VII,, and 
c) 0 to 99% by weight, with respect to the total amount of monomers 
employed, of at least one acyclic olefin of the formula VIII, 
at a temperature of -78.degree. to 150.degree. C. and a pressure 0.01 to 64 
bar, in the presence of a catalyst comprising a cocatalyst and a 
metallocene, and at a molecular weight distribution M.sub.w /M.sub.n of 
less than 2, always with respect to the polymer block forming, the 
reaction conditions are changed one or more times in such a way that the 
monomer/comonomer ratio changes by at least 10% or a further polymerizable 
monomer of the formulae I-VIII is metered into the monomer or the 
monomers; and 
the monomers of the formula I, II, III, IV, V, VI, VII and VIII are: 
##STR1## 
in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, 
R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are identical or 
different and are a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical and 
n is a number from 2 to 10. 
The catalyst may preferably comprise an aluminoxane of the formula (IX) 
##STR2## 
for the linear type and/or of the formula (X) 
##STR3## 
for the cyclic type, where, in the formulae (IX) and (X), the radicals 
R.sup.13 are identical or different and are a C.sub.1 -C.sub.6 -alkyl 
group, a C.sub.6 -C.sub.18 -aryl group, benzyl or hydrogen, and p is an 
integer from 2 to 50, and a metallocene of the formula XI in which 
M.sup.1 is titanium, zirconium, hafnium, vanadium, nioblum or tantalum, 
R.sup.14 and R.sup.15 are identical or different and are a hydrogen atom, a 
halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.6 -C.sub.10 
-alkoxy group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 
-aryloxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 
-arylalkyl group, a C.sub.7 -C.sub.40 -alkyl aryl group or a C.sub.8 
-C.sub.40 -arylalkenyl group, 
R.sup.16 and R.sup.17 are a mononuclear or polynuclear hydrocarbon radical 
which can form a sandwich structure with the central atom M.sup.1, 
R.sup.18 is 
##STR4## 
.dbd.BR.sup.19, .dbd.AIR.sup.19 --Ge--, --Sn--, --O--, --S--, .dbd.SO, 
.dbd.SO.sub.2, .dbd.NR.sup.19, .dbd.CO, .dbd.PR.sup.19 or P(O)R.sup.19, 
where R.sup.19, R.sup.20 and R.sup.21 are identical or different and are a 
hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 
-C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.1 
-C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 
-C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or a 
C.sub.7 -C.sub.40 -alkylaryl group, or R.sup.19 and R.sup.20, or R.sup.19 
and R.sup.21, form a ring, in each case together with the atoms linking 
them, and M.sup.2 is silicon, germanium or tin. 
The polyolefins used are derived from open-chain non-cyclic olefins, for 
example from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 
isobutylene, isoprene or butadiene. In addition to polyisoprene and 
polybutadiene, there may also be used elastomeric butadiene copolymers and 
terpolymers and/or their graft copolymers, and also elastomeric polyolefin 
copolymers and terpolymers and/or their graft copolymers. The polyolefins 
are preferably derived from 1-olefins, styrenes and/or their copolymers 
and terpolymers and also graft copolymers also falling under this 
classification. Preferred polyolefins comprise aliphatic 1-olefins, in 
particular those having 2 to 8 carbon atoms, for example ethylene, 
propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. 
Particularly preferred are 1-olefins having 2 to 6 carbon atoms, such as 
ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. 
Polyolefins that can be used include in particular also copolymers and 
terpolymers of various 1-olefins, which may also comprise cyclic olefins, 
for example of ethylene, propylene, hexadiene, dicyclopentadiene and 
ethylidene norbornene. Particularly preferred polyolefins are polyethylene 
and polypropylene. 
A process for the preparation of a suitable finely particulate block 
copolymer is the subject of U.S. patent application Ser. No. 19,094 filed 
on Feb. 18, 1993 which corresponds to the non-prior-published German 
Patent Application P 42 05 416.8, incorporated herein by reference. The 
block copolymers described there, which are included as additives in the 
blends prepared according to the invention, comprise at least two blocks 
with different amounts of olefins, one olefin being a cycloolefin C.sub.n 
H.sub.2n-2 were n=4 to 13 or an acyclic olefin. Corresponding homopolymers 
may also occur as impurities in the block copolymers. In general, 
different blocks of a block copolymer also have different glass transition 
temperatures. In the case of two-block copolymers the block with the low 
glass transition temperature is termed the "soft block", and the block 
with the higher glass transition temperature is termed the "hard block". 
Surprisingly, the polymer blends with these block co-polymers prepared by 
the process according to the invention have outstanding mechanical 
properties. Their toughness is in all cases better than that of pure 
cycloolefin polymers, and their strength, hardness and modulus are in some 
cases 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 invention have an improved melt 
viscosity, 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 parts 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 sum of 
(A)+(B)+(C) being 100 parts by weight. Furthermore, additives known per 
se, for example fillers or dyes, can be incorporated. 
For the blends according to the invention suitable cycloolefin polymers (A) 
comprise structural units that are derived from at least one monomer of 
the formulae I to VII 
##STR5## 
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and 
R.sup.8 are the same or different and are a hydrogen atom or a C.sub.1 
-C.sub.8 -alkyl radical, the same radicals in the various formulae being 
able to be different, and n is an integer from 2 to 10. 
The cycloolefin polymers (A) may comprise, in addition to the structural 
units that are derived from at least one monomer of the formulae I to VII, 
further structural units that are derived from at least one acyclic 
1-olefin of the formula (VIII) 
##STR6## 
where R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are the same or different 
and are a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical. 
Preferred comonomers are ethylene or propylene. In particular copolymers of 
polycyclic olefins of the formulae I or III, and the acyclic olefins of 
the formula VIII, are used. Particularly preferred cycloolefins are 
norbornene and tetracyclododecene, which may be substituted by C.sub.1 
-C.sub.6 -alkyl, ethylene-norbornene copolymers being particularly 
important. Of the monocyclic olefins of the formula VII, preference is 
given to cyclopentene, which may be substituted. Polycyclic olefins, 
monocyclic olefins and open-chain olefins are understood to include also 
mixtures of two or more olefins of the respective type. This means that 
cycloolefin homopolymers and copolymers such as bipolymers, terpolymers 
and multipolymers can be used. 
The cycloolefin polymerizations proceeding with scission of the double bond 
may be catalyzed using more novel catalyst systems (EP-A-0 407 870, EP-A-0 
203 799), and also with a conventional Ziegler catalyst system (DD-A-222 
317). 
Cycloolefin homopolymers and copolymers that comprise 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, 
whose central atom is a metal from the group titanium, zirconium, 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 
(cf. J. Organomet. Chem. 288 (1985) 63-67, EP-A-387 690). The aluminoxane 
acting as co-catalyst can be obtained by various methods (cf. S. 
Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-302 424). The structure and 
also the polymerization of these cycloolefins is 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. These 
compounds are cycloolefin copolymers that differ as regards their chemical 
uniformity and their polydispersity. 
Preferably cycloolefin polymers are used having a viscosity number greater 
than 20 cm.sup.3 /g (measured in decalin at 135.degree. C. in a 
concentration of 0.1 g/100 ml) and a glass transition temperature (Tg) of 
from 100.degree. to 240.degree. C. 
The blends may also comprise cycloolefin polymers that have been 
polymerized with ring opening in the presence of, for example, tungsten-, 
molybdenum-, rhodium- or rhenium-containing catalysts. The resultant 
cycloolefin polymers have double bonds that can be removed by 
hydrogenation (U.S. Pat. No. 3,557,072 and U.S. Pat. No. 4,178,424). 
The cycloolefin block copolymers (C) contained in the blends prepared 
according to the invention are formed from a monomer mixture comprising 
one or more cycloolefins of the formulae I to VI, in particular formulae I 
or III, and at least one olefin selected from the group of cycloolefins of 
the formula VII and the acyclic olefins of the formula VIII. 
Preference is given to those compounds of the formulae I and III in which 
the radicals R.sup.1 to R.sup.6 are hydrogen or a C.sub.1 -C.sub.6 -alkyl 
radical, and compounds of the formula VIII in which R.sup.9, R.sup.10 and 
R.sup.11 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 copolymer, from 0.1 to 95% by weight, based 
on the total amount of the monomers used, of at least one monomer of the 
formulae I, II, III, IV, V or VI 
##STR7## 
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and 
R.sup.8 are the same or different and are a hydrogen atom or a C.sub.1 
-C.sub.8 -alkyl radical, the same radicals in the various formulae being 
able to be different, from 0 to 95% by weight, based on the total amount 
of the monomers used, of a cycloolefin of the formula VII 
##STR8## 
where n is a number from 2 to 10, and from 0 to 99% by weight, based on 
the total amount of the monomers used, of at least one acyclic olefin of 
the formula VIII 
##STR9## 
where R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are the same or different 
and are a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical, are 
polymerized at temperatures of from -78.degree. to 150.degree. C. and at a 
pressure of from 0.01 to 64 bar, in the presence of a catalyst comprising 
a cocatalyst and a metallocene of the formula XI 
##STR10## 
where M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or 
tantalum, 
R.sup.14 and R.sup.15 are the same or different and are a hydrogen atom, a 
halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 -C.sub.10 
-alkoxy group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 
-aryloxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 
-arylalky group, a C.sub.7 -C.sub.40 -alkylaryl group or a C.sub.8 
-C.sub.40 -arylalkenyl group, 
R.sup.16 and R.sup.17 are a mononuclear or polynuclear hydrocarbon radical 
which together with the central atom M.sup.1 can form a sandwich structure 
R.sup.18 is 
##STR11## 
.dbd.BR.sup.19, .dbd.AIR.sup.19 --Ge--, --Sn--, --O--, --S--, .dbd.SO, 
.dbd.SO.sub.2, .dbd.NR.sup.19, .dbd.CO, .dbd.PR.sup.19, or P(O)R.sup.19, 
where R.sup.19, R.sup.20 and R.sup.21, are the same or different and a 
hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 
-C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a 
C.sub.6 -C.sub.10 -aryl group, a C.sub.1 -C.sub.10 -alkoxy group, a 
C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a 
C.sub.8 -C.sub.40 -arylalkenyl group or a C.sub.7 -C.sub.40 -alkylaryl 
group, or R.sup.19 and R.sup.20 or R.sup.19 and R.sup.21 in each case form 
a ring with the atoms that connect them, and 
M.sup.2 is silicon, germanium or tin. The reaction conditions are changed - 
always at a molecular weight distribution M.sub.w /M.sub.n of less than 2, 
always based on the polymer block that is being formed--in such a way that 
the monomer-comonomer ratio changes by at least 10%, or a further 
polymerizable monomer of the formulae I-VIII is metered into the monomer 
or monomers. 
The polymerization is carried out in such a way that a two-stage or 
multistage polymerization takes place according to the number of changes 
in the parameters that are made or according to the monomer composition, a 
homopolymer sequence of one of the monomers of the formulae I to VIII also 
being able to be polymerized in the first polymerization stage. Alkyl is 
straight-chain or branched alkyl. The monocyclic olefin VII may also be 
substituted (e.g. by alkyl or aryl radicals). 
The polymerization takes place in dilute solution (&lt;80% by vol. of 
cycloolefin), in concentrated solution (&gt;80% by vol. of cycloolefin), or 
directly in the liquid, undiluted cycloolefin monomer. 
The temperature and reaction time must be suitably matched depending on the 
activity of the catalyst, the desired molecular weight and desired 
molecular weight distribution of the respective polymer block. Also, the 
concentration of the monomers and also the nature of the solvent must be 
taken into account, especially as these parameters basically determine the 
relative incorporation rates of the monomers and are thus decisive for the 
glass transition temperature and heat resistance of the polymers. 
The lower the polymerization temperature is chosen within the range from 
-78.degree. to 150.degree. C., preferably from -78.degree. to 80.degree. 
C. and particularly preferably from 20.degree. to 80.degree. C., the 
longer the polymerization duration can be, with almost the same breadth of 
molecular weight distribution M.sub.w /M.sub.n for the respective polymer 
blocks. 
If the sudden change in the reaction conditions is effected at a point in 
time in which the molecular weight distribution M.sub.w /M.sub.n of the 
forming polymer block is equal to 1, then it can be assumed with certainty 
that all polymer blocks formed in this polymerization 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 is 100% for this extreme case. The 
more the molecular weight distribution M.sub.w /M.sub.n of the polymer 
blocks formed in a polymerization stage deviates from 1, i.e. M.sub.w 
/M.sub.n &gt;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 preparing block copolymers this means that the more the 
value M.sub.w /M.sub.n of the polymer block X prepared in the 
polymerization stage X is 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 becomes 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 
copolymers, this means that the time windows for the individual 
polymerization stages shall as far as possible be chosen so that they 
correspond to a M.sub.w /M.sub.n 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 so 
that chemically uniform polymer blocks are formed. It is 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 types of monomers, this 
gradient can be achieved by continuously changing the concentration of a 
single monomer component. 
Blocks with structural gradients can also be produced in those 
polymerization stages in which the concentration of several monomer 
components is simultaneously continuously changed. 
The changes to be made in the monomer ratios can be achieved for example by 
changing the pressure of the acyclic olefin, by changing the temperature 
and thus the solubility of gaseous olefins, by dilution with solvents at 
constant pressure of the acyclic olefin or also by metering in a liquid 
monomer. Furthermore, several of the aforementioned parameters can be 
simultaneously altered. 
Such sudden and also continuous changes in the monomer ratio--and thus the 
preparation of block copolymers--can be effected not only under batchwise 
control of the reaction but also under continuous control of the reaction. 
Continuous and also multistage polymerization processes are particularly 
advantageous since they permit an economically favorable use of the 
cycloolefin. Also, in continuous processes 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 via 
the throughput and reaction volume of the different reaction vessels (i.e. 
these two quantities determine the residence time at the different 
reaction locations). 
Preferred cycloolefin block copolymers that may be mentioned for the blends 
are norbornene/ethylene block copolymers, norbornene/ethylene/propylene 
block copolymers, dimethanooctahydronaphthalene 
(tetracyclododecene)/ethylene block copolymers, 
dimethanooctahydronaphthalene/ethylene/propylene block copolymers and 
block copolymers in which each polymer sequence or polymer block is built 
up from a copolymer, i.e. a bipolymer, terpolymer or multipolymer, and 
also norbornene or dimethanooctahydronaphthalene has been incorporated in 
at least one polymerization stage. The particularly preferred 
norbornene/ethylene block copolymers, norbornene/ethylene/propylene block 
copolymers and corresponding dimethanooctahydronaphthalene block 
copolymers are built up from norbornene/ethylene, 
norbornene/ethylene/propylene copolymer sequences or corresponding 
dimethanooctahydronaphthalene copolymer sequences of different 
composition, i.e they comprise blocks (polymer segments) that in each case 
are norbornene/ethylene copolymers, norbornene/ethylene/propylene 
terpolymers or corresponding dimethanooctahydronaphthalene copolymers or 
terpolymers. 
The cycloolefin block copolymers prepared according to the described 
process can for the purposes of the present invention 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 size of the particles 
(disperse phase) in the blend. Compatibilization polymers is generally 
more successful the greater the structural similarities 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 cycloolefin block copolymers that comprise, as 
predominantly incorporated monomer component or components in the blocks, 
those that are also contained as monomer component or components in the 
polymers to be compatibilized. If the polyolefin (B) is polyethylene, then 
preferably the block copolymer (C) should comprise at least one block 
predominantly of ethylene units and at least one block predominantly of 
cycloolefin units, in particular those that are present in the cycloolefin 
copolymer (A). The same also applies to polypropylene. The blends 
containing phase mediators generally have dramatically improved mechanical 
properties. Also, they can stabilize the phase structures by preventing 
coalescence. 
The polyolefins (B) used in the blends are derived from open-chain 
noncyclic olefins, for example from ethylene, propylene, 1-butene, 
1-hexene, 4-methyl-1-pentene, isobutylene, isoprene or butadiene. In 
addition to polyisoprene and polybutadiene, there may also be used 
elastomeric butadiene copolymers and terpolymers and/or their graft 
copolymers, and also elastomeric polyolefin copolymers and terpolymers 
and/or their graft copolymers. The polyolefins are preferably derived from 
1-olefins, styrenes and/or their copolymers and terpolymers and also graft 
copolymers being included in this classification. Preferred polyolefins 
comprise aliphatic 1-olefins, in particular those having 2 to 8 carbon 
atoms, for example ethylene, propylene, 1-butene, 1-hexene, 
4-methyl-1-pentene and 1-octene. 
Polyolefins that can be used include in particular also copolymers and 
terpolymers of various 1-olefins, which may also comprise cyclic olefins, 
for example of ethylene, propylene, hexadiene, dicyclopentadiene and 
ethylidene norbornene. 
The polyethylenes (B) preferably used in the blends are high density (HDPE) 
polyethylene and medium density (MDPE) polyethylene. Such polyethylenes 
are prepared by the low-pressure process using suitable catalysts. 
Characterizing properties are: low density compared to other plastics 
(&lt;0.96 g/cm.sup.3), high toughness and elongation at break, very good 
electrical and dielectric properties, very good resistance to chemicals, 
and, depending on the type, good resistance to stress crack formation and 
good processability and machinability. 
Polyethylene molecules contain branchings. The degree of branching of the 
molecular chains and the length of the side chains substantially influence 
the properties of the polyethylene. The HDPE and MDPE types are slightly 
branched and have only short side chains. 
Polyethylene crystallizes from the melt on cooling: the long molecular 
chains arrange themselves in a folded manner in domains and form very 
small crystallites, which are joined together with amorphous zones to form 
superlattices, i.e. spherulites. The crystallization is increasingly 
possible the shorter the chains and the less the degree of branching. The 
crystalline fraction has a higher density than the amorphous fraction. 
Different densities are therefore obtained, depending on the crystalline 
fraction. This degree of crystallization is 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/cm.sup.3 to 0.965 g/cm.sup.3 ; medium 
density polyethylene (MDPE) reaches a degree of crystallization of 50 to 
60% at a density of from 0.930 g/cm.sup.3 to 0.940 g/cm.sup.3. 
The properties of polyethylene are largely determined by density, molecular 
weight and molecular weight distribution. For example, the impact strength 
and notched impact strength, tear strength, elongation at break and 
resistance to stress crack formation increase with the molecular weight. 
HDPE with a narrow molecular weight distribution and having a small low 
molecular weight fraction is more impact resistant, even at low 
temperatures, than HDPE having a broad molecular weight distribution, 
within the same ranges for the melt flow index and viscosity number. Types 
having a broad molecular weight distribution are in turn more easily 
processable. 
The higher the molecular weight of polyethylene, the more difficult it 
becomes to prepare blends by means of extruders. Whereas a polyethylene 
with a mean molecular weight of about 4.9.times.10.sup.+5 g/mol can just 
be used as a single polyethylene component, polyethylene types having for 
example molecular weights of between 0.5 and 8.times.10.sup.6 g/mol can be 
processed by means of extrusion or injection molding only in blended form, 
i.e. as a blend according to the invention with correspondingly increasing 
contents of components A and C. In order to optimize the processability of 
such blends while largely retaining the mechanical properties, in addition 
to high molecular weight polyethylene HDPE (0.1-0.5.times.10.sup.6 g/mol) 
may also be incorporated as part of the component B into the blends 
according to the invention. These ultrahigh molecular weight low-pressure 
polyethylenes (UHMWPE) may specifically also be constituents of the 
polymer blends. 
Polypropylene is an isotactic, syndiotactic or atactic polypropylene 
prepared using stereospecifically acting 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, has the 
properties of a technically usable material. 
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 comprise 
non-isotactic fractions and thus do not comprise crystallizable fractions. 
Furthermore, amorphous regions are formed due to the convolutions of the 
chains in the melt, particularly at a high degree of polymerization. The 
crystalline fraction depends on the production conditions of the molded 
parts and is from 50% to 70%. The partly crystalline structure imparts a 
certain strength and rigidity on account of the strong secondary forces in 
the crystallite, whereas the unordered regions with the higher mobility 
impart flexibility and toughness to their chain segments above the glass 
transition temperature. 
The proportion of cycloolefin polymers (A) in the blends according to the 
invention is preferably from 0 to 90% by weight and particularly 
preferably from 0 to 85% by weight, and the proportion of polyolefins (B) 
in the blends prepared according to the invention is preferably at most 
90% by weight and particularly preferably at most 85% by weight. The 
proportion of the cycloolefin block copolymers is 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 the invention may comprise one or more 
cycloolefin polymers, one or more polyolefins, in particular polyethylenes 
or polypropylenes, 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 stabilizers, UV stabilizers, antistats, flameproofing 
agents, plasticizers lubricants, pigments, dyes, optical brighteners, 
processing auxiliaries, inorganic and organic fillers, i.e. in particular 
also reinforcing materials such as glass fibers, carbon fibers or 
high-modulus fibers. The blends may be used particularly advantageously 
for the production of moldings by the compression molding, injection 
molding or extrusion processes. Examples of moldings include sheets, 
fibers, films and hoses. 
The following polymers were prepared by standard methods: cycloolefin 
copolymers A1 [COC A1], A2 [COC A2], A3[COC A3]and A4[COC A4] 
Preparation of COC A1 
A clean and dry 75 dm.sup.3 capacity polymerization reactor equipped with a 
stirrer was flushed with nitrogen and then with ethylene. 20550 g of 
norbornene melt (Nb) were then placed in the polymerization reactor. The 
reactor contents were heated to 70.degree. C. while stirring and ethylene 
was injected to a pressure of 6 bar. 
250 cm.sup.3 of a solution of methylaluminoxane in toluene (10.1% by weight 
of methylaluminoxane having a molecular weight of 1300 g/mol according to 
cryoscopic measurement) were then metered into the reactor and the mixture 
was stirred for 15 minutes at 70.degree. C., the ethylene pressure being 
maintained at 6 bar by injecting in further ethylene. In parallel to this 
500 mg of diphenyimethylene (9-fluorenyl ) cyclopentadienyl zirconium 
dichloride were dissolved in 250 cm.sup.3 of a solution of 
methylaluminoxane in toluene (concentration and quality see above) and 
preactivated by standing for 15 minutes. The solution of the complex 
(catalyst solution) was then metered into the reactor. In order to stop 
the molecular weight increasing, hydrogen can be added discontinuously 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 at 70.degree. C. for 305 minutes while stirring, the 
ethylene pressure being maintained at 6 bar by injecting in further 
ethylene. The reactor contents were then quickly discharged into a stirred 
vessel containing 40 1 of liquid saturated aliphatic hydrocarbons 
(.RTM.Exxsol 100/110), 1000 g of .RTM.Celite J 100 and also 200 cm.sup.3 
of deionized water at 70.degree. C. The mixture was filtered so 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 80.degree. C. under reduced pressure within 15 hours. 
Yield: 4400 g 
Preparation of COC A2 
The preparation of COC A2 was performed in a similar manner to COC A1, 1350 
ml of hydrogen being added immediately 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 being continuously added after the catalyst had been 
metered in. The other altered reaction conditions are summarized in Table 
1. 
Preparation of COC A4 
The preparation of COC A4 was performed in a similar manner to COC A1. The 
altered reaction conditions are summarized in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Norbornene Metallocene 
Catalyst Amount of 
Cycloolefin 
amount T Pressure Amount 
solution 
Time product 
copolymer 
[g] [.degree.C.] 
[bar] Type 
[mg] [cm.sup.3 ] 
[min.] 
[g] 
__________________________________________________________________________ 
A2 20550 70 3.5 A 250 750 135 5716 
A3 10700* 70 3 A 350 850 72 6000 
A4 10700* 70 2.9 A 350 1500 55 4523 
__________________________________________________________________________ 
*in 27 1 of Exxsol 
Metallocene A: Diphenylmethylene (9-fluorenyl) cyclopentadienyl zirconium 
dichloride 
Cycloolefin copolymer A5 [COC A5] 
A clean and dry 75 dm.sup.3 capacity polymerization reactor equipped with a 
stirrer was flushed with nitrogen and then with ethylene. 27 1 of Exxsol 
and 10700 g of norbornene melt were then placed in the polymerization 
reactor. The reactor was heated to 70.degree. C. while stirring and 
ethylene was injected to a pressure of 2.5 bar. 
500 cm.sup.3 of a solution of methylaluminoxane in toluene (10.1% by weight 
of methylaluminoxane having a molecular weight of 1300 g/mol according to 
cryoscopic measurement) were then metered into the reactor and the mixture 
was stirred for 15 minutes at 70.degree. C., 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 zirconium dichloride 
were dissolved in 300 cm.sup.3 of a solution of methylaluminoxane in 
toluene (concentration and quality see above) and preactivated by standing 
for 15 minutes. The solution of the metallocene (catalyst solution) was 
then metered into the reactor. Polymerization was carried out for 90 
minutes at 70.degree. C. while stirring, the ethylene pressure being 
maintained at 2.5 bar by injecting in further ethylene. The reactor 
contents were then quickly discharged into a stirred vessel containing 40 
1 of Exxsol 100/110, 1000 g of Celite J 100 and also 200 cm.sup.3 of 
deionized water at 70.degree. C. The mixture was filtered so 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 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 80.degree. C. under reduced pressure within 15 hours. 
Yield: 5100 g 
The physical characteristics of the five cycloolefin copolymers COC A1, COC 
A2, COC A3, COC A4 and COC A5 are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Incorporation* of &lt;Mw&gt; &lt;Mn&gt; 
Cycloolefin 
Ethylene 
Norbornene 
VN .times. 10.sup.-4 
.times. 10.sup.-4 
&lt;Mw&gt; 
copolymer 
[mol %] 
[mol %] [cm.sup.3 /g] 
[g/mol] 
[g/mol] 
&lt;Mn&gt; 
__________________________________________________________________________ 
A1 48 52 208 38.3 17.4 2.2 
A2 45 55 106 14.8 4.3 3.4 
A3 52 48 76 8.2 2.6 3.2 
A4 46 54 108 13.6 6.8 2.0 
A5 52 48 142 28.0 12.8 2.2 
__________________________________________________________________________ 
*measured by .sup.13 C nuclear magnetic resonance spectroscopy 
VN: viscosity number measured according to DIN 53728 
GPC:&lt;Mw&gt;,&lt;Mn&gt;; 150-C ALC Millipore Waters Chromatograph 
Column set: 4 Schodex columns AT-80 M/S 
Solvent: o-dichlorobenzene at 135.degree. C. 
Flow rate: 0.5 ml/min., concentration 0.1 g/dl 
RI detector, calibration: polyethylene (901 PE) 
Further characteristics of the cycloolefin copolymers A1, A2, A3, A4 and A5 
can be found in the examples. 
Preparation of cycloolefin block copolymers COC C1, COC C2, COC C3 and COC 
C4 
Preparation of COC C1 
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 methylaluminoxane in toluene were then placed in 
the autoclave. The autoclave was heated to 20.degree. C. while stirring 
and ethylene was injected in to a pressure of 1.0 bar. 
Parallel to this 90.7 mg (0.2 mmol) of rac-dimethylsilylbis(1-indenyl) 
zirconium dichloride were dissolved in 20 ml of methylaluminoxane solution 
(see above) and preactivated by standing for 15 minutes. The 
metallocenemethylaluminoxane solution was then metered into the autoclave. 
Polymerization was then carried out for 45 minutes at 20.degree. C. while 
stirring, the ethylene pressure being maintained at 1.0 bar by injecting 
in further ethylene. 
After 45 minutes a solution of 520 ml of toluene and 20 ml of a 20% 
strength solution of trimethylaluminum in .RTM.Exxsol was then metered 
into the autoclave together with ethylene at a pressure of 15.0 bar and 
polymerized for 2 minutes at this pressure. The stopper solution of 30 ml 
of isopropanol and 20 ml of Exxsol was then metered into the autoclave 
under excess pressure. The pressure of the polymer solution was released 
while stirring constantly, and the solution was then discharged. 
The solution was precipitated in acetone and washed twice with acetone. The 
polymer obtained was then stirred into a concentrated hydrochloric 
acid-water solution, in which it stood for about 2 hours. The polymer was 
then washed until it gave a neutral reaction and was stirred twice more 
with acetone. Drying was carried out at 50.degree. C. under a reduced 
pressure within 15 hours. 
Yield: 36.6 g 
Preparation of COC C2 
The preparation of COC C2 was performed in a similar manner to COC C1, 85 
mg (0.19 mmol) of rac-dimethylsilylbis(1-indenyl) zirconium dichloride 
being used and the solution of 520 ml of toluene and 20 ml of a 20% 
strength solution of trimethylaluminum in .RTM.Exxsol being metered in and 
ethylene being injected to a pressure of 15.0 bar after 30 minutes. 
Yield: 96.4 g 
Preparation of COC C3 
A clean and dry 75 dm.sup.3 capacity polymerization reactor equipped with a 
stirrer was flushed with nitrogen and then with ethylene. 50 1 of Exxsol 
and 2.4 kg of norbornene melt were then placed in the polymerization 
reactor. The reactor was heated to 40.degree. C. while stirring and 
ethylene was injected in to a pressure of 1 bar. 
500 cm.sup.3 of a solution of methylaluminoxane in toluene (10.1% by weight 
of methylaluminoxane having a molecular weight of 1300 g/mol according to 
cryoscopic measurement) were then metered into the reactor and the mixture 
was stirred for 15 minutes at 40.degree. C., the ethylene pressure being 
maintained at 1 bar by injecting in further ethylene. Parallel to this 
2000 mg of rac-dimethylsilylbis(1-indenyl) zirconium dichloride were 
dissolved in 500 cm.sup.3 of a solution of methylaluminoxane in toluene 
(concentration and quality see above) and preactivated by standing for 15 
minutes. The prepared catalyst solution was then metered into the reactor. 
Polymerization was then carried out for 45 minutes at 40.degree. C. while 
stirring, the ethylene pressure being maintained at 1 bar by injecting 
further ethylene. 1 1 of propylene (liquid) was 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 reactor contents were then quickly discharged into a stirred vessel 
containing 40 1 of Exxsol 100/110, 1000 g of .RTM.Celite J 100 and also 
200 cm.sup.3 of deionized water at 70.degree. C. The mixture was filtered 
so 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 
80.degree. C. under reduced pressure within 15 hours. 
Yield: 3200 g 
Preparation of COC C4 
A clean and dry 75 dm.sup.3 capacity polymerization reactor equipped with a 
stirrer was flushed with nitrogen and then with ethylene. 16.5 1 of 
toluene and 3.5 1 of norbornene melt were then placed in the 
polymerization reactor. The reactor was heated to 40.degree. C. while 
stirring and ethylene was injected to a pressure of 1 bar. 
500 cm.sup.3 of a solution of methylaluminoxane in toluene (10.1% by weight 
of methylaluminoxane having a molecular weight of 1300 g/mol according to 
cryoscopic measurement) were then metered into the reactor and the mixture 
was stirred for 15 minutes at 40.degree. C., the ethylene pressure being 
maintained at 1 bar by injecting in further ethylene. Parallel to this 800 
mg of rac-dimethylsilylbis(1-indenyl) zirconium dichloride were dissolved 
in 500 cm.sup.3 of a solution of methylaluminoxane in toluene 
(concentration and quality see above) and preactivated by standing for 15 
minutes. 14 1 of toluene together with 2000 cm.sup.3 of a solution of 
methylaluminoxane in toluene (concentration and quality see above) were 
placed in a pressure lock and saturated with propylene at 5 bar. The 
pressure was then raised to 15 bar with ethylene and further ethylene was 
injected until the solution was saturated. Following this the solution of 
the metallocene (catalyst solution) was metered into the reactor. 
Polymerization was then carried out for 30 minutes at 40.degree. C. while 
stirring, the ethylene pressure being maintained at 1 bar by injecting in 
further ethylene. The contents of the pressure lock were then abruptly 
metered into the polymerization reactor and the reaction pressure was 
maintained at 13.5 bar with ethylene. After 5 minutes the reactor contents 
were quickly discharged into a stirred vessel containing 40 1 of Exxsol 
100/110, 1000 g of .RTM.Celite J 100 and also 200 cm.sup.3 of deionized 
water at 70.degree. C. The mixture was filtered so 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 
50.degree. C. under reduced pressure within 15 hours. 
Yield: 5727 g 
The physical characteristics of the cycloolefin block copolymers are given 
in Table 3 and in the examples: 
TABLE 3 
__________________________________________________________________________ 
Cycloolefin- &lt;Mw&gt; &lt;Mn&gt; 
block- VN .times. 10.sup.-4 
.times. 10.sup.-4 
&lt;Mw&gt; Tg 1 Tg 2 
copolymer 
[cm.sup.3 /g] 
[g/mol] 
[g/mol] 
&lt;Mn&gt; [.degree.C.] 
[.degree.C.] 
__________________________________________________________________________ 
C1 148.8 11.5 5.8 2.0 27.8 120.0 
C2 110.9 8.4 4.5 1.9 25.1 152.8 
C3 122.6 11.2 5.9 1.9 29.5 107.8 
C4 129.0 8.9 1.9 4.7 -11.5 150.8 
__________________________________________________________________________ 
VN: Viscosity number determined according to DIN 53728 
GPC:&lt;Mw&gt;, &lt;Mn&gt;; 150-C ALC Millipore Waters Chromatograph 
Column set: 4 Schodex columns AT-80 M/S 
Solvent: o-dichlorobenzene at 135.degree. C. 
Flow rate: 0.5 ml/min., concentration 0.1 g/dl 
RI detector, calibration: polyethylene (809 PE) 
Tg: Glass transition temperature stages measured with a differential 
scanning calorimeter (DSC-7) from Perkin-Elmer (Uberlingen)--heating-up 
and cooling rate 20 K/minute--and with an automatic torsion pendulum from 
Brabender (Duisburg) 
Polyethylene (B1/B2/B3/B4) 
The high-density polyethylenes B1, B2, B3 and B4 used can be obtained 
commercially. B1 is marketed for example as .RTM.Hostalen GF 4760 by 
Hoechst AG, Frankfurt am Main. B2 is .RTM.Hostalen GD 4760, B3 is 
.RTM.Hostalen GM 9240 HT and B4 is .RTM.Hostalen GURX106 (UHMWPE). 
Polypropylene (B5) 
The isotactic polypropylene B5 used can be obtained commercially and is 
marketed as .RTM.Hostaien PPH 1050 by Hoechst AG, Frankfurt am Main. 
Preparation of the blends 
The aforedescribed polymers were first of all dried (115.degree. C., 24 
hours, reduced pressure) and were then kneaded and extruded in various 
weight ratios in a laboratory compounder (HAAKE (Karlsruhe), .RTM.Rheocord 
System 40/ Rheomix 600)) and laboratory extruder (HAAKE (Karlsruhe) 
.RTM.Rheocord System 90/Rheomex TW 100)) under a shielding gas (Ar). The 
ground and granulated blends obtained were dried (115.degree. C., 24 
hours, reduced pressure) and were then either press molded into sheets 
(120.times.1 mm) (vacuum press: .RTM.Polystat 200 S, Schwabenthan 
(Berlin)) or injection molded into moldings (large dumbbell-shaped test 
pieces according to ISO/DIS 3167, small standard test piece according to 
DIN 53451) (injection molding machine: KM 90-210 B with .RTM.Microcontrole 
MC 3, Krauss Maffei (Munich)). The resultant press-molded sheets, 
dumbbell-shaped test pieces and small standard test pieces were 
investigated as regards their physical properties. 
The following apparatus was used for this purpose: 
A differential scanning calorimeter (DSC-7) from Perkin-Elmer (Uberlingen) 
for measuring for example glass transition temperature stages, melting 
points 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: .RTM.Instron 4302) from Instron (Offenbach). 
A melt flow index test apparatus (MPS-D) from Goettfert (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 least 115 mm, outlet nozzle 2.095 (+/-0.005) mm, a 
melting time of 5 minutes being selected. 
A hardness tester (type: Zwick 3106) from Zwick (Ulm) for measuring the 
ball indentation hardnesses according to DIN ISO 2039. 
A pendulum impact tester (type: Zwick 5102) from Zwick (Ulm) for measuring 
the impact strengths according to DIN 53453. 
The heat distortion temperature (HDT) was measured according to DIN 53461. 
The Izod notched impact strength was measured according to ISO 180/1A.