Fiber-reinforced cycloolefin copolymer material, process for its preparation and shaped articles from the material

A fiber-reinforced cycloolefin polymer material comprises 1 to 99% by weight of reinforcing fibers, in particular glass fibers, and 99 to 1% by weight of a cycloolefin copolymer which is built up from PA1 a) at least one (polycyclo)olefin which is derived from norbornene, for example tetracyclododecene, and b) at least one olefin which is chosen from monocycloolefins having 4 to 12 C atoms (VII) and/or the group of acyclic olefins VIII ##STR1## in which 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. VII is preferably ethylene. The monomer units of the (polycyclo)olefin in the cycloolefin copolymer molecule are in each case separated by monomer units of the cyclic olefins VII and/or of the acyclic olefins of the formula VIII.

The present invention relates to "chemically uniform" cycloolefin 
copolymers which comprise as monomers at least one polycycloolefin, such 
as, for example, norbornene, and at least one monocycloolefin and/or one 
acyclic olefin, and are reinforced by fibers, in particular glass fibers. 
Cycloolefin copolymers are a class of polymer having an outstanding level 
of properties. They are distinguished, inter alia, by a high heat 
distortion point, hydrolytic stability, a low absorption of water, 
resistance to weathering and a high rigidity. 
It is known that cycloolefins can be polymerized by means of various 
catalysts. The polymerization here proceeds via ring opening (U.S. Pat. 
No. 3,557,072) or with opening of the double bond (EP 156464, U.S. Pat. 
No. 5,087,677), depending on the catalyst. 
It is known that reinforcing substances can be incorporated into 
cycloolefin copolymers. JP 3207739, DD 203059 and EP 451858 thus report 
thermoplastic combinations which comprise random polymers of cycloolefins 
and ethylene or polycycloolefins and ethylene. Such thermoplastic 
combinations are distinguished, for example, by a particularly high 
rigidity. However, these materials have the decided disadvantage that, 
because of their amorphous character, they have to be processed at a 
temperature of at least 170.degree. C. above the glass transition 
temperature. Since thermal stability of the cycloolefin polymers is 
guaranteed only up to 350.degree. C., heat distortion points of only up to 
a maximum of 180.degree. C. can be established with the mixtures described 
in JP 3207739, DD 203059 and EP 451858. 
The aim of the development of polymeric materials is always to establish a 
maximum heat distortion point. The object was therefore to provide 
fiber-reinforced materials, based on cycloolefin polymers, which have a 
heat distortion point of at least 180.degree. C. and a good thermoplastic 
processability. This object is achieved by the present invention. 
A fiber-reinforced cycloolefin copolymer material has now been found which 
comprises 1 to 99% by weight of reinforcing fibers and 99-1% by weight of 
at least one cycloolefin copolymer which is built up from at least one 
polycycloolefin of the formulae I to VI 
##STR2## 
in which 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 identical or different and are a hydrogen atom or a C.sub.6 
-C.sub.16 -aryl or a C.sub.1 -C.sub.8 -radical, 
and at least one olefin which is chosen from the group of monocycloolefins 
of the formula VII 
##STR3## 
in which n is a number from 2 to 10, and/or the group of acyclic olefins 
of the formula VIII 
##STR4## 
in which 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. 
The cycloolefin polymer material is distinguished in that the 
polycycloolefins of the formulae I to VI, the monocycloolefins of the 
formula VII and/or the acyclic olefins of the formula VIII are not 
randomly distributed in the polymer molecule, but two polycycloolefin 
units are not immediately adjacent, but are in each case separated by at 
least one unit VII and/or VIII. The monomer VIII should preferably always 
be present and the monomer VII can additionally be present. 
Preferably, in each case only one unit VII or VIII, in particular 
exclusively VIII, is positioned between two polycycloolefin units. 
Polymers having the regular arrangement of the monomers described above 
are called "chemically uniform" below, this term in part being used more 
narrowly here than in EP 0 503 422. 
If the fiber-reinforced cycloolefin copolymer material comprises a 
plurality of cycloolefin copolymers, each of the copolymers is "chemically 
uniform". The preparation of chemically uniformcycloolefin copolymers is 
described in European Patent Application EP 0 503 422, which is expressly 
referred to here. 
The preparation of a "chemically uniform" cycloolefin copolymer is carried 
out in accordance with EP 0 503 422 by polymerization of 0.1 to 99.9% by 
weight, based on the total amount of monomers, of at least one monomer of 
the formulae I, II, III, IV, V or VI 
##STR5## 
in which 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 identical or different and are a hydrogen atom or a C.sub.6 
-C.sub.16 -aryl or a C.sub.1 -C.sub.8 -alkyl radical, it being possible 
for the same radicals in the various formulae to have a different meaning, 
0 to 99.9% by weight, based on the total amount of monomers, of a 
cycloolefin of the formula VII 
##STR6## 
in which n is a number from 2 to 10, and 0 to 99.9% by weight, based on 
the total amount of monomers, of at least one acyclic olefin of the 
formula VIII 
##STR7## 
in which 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, at 
temperatures of -78.degree. to 150.degree. C. under a pressure of 0.01 to 
64 bar in the presence of a catalyst which comprises an aluminoxane of the 
formula IX 
##STR8## 
(=linear type) and/or of the formula X 
##STR9## 
(=cyclic type), in which, 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 or 
phenyl or benzyl and n is an integer from 0 to 50, and a metallocene of 
the formula XI 
##STR10## 
in which M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium 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.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 
-arylalkyl 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 identical or different and are a mono- or 
polynuclear hydrocarbon radical which can form a sandwich structure with 
the central atom M.sup.1, 
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 
.dbd.P(O)R.sup.19, in which 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 
-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 and R.sup.21, in each 
case with the atoms joining them, form a ring, and 
M.sup.2 is silicon, germanium or tin. The part of the metallocene molecule 
here formed by M.sup.1 and the substituents R.sup.16 -R.sup.17 displays 
C.sub.1 -symmetry or, if R.sup.16 and R.sup.17 are identical, is in the 
meso-form. 
The term alkyl here is straight-chain or branched alkyl. 
The monocyclic olefin VII can also be substituted (for example by aryl or 
alkyl radicals). 
The polymerization is preferably carried out in liquid polycycloolefin 
I-VI, in mixtures of polycycloolefin or in concentrated solutions. 
In the process for the preparation of "chemically uniform" cycloolefin 
copolymers which are suitable for the preparation of the fiber-reinforced 
materials according to the invention, at least one polycyclic olefin of 
the formulae I, II, III, IV, V or VI, preferably one cycloolefin of the 
formula I or III, is polymerized. 
The second comonomer here is preferably an acyclic olefin of the formula 
VIII, in which 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. 
Ethylene or propylene are preferred. If appropriate, a monocyclic olefin 
of the formula VII, in which n is a number from 2 to 10 is also 
additionally used. 
In particular, copolymers of polycyclic olefins, preferably of the formulae 
I and III, with the acyclic olefins VIII are prepared. 
Particularly preferred cycloolefins are norbornene and tetracyclododecene, 
it being possible for these to be substituted via (C.sub.1 
-C.sub.6)-alkyl. They are preferably copolymerized with ethylene; 
ethylene/norbornene copolymers are of particular importance. 
Polycyclic olefins, monocyclic olefins and open-chain olefins are also to 
be understood as meaning mixtures of two or more olefins of the particular 
type. This means that, in addition to polycyclic bicopolymers, ter- and 
multicopolymers can also be prepared. 
The fiber-reinforced materials according to the invention are particularly 
suitable for the production of extruded components, such as sheets, tubes, 
pipes, rods and fibers, and also for the production of injection molded 
articles of any shape and size. 
The particular advantage of the chemically uniform cycloolefin copolymers 
is their particularly simple ease of preparation and their particularly 
pronounced stability to non-polar solvents. The advantageous properties 
known of other random cycloolefin copolymers, such as hydrolytic 
stability, low absorption of water and resistance to weathering, however, 
are retained. 
The degree of crystallinity of chemically uniform cycloolefin copolymers is 
between 0.1 and 50%, preferably between 2 and 40%. 
This can be determined by the radiography method known from the literature 
(cf. K. Kakudo, N, Kasai, X-Ray Diffraction by Polymers, Elsevier, 
Amsterdam 1972). 
Preferably, the fiber-reinforced cycloolefin copolymer comprises a single 
polycycloolefin of the formulae I to VI and either at least one 
monocycloolefin of the formula VII or at least one acyclic olefin of the 
formula VIII. Blocks of polycycloolefin are absent in the polymer 
molecule. In the limiting case, the polycycloolefin and the olefin VII 
and/or VIII are arranged regularly and alternately in the polymer 
molecule. 
It is particularly preferable if a 1-olefin, such as ethylene, propylene or 
but-1-ene, is used as the acyclic olefin of the formula VIII. It is 
particularly preferable if the copolymer comprises equimolar amounts of 
norbornene and ethylene and the two monomer molecules are arranged 
regularly and alternately in the polymer. 
The fibers used for the reinforcement can be of carbon, metal, ceramic or 
aramid. Materials of high strength which are impermeable to light can be 
produced in this manner. For economic reasons, it is advantageous to use 
glass fibers for the reinforcement. If the cycloolefin copolymer employed 
is transparent and the refractive indices of the copolymer and glass fiber 
coincide, a transparent fiber-reinforced cycloolefin polymer material can 
be obtained. If the difference in the refractive indices is too high or 
the cycloolefin copolymer employed has too high a crystallinity, i.e. is 
no longer transparent, the fiber-reinforced cycloolefin copolymer material 
is also not transparent. However, transparency is not important for many 
intended uses. The material according to the invention is usually further 
processed in the form of granules. Material reinforced with long fibers 
can be used for wrapping pipes. 
The cycloolefin copolymers (="COC") according to EP 503 422 are partly 
crystalline and therefore have a melting point. The melt can be processed 
at about 10-20 K. above the melting point, i.e. at about 
295.degree.-310.degree. C. The fiber material can be incorporated, for 
example, into the melt. 
On the other hand, amorphous COC have only a glass transition temperature 
and cannot be processed until about 170 K. above the glass transition 
temperature (at about 350.degree. C.). 
The COC according to EP 503 422 are transparent up to a partial 
crystallinity of 20%. They become less and less transparent at a partial 
crystallinity of 20-40%. The degree of crystallinity can be reduced by 
quenching from the melt. The use of symmetric monomer molecules, the 
reduction in the number of monomers and approaching an equimolar molar 
ratio during synthesis of COC increases the tendency toward 
crystallization. A COC which is derived from methyl-norbornene as the 
polycyclic olefin will have a lower tendency toward crystallization than 
an analogous COC derived from norbornene. 
The COC which can be prepared by the process according to EP 503 422 are 
practically free from blocks which comprise monomers of the formulae I to 
VI ("norbornene blocks"). In general, a polycyclic monomer of the formulae 
I to VI is followed by at least one monomer of the formulae VII and/or 
VIII. 
It is surprising that when reinforcing fibers, in particular glass fibers, 
are incorporated into the COC according to EP 503 422, the ductility (for 
example the elongation at break) increases at temperatures above the glass 
transition temperature. This effect is otherwise known only for partly 
crystalline polymers having a degree of crystallinity of at least 20%, 
while in the "chemically uniform" COC, it already occurs at significantly 
lower degrees of crystallinity (at least from 5%). The fiber-reinforced 
materials according to the invention are superior to the fiber-reinforced 
materials according to EP 451 858 which comprise an amorphous COC. This 
manifests itself in the higher heat distortion point and in the improved 
thermoplastic processability of the COC according to EP 503422. 
The surprising fact that chemically uniform cycloolefin copolymers can be 
reinforced particularly well with glass fibers is possibly because they 
display a very low shrinkage after processing and the glass fiber is thus 
not detached from the polymer matrix. This leads to a better geometric 
adhesion. 
The shrinkage is stated as the so-called processing rate, which is 
determined in accordance with DIN 53464. The processing rate of chemically 
uniformcycloolefin copolymers is less than 0.4%. 
A significant improvement in the mechanical properties of filled and 
non-filled chemically uniform cycloolefin copolymers can be achieved by 
after-treatment with heat and/or by the use of a suitable nucleating 
agent. 
The content of reinforcing fibers, in particular glass fibers, in the 
material according to the invention is preferably 10 to 90% by weight, in 
particular 50 to 75% by weight. 
To prepare a fiber-reinforced cycloolefin copolymer material according to 
the invention, the melt of a chemically uniformcycloolefin copolymer 
defined above in more detail is mixed with the desired content of 
reinforcing fibers. 
The glass fibers used usually have sizes which protect the glass filaments 
from mechanical load and bond strands of glass loosely to one another. 
The main constituents of sizes are, according to WO 86/01811, film-forming 
polymers and lubricants and, if required, adhesion promoters and other 
additives. The film-forming polymers are dispersible, soluble or 
emulsifiable in an aqueous medium, as is the reaction product with process 
auxiliaries. The content of water in the aqueous chemical combination of 
the size constituents is designed such that these result in the effective 
content of solid on the glass fiber. 
The aqueous chemical combination for the treatment of glass fibers can be 
employed in any method for the preparation of cut glass fibers or 
continuous glass fibers. For example, it can be used in the wet cutting 
operation in which the fibers are combined in bundles and cut directly 
during the formation process, or the chemically treated glass fibers are 
combined in bundles or strands and wound up and only subsequently cut. 
In the case of the glass fiber-reinforced plastic materials which belong to 
the prior art, the problem occurs that the (polar) glass fibers sometimes 
adhere poorly to non-polar polymers and therefore the mechanical 
resistance of the shaped articles is not optimum. Adhesion promoters have 
therefore already been employed in this connection for better coupling. 
These adhesion promoters are applied to the glass fiber either during 
treatment with the aqueous chemical combination of the size constituents 
or by a separate treatment with a solution of the adhesion promoter. 
It is furthermore possible to introduce the adhesion promoters into the 
melt of the polymer. This method has the advantage that no solutions have 
to be processed. The adhesion promoters can also advantageously be 
incorporated into the composite by preparing masterbatches which utilize 
the dilution principle, as is possible with the other additives. 
This addition of adhesion promoters is also advantageous in the process 
according to the invention for the preparation of glass fiber-reinforced 
chemically uniform cycloolefin copolymers. According to the invention, it 
is possible either to add a polymer melt adhesion promoter or to coat the 
glass fibers with an adhesion promoter. 
Known adhesion promoters can be chosen from the group comprising 
vinylsilanes, methacrylylsilanes, aminosilanes, epoxysilanes and 
methacrylate-chromium chloride complexes. 
Polymer-based organic adhesion promoters are preferred, the organic 
adhesion promoters which are functionalized cycloolefin copolymers being 
particularly preferred. A functionalized, "chemically uniform" cycloolefin 
copolymer is advantageously employed here as the adhesion promoter. 
The functionalized "chemically uniform" cycloolefin copolymer is preferably 
prepared by grafting a chemically uniform cycloolefin copolymer with a 
polar monomer. It is particularly advantageous if the polar monomer used 
for the grafting is chosen from the group comprising 
alpha,beta-unsaturated carboxylic acids, alpha,beta-unsaturated carboxylic 
acid derivatives, organic silicon compounds having an olefinically 
unsaturated and hydrolyzable group, olefinically unsaturated compounds 
having the hydroxyl group and olefinically unsaturated epoxy monomers. 
Similar grafted polymers, which needless to say are not derived from 
"chemically uniform" cycloolefin copolymers, are already known. 
The invention thus relates to an adhesion promoter which is prepared by 
grafting a "chemically uniform" cycloolefin copolymer, described above 
with a polar monomer. The content of grafted polar monomer in the polymer 
is 0.01 to 50% by weight. No particular requirements are placed on the 
glass used. The glass fibers are preferably made of magnesium 
alumosilicate having a refractive index of 1.50 to 1.56 and comprise 60 to 
68% by weight of SiO.sub.2, 23 to 29% by weight of Al.sub.2 O.sub.3 and 8 
to 12% by weight of MgO. The fiber material to be incorporated usually has 
an average fiber length of 0.0001-7 mm, in particular 0.1 to 2 mm.

The invention is illustrated in more detail by the examples. 
EXAMPLES 
Example 1 
A 70 l reactor was filled with ethylene, and 17.6 of an 85 percent strength 
by weight solution of norbornene in toluene and 12.4 l of decalin were 
introduced. The solution was saturated with ethylene by forcing in 
ethylene (6 bar) several times. A pressure of 3.0 bar (increased pressure) 
was established, 950 cm.sup.3 of a toluene solution of methylaluminoxane 
(10.1% by weight of methylaluminoxane of molecular weight 1300 g/mol 
according to cryoscopic determination) were introduced into the reactor 
and the mixture was stirred at 70.degree. C. for 15 minutes. A solution of 
157 mg of isopropylene(9-fluorenyl)(1-(3-methyl)cyclopentadienyl)zirconium 
dichloride in 80 cm.sup.3 of a toluene solution of methylaluminoxane was 
added after preactivation for 15 minutes (hydrogen can be metered in 
before the addition of the catalyst in order to regulate the molecular 
weight). Polymerization was carried out at 70.degree. C. for 30 minutes, 
while stirring (750 revolutions per minute), the ethylene pressure being 
kept at 3.0 bar by topping up. The reaction solution was then introduced 
into a second reactor into which 200 ml of isopropanol had initially been 
introduced as a stopping agent. The reaction solution stopped in this way 
was drained into a precipitation reactor and stirred here into 200 l of 
acetone. This precipitation bath was then passed over a pressure suction 
filter so that the solid which had precipitated could be isolated. This 
solid was washed with acetone several more times and then dried at 
80.degree. C. under a pressure of 0.2 bar for 14 hours. 
1.89 kg of a colorless polymer were obtained. A viscosity number (decalin, 
135.degree. C.) of 75 cm.sup.3 /g, a glass transition temperature of 
137.degree. C. and a melting point of 287.degree. C. were measured. 
According to the NMR spectrum, the norbornene/ethylene incorporation ratio 
is about 50 mol % of norbornene to 50 mol % of ethylene. This cycloolefin 
copolymer is called COC A1 below. 
Example 2 
A 70 l reactor was filled with ethylene, and 17.6 l of an 85 percent 
strength by weight solution of norbornene in toluene and 12.4 l of decalin 
were introduced. The solution was saturated with ethylene by forcing in 
ethylene (6 bar) several times. A pressure of 6.0 bar (increased pressure) 
was established, 950 cm.sup.3 of a toluene solution of methylaluminoxane 
(10.1% by weight of methylaluminoxane of molecular weight 1300 g/mol 
according to cryoscopic determination) were introduced into the reactor 
and the mixture was stirred at 70.degree. C. for 15 minutes. A solution of 
75 mg of diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium 
dichloride in 40 cm.sup.3 of a toluene solution of methylaluminoxane was 
added after preactivation for 15 minutes (hydrogen can be metered in 
before addition of the catalyst in order to regulate the molecular 
weight). Polymerization was carried out at 70.degree. C. for 30 minutes, 
while stirring (750 revolutions per minute), the ethylene pressure being 
kept at 6.0 bar by topping up. The reaction solution was then introduced 
into a second reactor into which 200 ml of isopropanol had initially been 
introduced as a stopping agent. The reaction solution stopped in this way 
was drained into a precipitation reactor and stirred here into 200 l of 
acetone. This precipitation bath was then passed over a pressure suction 
filter so that the solid which had precipitated could be isolated. This 
solid was washed with acetone several more times and then dried at 
80.degree. C. under a pressure of 0.2 bar for 14 hours. 
7.8 kg of polymer which has a glass transition temperature of 181.degree. 
C. and a viscosity number (measured in decalin at 135.degree. C.) of 108 
were obtained. The polymer is composed of 46% by weight of ethylene and 
54% by weight of norbornene, which are randomly distributed in the 
polymer. 
This polymer is called COC A2 below. 
Example 3 
Filling the polymers with glass fibers and granulation 
COC A1 was extruded together with 30 percent by weight of glass fibers in 
an extruder and processed to granules. The extrusion temperature was 
between 260.degree. and 300.degree. C. (different temperatures in 
different heating zones of the extruder). A vacuum of 100 mbar was applied 
for devolatilization of the polymer melt. The glass fibers used were 
textile glass roving P 365 (commercial product from VETROTEX; 
Herzogenrath, Federal Republic of Germany). The nominal filament diameter 
(DIN 53811) of the glass fibers is 14 .mu.m, the roving fineness (DIN 
53830) is 2400 tex and the strand fineness (DIN 53830) is 300 tex. 
Colorless granules of COC A1 filled with 30 percent by weight of glass 
fibers were obtained. 
To prepare COC A2 granules filled with 30% by weight of glass fibers, the 
extrusion temperature had to be increased to 310.degree. to 350.degree. C. 
The other conditions correspond to the extrusion conditions mentioned 
above for glass fiber-filled COC A1. Since 350.degree. C. is already the 
upper processing temperature for COC, damage to the polymer already 
occurred during this granulation and revealed itself in a significant 
yellow coloration of the granules. 
The processability of thermoplastic polymers is characterized by the MFI. 
The higher the MFI (DIN 53735) at the processing temperature, the lower 
the viscosity of the polymer melt and the better the material can be 
processed by extrusion and injection molding. The MFI was therefore 
determined on the resulting granules. The value found is shown in Table 1 
together with comparison values for other glass fiber-filled cycloolefin 
copolymers. 
TABLE 1 
______________________________________ 
MFI of COC A1 and COC A2 each filled with 
30% by weight of glass fibers 
______________________________________ 
MFI (g/10 minutes) 
310.degree. C.; 10 kg 
COC A1 284 
COC A2 73 
______________________________________ 
The data presented clearly show that glass fiber-filled compositions of COC 
A1 have a superior thermoplastic processability. 
Example 4 
Standard test specimens were produced by injection molding from the 
granules prepared under Example 2. The HDT-B of these standard test 
specimens was determined in accordance with DIN 53461. The values 
determined are summarized in Table 2. 
TABLE 2 
______________________________________ 
HDT-B of COC-A1 and COC-A2 each filled 
with 30% by weight of glass fibers 
______________________________________ 
HDT-B/.degree.C. 
COC A1 244 
COC A2 177 
______________________________________ 
These values demonstrate that the chemically uniform cycloolefin copolymer 
filled with glass fibers has a significantly higher heat distortion point 
than the corresponding composites based on cycloolefin copolymers COC A2. 
Example 5 
Standard test specimens were produced by injection molding from glass 
fiber-reinforced COC A1 and COC A2 (in each case 30% of glass fibers) and 
from non-filled COC A1. The mechanical properties were determined on these 
by tensile stress tests. The determination of the mechanical properties 
was carried out at room temperature and at 210.degree. C. The 
corresponding values are shown in Table 3, 4, 5, and 6. 
TABLE 3 
______________________________________ 
Mechanical properties of COC A1 with and without glass 
fibers at 23.degree. C. 
Tensile stress 
Elongation 
E modulus 
at break in at break in 
in MPa MPa % 
______________________________________ 
COC A1 3971 43.7 1.8 
without glass 
fibers 
COC A1 with 
10230 83.5 1.8 
30% by weight of 
glass fibers 
______________________________________ 
TABLE 4 
______________________________________ 
Mechanical properties of COC A1 with and without glass fibers 
at 210.degree. C. 
Tensile stress 
Elongation 
E modulus 
at break in at break in 
in MPa MPa % 
______________________________________ 
COC A1 35 3.9 55.6 
without glass 
fibers 
COC A1 with 
463 1.9 17.3 
30% by weight of 
glass fibers 
______________________________________ 
The values shown in Tables 3 and 4 show that by introduction of glass 
fibers into chemically uniform polymers, a significant improvement in the 
mechanical properties of the polymer is achieved. The superior rigidity of 
the glass fiber-filled COC A1 at 210.degree. C. is particularly clear. 
TABLE 5 
______________________________________ 
Mechanical properties of COC A1 and COC A2, filled with 30% 
by weight of glass fibers, at 23.degree. C. 
Tensile stress 
Elongation 
E modulus 
at break in at break in 
in MPa MPa % 
______________________________________ 
COC A1 10,230 83.5 1.8 
COC A2 8320 75.1 1.6 
______________________________________ 
TABLE 6 
______________________________________ 
Mechanical properties of COC A1 and COC A2, filled with 30% 
by weight of glass fibers, at 210.degree. C. 
Tensile stress 
Elongation 
E modulus 
at break in at break in 
in MPa MPa % 
______________________________________ 
COC A1 463 1.9 17.3 
COC A2 no longer measurable 
______________________________________ 
The values summarized in Table 5 and 6 show that the mechanical properties 
of a chemically uniform cycloolefin copolymer filled with glass fibers are 
significantly superior to those of a random cycloolefin copolymer filled 
with glass fibers. 
Examples 1 to 5 demonstrate that only with glass fiber-reinforced 
chemically uniform cycloolefin copolymers is it possible to realize a heat 
distortion point (HDT-B) of greater than 180.degree. C., good mechanical 
properties, such as high rigidity, and at the same time a good 
processability. 
The tear strength, i.e. the tensile stress at which the standard tensile 
specimen breaks, and the elongation at break, i.e. the maximum elongation, 
were determined in accordance with DIN 53455 with the aid of an 
.RTM.Instron tensile tester (Instron, Offenbach, Federal Republic of 
Germany). The E modulus (elasticity) is calculated from the tensile 
stress-elongation curve in accordance with DIN 53457. The heat distortion 
point HDT-B was determined in accordance with DIN 53461. The MFI was 
determined in accordance with DIN 53735. The viscosity number was 
determined in accordance with DIN 53726. 
The granules were prepared with the aid of a Leistritz LSM 30.34 laboratory 
extruder (Leistritz; Nuremberg, Federal Republic of Germany). 
The standard test specimens were produced by injection molding using a 
Krauss Maffei KM 90-210 B injection molding machine (Krauss Maffei, 
Kunststofftechnik GmbH; Dusseldorf; Federal Republic of Germany).