Title of Invention

POLYPROPYLENE OF IMPROVED PROCESSABILITY FOR PRODUCTION OF PIPES

Abstract The present invention relates to a polymer composition, comprising (i) a polypropylene-based matrix which comprises a polypropylene random copolymer prepared by copolymerization of propylene with an olefin comonomer, wherein the amount of olefin comonomer units is within the range of 0.2 wt% to 5 wt%, based on the weight of the polypropylene-based matrix, and (ii) an elastomeric copolymer of propylene and at least one olefin comonomer, the polymer composition having a storage modulus G' at a loss modulus G"=5 kPa of G'(5 kPa) < 3100 Pa, measured at 220°C.
Full Text The present invention relates to a polymer composition having improved
processability for the preparation of pipes of high surface-smoothness and excellent
mechanical properties. Furthermore, it relates to a process for preparing such a polymer composition and to pipes made therefrom.
Pipes made of polymeric material are frequently used for various purposes such as
fluid transport, i.e. transport of liquids and gases. The fluid may be pressurized, e.g.
when transporting natural gas or tap water, or non-pressurized, e.g. when transporting
sewage (waste-water), drainage, for storm water applications or indoor sewage (soil
and waste discharge). Moreover, the transported fluid may have varying temperature,
usually within the range of 0°C to 50°C. Pressureless (non-pressure) pipes may also
be used for cable and pipe protection and for culvert system (e.g. road and rail).
Polypropylene-based polymers have many characteristics which make them suitable
for applications like pipes, fittings, moulded articles, foams. Polypropylene as a pipe
material is mainly used in non-pressure applications (pipes and fittings) and profiles.
However, polypropylene is also used for pressure pipes, mainly hot water and
industrial pipes.
For non-pressure pipe systems, high stiffness is needed to provide sufficient
resistance, e.g. to soil pressure. Normally, polypropylene products of high stiffness
are based on high molecular weight materials which are often nucleated by adding
nucleating agents, i.e. crystallization starts at a higher temperature and crystallization
speed is high.. However, in polymers of high molecular weight the tendency of
polymeric chains to be oriented is more pronounced. As a consequence, these high
molecular weight polymers will result in high process shrinkage since the oriented
polymeric chains are striving to go back in the non-oriented stage when the melt is
leaving the die or extruder die head. Since shrinkage normally increases with
increasing extrusion speed, this poses a significant restriction to production rate.

Furthermore, due to the tendency of high molecular weight polymers to be oriented,
residual stress in the final product is increasing due to fast crystallization of the high
modulus material if cooling is applied before the material has been able to recover
after orientation in the melt, whereas surface properties such as surface smoothness
are poor. However, surface properties of the final polymer are relevant for the notch
resistance of the final product. Thus, pipe surfaces having imperfections and/or
scratches result in very low notch resistance.
To increase output rate of the extruder (e.g. for pipe production), a polymer of high
flowability would be preferred. Furthermore, at a specific output rate, melt pressure
and melt temperature at the end of the extruder should be on a low level but also
sufficiently high to ensure a good melt homogeneity (e.g. normally above 190°C for
polypropylene). When increasing the output of the extruder, the melt pressure and
hence the melt temperature are increasing based on the flow restrictions, i.e. the die
or die head. With regard to melt pressure, restrictions result from the extruder
equipment whereas at high melt temperature polymer degradation is more likely to
occur. For improving flowability, the polymeric melt should be of low viscosity, e.g.
by reducing molecular weight. However, as discussed above, high molecular weight
is preferred for realizing high stiffness. Furthermore, by using low viscosity material,
the resulting mechanical properties are usually not sufficient for meeting the
requirements as defined in international standards like EN 1852, prEN13476.
Normally, melt flow rate values of polymers for non-pressure pipe applications are
kept at a low level to fulfil the standard requirements.
As discussed above, to realize a specific output rate a lower melt temperature would
be preferred. However, a too low melt temperature normally results in worse surface
properties, e.g. poor surface smoothness, and as a consequence thereof in worse
mechanical properties, e.g. low notch resistance.
Thus, there is still a need for polypropylene-based compositions for pipes having
improved processability while maintaining mechanical properties on a high level.
Considering the problems discussed above, it is an object of the present invention to
provide a polypropylene-based composition that can be processed at lower melt

temperature and/or melt pressure but still results in a material of high stiffness,
excellent surface properties like high surface smoothness, good long term properties,
high notch resistance and high impact values at low temperature.
These objects are solved by providing a polymer composition, comprising
(i) a polypropylene-based matrix which comprises at least one polypropylene
random copolymer prepared by copolymerization of propylene with an olefin
comonomer, wherein the amount of olefin comonomer units within the matrix is from
0.2 wt% to 5.0 wt%, based on the weight of the polypropylene-based matrix, and
(ii) an elastomeric copolymer of propylene and at least one olefin comonomer,
the polymer composition having a storage modulus G' at a loss modulus G"=5 kPa of
G'(5 kPa) An essential feature of the invention is the presence of a polypropylene random
copolymer, prepared by copolymerization of propylene with an olefin comonomer.
As will be discussed below, the polypropylene-based matrix can be made of one
polypropylene random copolymer only or can optionally comprise further polymeric
components such as a polypropylene homopolymer or a second polypropylene
random copolymer.
According to the present invention, the polypropylene-based matrix needs to have an
amount of olefin comonomer units originating from the one or more random
copolymer components within the range of 0.2 wt% to 5.0 wt%.
As already indicated above, a random copolymer is one of the three main types of
polypropylene. In general, a polypropylene random copolymer is obtained when
propylene is polymerized with at least one comonomer so as to result in a random or
statistical distribution of the comonomer within the polymer chain. The amount and
type of comonomer has a significant influence on a number of properties like
crystallization behaviour, stiffness, melting point or flowability of the polymer melt.
To solve the objects of the present invention, in particular to provide an improved
balance between processability and mechanical properties, it is necessary to keep the

amount of olefin comonomer units originating from the polypropylene random
copolymer within the range given above.
In a preferred embodiment, the polypropylene-based matrix has an amount of olefin
comonomer units within the range of 0.2 wt% to 4.0 wt%. In other preferred
embodiments, the amount of olefin comonomer units within the matrix is from 0.5
wt% to 3.0 wt%, from 0.5 wt% to 2.0 wt%, or from 0.5 wt% to 1.5 wt%.
The olefin comonomer is preferably selected from ethylene, C4 to C10 alpha-olefins
such as 1-butene, 1-hexene or 1-octene, or mixtures thereof. Ethylene is the preferred
comonomer.
When ethylene is used as the olefin comonomer, its amount within the
polypropylene-based matrix is preferably within the range of 0.2 to 5.0 wt%, more
preferably 0.2 wt% to 4.0 wt%, even more preferably 0.4 wt% to 3.0 wt%, and most
preferably 0.6 wt% to 2.0 wt%.
In case the matrix is made of the polypropylene random copolymer only, the ranges
given above correspond to the amount of comonomer units within the random
copolymer. However, if further components are present in the polypropylene-based
matrix, the random copolymer can have an amount of olefin comonomer units
exceeding the ranges given above.
In a preferred embodiment, the polypropylene-based matrix is unimodal. In such a
case, the matrix is preferably made of the polypropylene random copolymer only.
However, it might also comprise one or more additional polymeric components
having a molecular weight adapted to the molecular weight of the random copolymer
so as to maintain the unimodal molecular weight distribution.
According to another preferred embodiment, the polypropylene-based matrix is
multimodal, e.g. bimodal.
The expression "multimodal" used herein refers to the modality of the polymer, i.e.
the form of its molecular weight distribution curve, which is the graph of the
molecular weight fraction as a function of its molecular weight. As will be explained
below, the polymer components of the present invention can be produced in a

sequential step process, using reactors in serial configuration and operating at
different reaction conditions. As a consequence, each fraction prepared in a specific
reactor will have its own molecular weight distribution. When the molecular weight
distribution curves from these fractions are superimposed to obtain the molecular
weight distribution curve of the final polymer, that curve may show two or more
maxima or at least be distinctly broadened when compared with curves for the
individual fractions. Such a polymer, produced in two or more serial steps, is called
bimodal or multimodal, depending on the number of steps.
As already indicated above, the polypropylene-based matrix can comprise further
polymeric components, in particular for obtaining a multimodal matrix.
Preferably, the polypropylene-based matrix further comprises a polypropylene
homopolymer. Within the context of the present invention, a polypropylene
homopolymer is defined to be a polymer consisting of more than 99.8 wt%,
preferably more than 99.9 wt%, even more preferably 99.99 wt% of propylene units.
If units other than propylene units are present, these originate preferably from an
olefin such as ethylene.
The polypropylene homopolymer can be unimodal or multimodal.
In a preferred embodiment, the polypropylene homopolymer fraction has a melt flow
rate MFR2.16kg/230°c of less than 20 g/10 min. In general, melt flow rate is related to
flowability of the polymeric melt at a specific temperature when subjected to a
specific load. High melt flow rate values indicate a polymeric melt of low viscosity,
and vice versa.
As will be explained below in greater detail, if a polypropylene homopolymer is
present, it can be prepared in a first step, i.e. before preparing the polypropylene
random copolymer and the elastomeric copolymer, or at a later stage. If prepared in a
later stage, the homopolymer can be reactor-blended with the random copolymer
already prepared before, thereby resulting in a matrix from which only a total melt
flow rate can be determined but not the melt flow rate of each component within the
blend. However, even if obtained as a reactor blend, the MFR2.16kg/230°c of the

polypropylene homopolymer refers to a pure homopolymer fraction. In other words,
it is the melt flow rate value of the polypropylene homopolymer that would have been
obtained if polymerized without the presence of further components.
In other preferred embodiments, the polypropylene homopolymer fraction has a melt
flow rate MFR2.16kg/230°c of less than 10 g/10 min, less than 5 g/10 min or even less
than 3 g/10 min.
Preferably, the average molecular weight of the polypropylene random copolymer is
higher than the average molecular weight of the polypropylene homopolymer, if
present.
In another preferred embodiment, the polypropylene-based matrix comprises a
second polypropylene random copolymer fraction, either as an alternative to the
polypropylene homopolymer or in addition to the homopolymer, wherein both
random copolymers differ in their amount of olefin comonomer units. Of course, the
amount of olefin comonomer units of each polypropylene random copolymer fraction
has to be chosen so as to result in a polypropylene-based matrix with an olefin
comonomer content of 0.2 to 5 wt%.
A further essential feature of the polymer composition of the present invention is the
presence of an elastomeric copolymer of propylene and at least one olefin
comonomer. The presence of such an elastomeric propylene copolymer improves
impact performance of the final polymer. The conditions for the copolymerization are
within the limits of conventional conditions for ethylene-propylene rubber (EPM)
production. Typical conditions are disclosed e.g. in Encyclopedia of Polymer Science
and Engineering, second edition, vol. 6, p. 545-558. An elastomeric product is
obtained when the comonomer content of the polymer is within a certain range.
Suitable olefin comonomers to be copolymerized with propylene can be selected
from ethylene, C4 to C10 alpha-olefins such as 1-butene, 1-hexene or 1-octene, or
mixtures thereof. Preferably, ethylene is used.

Preferably, the elastomeric copolymer contains olefin comonomer units in an amount
of 10 to 70 wt%, more preferably 20 to 50 wt%, based on the weight of the
elastomeric copolymer.
When ethylene is used as an olefin comonomer, the elastomeric copolymer preferably
contains ethylene units in an amount of 10 to 70 wt%, based on the weight of the
elastomeric copolymer. In other preferred embodiments, the amount of ethylene units
within the elastomeric copolymer is from 10 wt% to 60 wt%, from 20 wt% to 55
wt%, from 25 wt% to 50 wt%, or from 30 wt% to 50 wt%.
As indicated above, the presence of an elastomeric ethylene-propylene copolymer
improves impact properties as determined e.g. by measurement of Charpy notched
impact strength. However, if the amount of elastomeric copolymer within the final
polymer composition is too high, this might have a detrimental effect on other
properties like stiffness or processability.
Preferably, the polymer composition of the present invention comprises an amount of
elastomeric copolymer within the range of 5 wt% to 30 wt%, based on the weight of
the polymer composition. In other preferred embodiments, the amount of elastomeric
copolymer within the final polymer composition is from 7 wt% to 20 wt% or from 10
wt%to 15wt%.
According to a further essential feature of the present invention, the polymer
composition has a storage modulus G' at a loss modulus G"=5 kPa, of G(5kPa) Pa, measured at 220°C. With a storage modulus of 3100 Pa or less, process shrinkage,
residual stress, surface smoothness and notch resistance as well as impact strength
can be further improved. This is insofar surprising as a reduction in melt elasticity
(i.e. storage modulus) normally has a detrimental effect on notch resistance and
impact strength, in particular at low temperature.
The storage modulus G' is related to the molecular weight distribution. In general,
storage modulus values increase with increasing molecular weight. However, G' is
also highly dependent on the shape of the molecular weight distribution curve. In

particular, it is a measure of the high molecular weight end of the molecular weight
distribution.
In a preferred embodiment, the polymer composition has a storage modulus G' at a
loss modulus G" of 5 kPa, of G'(5kPa) even more preferably 2500 Pa or less, and most preferably 2300 Pa or less, measured
at 220°C.
To have a material of high stiffness, the polymer composition preferably has a tensile
modulus of at least 1350 MPa. In further preferred embodiments, the polymer
composition of the present invention has a tensile modulus of at least 1400 MPa, at
least 1475 MPa, at least 1500 MPa or at least 1600 MPa.
In the so-called Rheotens test, a melt strand, e.g. generated by extrusion, is elongated
by drawing down with a defined acceleration. The haul off force as a function of
draw down velocity is recorded. The maximum values for haul off force and draw
down velocity, i.e. Fmax and vmax, at failure of the strand indicate melt strength and
drawability of the melt. Curves obtained by Rheotens tests of different polymers very
sensitively reflect a change in molecular weight distribution, phase structure (e.g.
degree of long chain branching) and crystallization speed. Further details about the
Rheotens test in general can be found e.g. in EP-A-1301343.
In a preferred embodiment, the polymer composition has a ratio of drawabiiity vmax to
melt strength Fmax of more than 2.1 mm/s*cN, measured according to the Rheotens
test at an extrusion temperature of 200 °C. More preferably, the ratio of drawabiiity
vmax to melt strength Fmax of the polymer composition in the Rheotens test is more
than 2.5 mm/s*cN, even more preferably more than 2.7 mm/s*cN.
With the Rheotens test, it is possible to characterize the ability of a material to
efficiently fill a mould which is a very relevant property e.g. in the manufacturing
process of single or double wall pipes (by vacuum and/or air pressure) before and
during cooling and crystallization in the mould blocks. Thus, by having a low force
combined with a good elongation ability, the mould filling will be fast and efficient,
giving a good processability. It is also beneficial to have a low force in general as

long as the elongation is sufficient for the filling of the mould, i.e. before the material
crystallizes and will break as seen in the Rheotens test.
In a preferred embodiment, the polymer composition has a haul off force F of 60 cN
or less at a velocity v = 80 mm/s in the Rheotens test at an extrusion temperature of
200 °C. More preferably, the haul off force F at a velocity v = 80 mm/s is 50 cN or
less, even more preferably 40 cN or less and most preferably 35 cN or less.
In another preferred embodiment, the polymer composition has a drawabiliy v of 40
mm/s or more at a haul off force F = 20 cN in the Rheotens test at an extrusion
temperature of 200 °C. More preferably, the drawability v at a haul off force F = 20
cN is 50 mm/s or more, even more preferably 60 mm/s or more.
To have a good balance between flowability of the melt and mechanical properties,
the polymer composition preferably has a melt flow rate MFR2.16kg/230oc within the
range of 0.2 to 10 g/10 min, more preferably 0.25 to 8 g/10 min, even more
preferably 0.4 to 6.5 g/10 min, and most preferably 0.5 to 5 g/10 min.
The polymer composition preferably has a polydispersity index PI, which is an
indication of the breadth of the molecular weight distribution, of 2.5 to 6.0. In other
preferred embodiments, PI of the matrix is within the range of 3.0 to 5.0, 3.0 to 4.5 or
3.0 to 4.0. The polydispersity index PI is calculated according to the following
equation:

wherein Gc in Pa is the cross over modulus at which G,=G"=GC, G' and G" indicating
the storage modulus and the loss modulus, respectively.
The measurements have been done according to ISO 6421-10. Measurements were
made at 220°C on a Physica MCR 300 rheometer with a plate-plate fixture, plate
diameter 25 mm, and a distance between the plates of 1.8 mm.
In addition to the components discussed above, the polymer composition may
comprise conventional adjuvants, such as additives, fillers and reinforcing agents.

As additives, the following can be mentioned: nucleating agents, process and heat
stabilizers, pigments and other colouring agents including carbon black. Depending
on the type of additive, these may be added in an amount of 0.01 to 5 wt%, based on
the weight of the polymer composition.
In a preferred embodiment, the polymer composition includes 0.05 to 3 wt%, based
on the weight of the polymer composition, of one or more alpha-nucleating agents
such as talc, polymerized vinyl compounds such as polyvinyl cyclohexane,
dibenzylidene sorbitol, sodium benzoate, and di(alkylbenzylidene)sorbitol. Except for
talc, the alpha-nucleating agent is usually added in small amounts of 0.0001 to 1
wt%, more preferably 0.001 to 0.7 wt%. Since talc can act both as a nucleating agent
and as a filler, it can be added in higher amounts. When added as a nucleating agent,
talc is preferably added in an amount of 0.05 to 3 wt%, more preferably 0.1 to 2 wt%,
based on the weight of the polymer composition. Further details about these
nucleating agents can be found e.g. in WO 99/24479 and WO 99/24501.
The present invention also provides a process for the preparation of the polymer
composition described above. The process of the present invention comprises the
following steps in any sequence;
(i) copolymerization of propylene with an olefin comonomer to result in a
polypropylene random copolymer, and
(ii) copolymerization of propylene with an olefin comonomer to result in an
elastomeric copolymer.
Since the polypropylene random copolymer is present in a higher amount, it is acting
as a matrix into which the elastomeric copolymer is included to improve impact
properties.
Preferably, the reaction steps (i) and (ii) are carried out in at least one loop reactor
and/or at least one gas phase reactor.
It is preferred to have the sequence (i) -> (ii).

The amount and feed rate of olefin comonomer fed into the reactor for
copolymerization with propylene are such that the polypropylene-based matrix has an
amount of olefin comonomer units of 0.2 to 5 wt%, based on the weight of the
matrix. Preferably, ethylene is used as the olefin comonomer.
When the matrix is made of the random copolymer only, the amount of olefin
comonomer units within the matrix corresponds to the amount of olefin comonomer
units within the random copolymer. However, the matrix may include further
polymeric components, as already discussed above.
According to a preferred embodiment, the first reaction step is carried out in a loop
reactor, this step optionally also comprising at least one gas phase reactor to which
the product of the loop reactor is transferred to continue polymerization. Preferably,
any reaction medium used and any non-reacted reagents are at least partly removed
before transfer from the loop reactor to the gas phase reactor is performed.
For the present invention, conventional loop and gas phase reactors which are
commonly known in the relevant technical field can be used.
In a preferred embodiment, reaction conditions are chosen which result in a unimodal
polypropylene random copolymer. Of course, when the polypropylene-based matrix
is made of the random copolymer only, a unimodal matrix is obtained.
However, within the present invention, it is also possible to effect polymerization of
the random copolymer under conditions which result in a multimodal, e.g. bimodal
polymer. This is preferably accomplished by using a loop reactor in serial
configuration with one or more gas phase reactors.
Preferably, the process of the present invention comprises an additional step (iii) for
polypropylene homopolymerization. When using such a polypropylene
homopolymerization step, the process steps are preferably carried out either in the
sequence (i)-»(iii)-»(ii) or the sequence (iii)->(i)->(ii)
If the polypropylene homopolymer is prepared first, reaction conditions are chosen so
as to preferably have a MFR2.16kg/230°C of less than 20g/10 min for the homopolymer.

By using a loop reactor and at least one gas phase reactor in serial configuration and
working at different conditions, a multimodal (e.g. bimodal) polypropylene
homopolymer can be obtained. However, within the context of the present invention,
the polypropylene homopolymer can also be unimodal.
As an alternative, the polypropylene random copolymer is prepared first. Again,
polymerization can be effected by using a loop reactor only or a loop reactor in serial
configuration with at least one gas phase reactor, the latter configuration resulting in a
multimodal (e.g. bimodal) polypropylene random copolymer.
Preferably, a loop reactor for preparing a polypropylene homopolymer or random
copolymer is operated at a temperature of 50 °C to 100 °C and a pressure of 3000 kPa
to 5500 kPa. In a preferred embodiment, at least one loop reactor is operated under
supercritical conditions. As an example, supercritical conditions can include a
temperature of at least 92°C and a pressure of at least 4600 kPa.
Preferably, a gas phase reactor for preparing a polypropylene homopolymer or
random copolymer is operated at a temperature of 50 °C to 110 °C and a pressure of
1500 kPa to 4000 kPa.
To further improve the balance between processability and mechanical properties of
the polymer composition, a specific split between a first process step producing a first
component and a second process step producing a second component can be chosen.
The split indicates the weight ratio between different polymeric components prepared
in different reaction steps.
Preferably, the split between process step (i) and process step (ii), irrespective of their
sequence, is from 95 : 5 to 70 : 30, more preferably from 95 : 5 to 80 : 20 and even
more preferably from 95 : 5 to 85 : 15.
When using a polypropylene homopolymerization step (iii), the split between the
combined process steps (i) and (iii) and the process step (ii) is preferably from 95 : 5
to 70 : 30, more preferably from 95 : 5 to 80 : 20 and even more preferably from 95 :
5 to 85: 15.

As a catalyst for the preparation of the polypropylene homopolymer and/or the
polypropylene random copolymer, any stereo-specific catalyst for propylene
polymerization can be used, which is capable of catalyzing polymerization and
copolymerization of propylene and comonomers at a pressure of 500-10000
kPa, in particular 2500-8000 kPa, and at a temperature of 40-110°C, in
particular 60-110°C.
Preferably, the catalyst comprises a high-yield Ziegler-Natta type catalyst
which can be used at high polymerization temperatures of 80°C or more.
Generally, the Ziegler-Natta catalyst used in the present invention comprises a
catalyst component, a cocatalyst component, an external donor, the catalyst
component of the catalyst system primarily containing magnesium, titanium,
halogen and an internal donor. Electron donors control the sterospecific
properties and/or improve the activity of the catalyst system. A number of
electron donors including ethers, esters, polysilanes, polysiloxanes, and
alkoxysilanes are known in the art.
The catalyst preferably contains a transition metal compound as a procatalyst
component. The transition metal compound is selected from the group
consisting of titanium compounds having an oxidation degree of 3 or 4,
vanadium compounds, zirconium compounds, cobalt compounds, nickel
compounds, tungsten compounds and rare earth metal compounds, titanium
trichloride and titanium tetrachloride being particularly preferred.
It is preferred to use catalysts which can withstand the high temperatures
prevailing in the loop reactor. The conventional Ziegler-Natta catalysts for
isotactic polymerization of propylene generally have an operating temperature
limit of around 80°C, above which they either become deactivated or lose their
stereo-selectivity. This low polymerization temperature may put a practical
limit on the heat removal efficiency of the loop reactor.
One preferred catalyst to be used according to the invention is disclosed in EP
591 224 which discloses a method for preparing a procatalyst composition from

magnesium dichloride, a titanium compound, a lower alcohol and an ester of
phthalic acid containing at least five carbon atoms. According to EP 591 224, a
trans-esterification reaction is carried out at an elevated temperature between
the lower alcohol and the phthalic acid ester, whereby the ester groups from the
lower alcohol and the phthalic ester change places.
Magnesium dichloride can be used as such or it can be combined with silica,
e.g. by absorbing the silica with a solution or slurry containing magnesium
dichloride. The lower alcohol used may preferably be methanol or ethanol,
particularly ethanol.
The titanium compound used in the preparation of the procatalyst is preferably
an organic or inorganic titanium compound, which is at the oxidation state of 3
or 4. Also other transition metal compounds, such as vanadium, zirconium,
chromium, molybdenum and tungsten compounds can be mixed with the
titanium compound. The titanium compound usually is a halide or oxyhalide, an
organic metal halide, or a purely metal organic compound in which only
organic ligands have been attached to the transition metal. Particularly
preferred are the titanium halides, especially titanium tetrachloride.
The alkoxy group of the phthalic acid ester used comprises at least five carbon
atoms, preferably at least eight carbon atoms. Thus, as the ester may be used
e.g. propylhexyl phthalate, dioctyl phthalate, di-isodecyl phthalate and
ditridecyl phthalate. The molar ratio of phthalic acid ester and magnesium
halide is preferably about 0.2:1.
The transesterification can be carried out, e.g. by selecting a phthalic acid ester
- a lower alcohol pair, which spontaneously or by the aid of a catalyst, which
does not damage the procatalyst composition, transesterifies the catalyst at an
elevated temperature. It is preferred to carry out the transesterification at a
temperature which is 110-115°C, preferably 120-140°C.
In a preferred embodiment, the Ziegler-Natta catalyst system can be modified
by polymerizing in the presence of the catalyst a vinyl compound of the formula


wherein R1 and R2 together form a 5 or 6-membered saturated, unsaturated or
aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon
atoms, and the modified catalyst is used for the preparation of the polymer
composition. The polymerized vinyl compound can act as a nucleating agent. Further
details about this modification are provided in EP 1 028 985.
The catalyst prepared by the method above is used together with an
organometallic cocatalyst and with an external donor. Generally, the external
donor has the formula

wherein
R and R' can be the same or different and represent a linear, branched or cyclic
aliphatic, or aromatic group;
R" is methyl or ethyl;
n is an integer of 0 to 3;
m is an integer of 0 to 3; and
n+m is 1 to 3.
In particular, the external donor is selected from the group consisting of
cyclohexyl methylmethoxy silane (CHMMS), dicyclopentyl dimethoxy silane
(DCPDMS), diisopropyl dimethoxy silane, di-isobutyl dimethoxy silane, and
di-t-butyl dimethoxy silane.
An organoaluminium compound is used as a cocatalyst. The organoaluminium
compound is preferably selected from the group consisting of trialkyl
aluminium, dialkyl aluminium chloride and alkyl aluminium sesquichloride.
According to the invention, such catalysts are typically introduced into the first
reactor only. The components of the catalyst can be fed into the reactor

separately or simultaneously or the components of the catalyst system can be
precontacted prior to the reactor.
Such precontacting can also include a catalyst prepolymerization prior to
feeding into the polymerization reactor proper. In the prepolymerization, the
catalyst components are contacted for a short period with a monomer before
feeding to the reactor.
As discussed above, in preferred embodiments the random copolymer and optionally
the homopolymer are prepared first, whereas the elastomeric copolymer is prepared
in a final step. Preferably, the elastomeric copolymer is prepared in a gas phase
reactor. Optionally, two or more gas phase reactors can be used. The one or more gas
phase reactors for the preparation of the elastomer can be in serial configuration with
the reactors used for the preparation of the homopolymer and random copolymer.
When using such a reactor configuration, the elastomeric copolymer is produced in
the presence of the homopolymer/random copolymer matrix and dispersed therein.
As an alternative, the elastomeric copolymer can be prepared separately and mixed
with the polypropylene-based matrix at a later stage.
In general, the conditions for the preparation of the elastomeric copolymer are within
the limits of conventional conditions for ethylene-propylene rubber (EPM)
production. Typical conditions are disclosed e.g. in Encyclopedia of Polymer Science
and Engineering, second edition, vol. 6, p. 545-558. An elastomeric product is
obtained when the comonomer content of the polymer is within a certain range.
The catalytic system described above for the preparation of the polypropylene
homopolymer and random copolymer can also be used for the preparation of the
elastomeric copolymer.
The present invention also provides a pipe and pipe fittings prepared from the
polymer composition discussed above, e.g. by extrusion or injection moulding. The
polymer composition can be used for pressure as well as non-pressure pipes.
Preferably, it is used for non-pressure pipes.

In particular, within the context of the present invention smooth solid wall pipes and
structured wall pipes can be mentioned. Structured wall pipes include e.g. single layer
corrugated pipes, ribbed pipes, twin wall pipes with hollow sections, multilayer pipes
with or without hollow sections or foamed layers, and spirally wound pipes with or
without hollow sections with smooth or corrugated pipe design.
In general, pipes with thin sections, either smooth solid wall pipes of smaller
diameter or structured wall pipes with thin sections are more sensitive to the
formation of cracks. Furthermore, due to the three-dimensional structure of structured
wall pipes, high local stress can be generated when subjected to external load
conditions. However, pipes made of the polymer composition of the present invention
have high notch resistance and high impact values at low temperature.
The pipe of the present invention preferably has a resistance to accelerated crack
growth in the notched pipe test according to ISO 13479 at 80°C and 4.2 MPa of at
least 50 h, more preferably at least 90 h, even more preferably at least 130 h, and
most preferably at least 200 h.
According to a preferred embodiment, the pipe has a Charpy impact strength,
measured according to ISO 179/leA at -20°C, of at least 3.0 kJ/m2, more preferably
at least 4.0 kJ/m2, even more preferably at least 5.0 kJ/m2, and most preferably at
least 6.0 kJ/m2.
The present invention also provides an article having a surface roughness Rz,
measured according to ISO 4287, of less than 18 µm, more preferably less than 14
urn, even more preferably less than 10 µm, and most preferably less than 6 µm.
Preferably, the article is a pipe, in particular one of those pipes mentioned above.
The invention is now described in further detail by making reference to the following
examples.

1. Measuring methods
fa) Melt flow rate
Melt flow rate was measured according to ISO 1133, either at 230°C and 2.16 kg
(MFR2.16kg/230°c) or at 230°C and 10 kg (MFR10kg/230°c).
(b) Tensile properties
Tensile modulus was determined according to ISO 527-2/1 B at 1 mm/min. and 23°C.
(c) Notch resistance
Notch resistance was determined in the notched pipe test according to ISO 13479 at
80°C and 4.2 MPa on a 32 mm diameter pipe with a wall thickness of 3 mm,
condition water-in-water. The circumferential (hoop) stress is based on the
dimensions of the unnotched pipes. The remaining pipe wall ligament after
machining of each notch was 0.8 times the wall thickness.
The pipe extruder used for preparing the pipe to be tested was a conventional pipe
extruder equipped with a die head for producing diameter 32 mm pipes with a wall
thickness of 3.0 mm.
Extruder screw diameter: 45 mm
Screw length: 30 * diameter D (30 D)
Line speed: 6 m/min
RPM: Adjusted in order to give the target output
Temperature settings: 180°C-220°C
(d) Storage modulus G'
Storage modulus G' was determined on a dynamic rheometer at G" = 5 kPa and
220°C. Measurements were made on a Physica MCR 300 rheometer with a plate-
plate fixture, plate diameter 25 mm, and a distance between the plates of 1.8 mm. The

frequency range was 0.01-100 Hz at a measuring temperature of 220°C. All
measurements were made in nitrogen atmosphere.
(e) Notched impact strength
Notched impact strength was determined according to ISO 179/leA at -20°C, based
on compression-moulded samples.
(f) Surface roughness Rz
Surface roughness Rz (average of 6 measurements) was determined according to ISO
4287 on the inner surface of the diameter 32 mm pipe samples.
(g) Rheotens test
The test is performed with a Rheotens apparatus from Gottfert in a standard
climatized room with controlled room temperature of 23 °C. The Rheotens apparatus
is combined with an extruder/melt pump for continuously feeding the melt strand.
The extrusion temperature is 200 °C, a capillary die with a diameter of 2 mm and a
length of 6 mm is used and the acceleration of the melt strand drawn down is 120
mm/s . The distance between the die and the wheels is 100 mm.
(h) Polydispersity index PI
The polydispersity index PI is calculated according to the following equation:

wherein Gc in Pa is the cross over modulus at which G'=G"=Gc.
The measurements have been made according to ISO 6421-10. Measurements were
made at 220°C. G' and G" indicate storage modulus and loss modulus, respectively.
Measurements were made on a Physica MCR 300 rheometer with a plate-plate
fixture, plate diameter 25 mm, and a distance between the plates of 1.8 mm.
All mechanical properties were determined on samples prepared 3 weeks ± 2 days
before the measurement.

2. Materials
Inventive examples 1 and 2 have been prepared using two loop reactors and one gas
phase reactor. The polypropylene-based matrix comprises a polypropylene random
copolymer in combination with a polypropylene homopolymer wherein the random
copolymer is prepared first, followed by the preparation of the homopolymer.
Ethylene was used as a comonomer for the random copolymer and the elastomer.
In inventive examples 3 and 4, the polypropylene-based matrix was obtained by
preparing a polypropylene random copolymer in a loop reactor, followed by
preparing a polypropylene homopolymer in a first gas phase reactor. Subsequently,
the elastomeric copolymer was produced in a second gas phase reactor. Ethylene was
used as a comonomer for the random copolymer and the elastomer.
In inventive examples 1, 2, 3 and 4, a Ziegler-Natta type catalyst was used which had
been modified by transesterification and polymerization of a vinyl compound as
described above.
The reference materials were prepared using either one or two loop reactors and a
gas, as shown in table 2. phase reactor. The reference materials have a pure
polypropylene homopolymer matrix (i.e. no olefin comonomer units within the
matrix) blended with an elastomeric ethylene-propylene copolymer. A Ziegler-Natta
type catalyst was used. For Ref. 2, a Ziegler-Natta type catalyst was used which had
been modified by transesterification and polymerization of a vinyl compound as
described above. Ref. 1 and 2 were nucleated with Further details about the manufacturing processes are given in Tables 1-2.






The results demonstrate that high notch resistance and high impact strength can be
obtained when the matrix has a low amount of olefin comonomer units within the
range defined above and the storage modulus of the polymer composition is kept
below 3100 Pa. Even at high MFR values, which improve processability, the notch
resistance of the inventive materials is still on a high level (see Ex. 3 and in particular

Ex. 4) whereas the reference material of high MFR value (see Ref. 3) has a very low
notch resistance.

We claim :
1. A polymer composition, comprising
(i) a polypropylene-based matrix which comprises at least one polypropylene random copolymer,
prepared by copolymerization of propylene with an olefin comonomer, wherein the amount of
olefin comonomer units within the matrix is from 0.2 wt% to 5 wt% based on the weight of the
polypropylene-based matrix, and
(ii) an elastomeric copolymer of propylene and at least one olefin comonomer,
the polymer composition having a storage modulus G' at a loss modulus G"=5 kPa of G'(G"=5
kPa) 2. The polymer composition as claimed in claim 1, wherein the olefin comonomer of the
polypropylene random copolymer is selected from ethylene, C4 to C10 alpha-olefins, or mixtures
thereof.
3. The polymer composition as claimed in claim 2, wherein the olefin comonomer is
ethylene.
4. The polymer composition as claimed in claim 3, wherein the ethylene comonomer units
within the polypropylene random copolymer are present in an amount of 0.2 to 4 wt%, based on
the amount of the polypropylene-based matrix.
5. The polymer composition as claimed in any of the preceding claims, wherein the
polypropylene-based matrix is ummodal.
6. The polymer composition as claimed in any of the claims 1 to 4, wherein the
polypropylene-based matrix comprises a polypropylene homopolymer.
7. The polymer composition as claimed in claim 6, wherein the polypropylene
homopolymer has a melt flow rate MFR2.16kg/230°c of less than 20 g/10 min.
8. The polymer composition as claimed in claim 6 or 7, wherein the polypropylene-based
matrix is multimodal.
9. The polymer composition as claimed in claim 8, wherein the weight average molecular
weight of the polypropylene random copolymer is higher than the weight average molecular
weight of the polypropylene homopolymer.
10. The polymer composition as claimed in any of the preceding claims, wherein the
olefin comonomer of the elastomeric copolymer is selected from ethylene, C4 to C10 alpha-

olefins, or mixtures thereof.
11. The polymer composition as claimed in claim 10, wherein the olefin comonomer is ethylene
and the elastomeric copolymer comprises in an amount of 10 to 70 wt% of ethylene comonomer units.
12. The polymer composition as claimed in any of the preceding claims, wherein elastomeric
copolymer comprises in an amount of 5 wt% to 30 wt%.
13. The polymer composition as claimed in any of the preceding claims, wherein G'(G"=5 kPa) 2900 Pa.
14. The polymer composition as claimed in any of the preceding claims, wherein the tensile
modulus is at least 1350 MPa.
15. The polymer composition as claimed in any of the preceding claims, having a ratio of
draw ability vmax, to melt strength Fmax of more than 2.1 mm/s*cN, measured according to the Rheotens
test at an extrusion temperature of 200 °C.
16. The polymer composition as claimed in claim 15, wherein the ratio of drawability to melt
strength is more than 2.5 mm/s*cN
17. The polymer composition as claimed in any of the preceding claims, having a haul off force F
of 60 cN or less at a velocity v = 80 mm/s in the Rheotens test at an extrusion temperature of 200 °C.
18. The polymer composition as claimed in any of the preceding claims, having a melt flow rate
MFR2.16kg/230°c within the range of C.2 to 10 g/10 min.
19. A process for preparing the polymer composition as claimed in any of the claims 1 to 18,
comprising of the following steps in any sequence:
(i) copolymerization of propylene with an olefin comonomer to result in a polypropylene random
copolymer, and
(ii) copolymerization of propylene with an olefin comonomer to result in an elastomeric copolymer.
20. The process as claimed in claim 19, wherein the process step (i) and/or the process step (ii) are
carried out in at least one loop reactor and/or at least one gas phase reactor.
21. The process as claimed in claim 19 or 20, wherein the process steps are carried out in the
following sequence: (i) -> (ii).

22. The process as claimed in any of the claims 19 to 21, wherein the first process step is carried out
in a loop reactor, and the second process step is carried out in separate gas phase reactor(s).
23. The process as claimed in claim 22, wherein the product of the first process step, carried out in a
loop reactor, is continued to be polymerised further in a gas phase reactor.
24. The process as claimed in claim 23, wherein the second process step, and the further
polymerisation step are carried out in separate gas phase reactors.
25. The process as claimed in any of the claim 19 to 24, further comprising a step (iii) for propylene
homopolymerization.
26. The process as claimed in claim 25, wherein the process steps are carried out either in the
sequence (i) -> (iii) -> (ii) or the sequence (iii) -» (i) -» (ii).
27. The process as claimed in any of the claims 19 to 26, wherein the split between the process step
(i), optionally in combination with process step (iii), and the process step (ii), irrespective of their
sequence, is from 95 : 5 to 70 : 30.
28. The process as claimed in any of the claims 19 to 27, using a Ziegler-Natta catalyst including an
electron donor.
29. The process as claimed in claim 26, wherein the Ziegler-Natta catalyst comprises a cocatalyst
component which has been prepared by bringing together magnesium dichloride, a lower alcohol selected
from methanol, ethanol or mixtures thereof, a titanium compound and an ester of phthalic acid having an
alkoxy group of at least five carbon atoms.
30. The process as claimed in claim 26, wherein the Ziegler-Natta catalyst is modified by
polymerizing in the presence of the catalyst a vinyl compound of the formula
■ I
wherein R1 and R2 together form a 5 or 6-membered saturated, unsaturated or aromatic ring or
independently represent an alkyl group comprising 1 to 4 carbon atoms, and the modified catalyst is

used for the preparation of the polymer composition.
31. The process as claimed in any of the claims 19 to 30, wherein a nucleating agent is added
selected from talc, polymerized vinyl compounds, dibenzylidene sorbitol, sodium benzoate,
di(alkylbenzylidene)sorbitol, or mixtures thereof.


Abstract

Title : POLYPROPYLENE OF IMPROVED PROCESS ABILITY FOR PRODUCTION OF PIPES
The present invention relates to a polymer composition, comprising
(i) a polypropylene-based matrix which comprises a polypropylene random
copolymer prepared by copolymerization of propylene with an olefin comonomer,
wherein the amount of olefin comonomer units is within the range of 0.2 wt% to 5
wt%, based on the weight of the polypropylene-based matrix, and
(ii) an elastomeric copolymer of propylene and at least one olefin comonomer,
the polymer composition having a storage modulus G' at a loss modulus G"=5 kPa of G'(5 kPa)

Documents:

03782-kolnp-2007-abstract.pdf

03782-kolnp-2007-claims.pdf

03782-kolnp-2007-correspondence others.pdf

03782-kolnp-2007-description complete.pdf

03782-kolnp-2007-form 1.pdf

03782-kolnp-2007-form 3.pdf

03782-kolnp-2007-form 5.pdf

03782-kolnp-2007-gpa.pdf

03782-kolnp-2007-international search report.pdf

03782-kolnp-2007-pct priority document notification.pdf

03782-kolnp-2007-pct request form.pdf

3782-KOLNP-2007-(17-05-2012)-CORRESPONDENCE.pdf

3782-KOLNP-2007-(19-12-2011)-ABSTRACT.pdf

3782-KOLNP-2007-(19-12-2011)-CLAIMS.pdf

3782-KOLNP-2007-(19-12-2011)-CORRESPONDENCE.pdf

3782-KOLNP-2007-(19-12-2011)-DESCRIPTION (COMPLETE).pdf

3782-KOLNP-2007-(19-12-2011)-FORM-1.pdf

3782-KOLNP-2007-(19-12-2011)-FORM-2.pdf

3782-KOLNP-2007-(19-12-2011)-FORM-3.pdf

3782-KOLNP-2007-(19-12-2011)-OTHER PATENT DOCUMENT.pdf

3782-KOLNP-2007-(19-12-2011)-OTHERS.pdf

3782-KOLNP-2007-ASSIGNMENT.pdf

3782-KOLNP-2007-CORRESPONDENCE 1.1.pdf

3782-KOLNP-2007-CORRESPONDENCE 1.2.pdf

3782-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

3782-KOLNP-2007-EXAMINATION REPORT.pdf

3782-KOLNP-2007-FORM 13 1.1.pdf

3782-KOLNP-2007-FORM 18 1.1.pdf

3782-kolnp-2007-form 18.pdf

3782-KOLNP-2007-FORM 3 1.2.pdf

3782-KOLNP-2007-FORM 3-1.1.pdf

3782-KOLNP-2007-FORM 5.pdf

3782-KOLNP-2007-FORM-13.pdf

3782-KOLNP-2007-GPA.pdf

3782-KOLNP-2007-GRANTED-ABSTRACT.pdf

3782-KOLNP-2007-GRANTED-CLAIMS.pdf

3782-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

3782-KOLNP-2007-GRANTED-FORM 1.pdf

3782-KOLNP-2007-GRANTED-FORM 2.pdf

3782-KOLNP-2007-GRANTED-SPECIFICATION.pdf

3782-KOLNP-2007-INTERNATIONAL SEARCH REPORT.pdf

3782-KOLNP-2007-OTHERS PCT FORM.pdf

3782-KOLNP-2007-OTHERS.pdf

3782-KOLNP-2007-PCT PRIORITY DOCUMENT NOTIFICATION.pdf

3782-KOLNP-2007-PCT REQUEST FORM.pdf

3782-KOLNP-2007-REPLY TO EXAMINATION REPORT 1.1.pdf

3782-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf


Patent Number 253625
Indian Patent Application Number 3782/KOLNP/2007
PG Journal Number 32/2012
Publication Date 10-Aug-2012
Grant Date 07-Aug-2012
Date of Filing 05-Oct-2007
Name of Patentee BOREALIS TECHNOLOGY OY
Applicant Address P.O. BOX 330, FIN-06101, PORVOO,
Inventors:
# Inventor's Name Inventor's Address
1 HARJUNTAUSTA JARMO TALKOOLIE 4D, FI-00630 HELSINKI
2 ALASTALO KAUNO KARJAPOLKU 4, FI-06400 PORVOO
3 LUND KENNETH O GRONGATAN 5, SE-451 51 UDDEVALLA
4 EK CARL-GUSTAF BERGSKADDEGATAN 8, SE-426 58 VASTRA FROLUNDA
PCT International Classification Number C08L 23/10
PCT International Application Number PCT/EP2006/004444
PCT International Filing date 2006-05-11
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05010973.5 2005-05-20 EUROPEAN UNION