Title of Invention

POLYOLEFIN COMPOSITION COMPRISING SILICON-CONTAINING FILLER

Abstract The present invention relates to a polyolefin composition comprising a polyolefin base resin comprising an olefin homo- or copolymer (A) having hydrolysable silicon-containing groups, and an inorganic mineral filler (B) containing on its surface silanol groups or precursors thereof.
Full Text Polyolefin composition comprising silicon-containing filler
The present invention relates to a polyolefin composition with improved
mechanical strength, especially toughness and impact strength and heat
resistance. Especially, the present invention relates to polyolefin
compositions wherein a silicon compound-containing filler is strongly
embedded in a polyolefin. The present invention further relates to an article
made of the polyolefin composition and the use of the polyolefin
composition for the production of an article.
Due to their chemical and thermal resistance as well as their mechanical
strength polyolefin compositions are used in various applications such as
moulding, film or other applications.
For demanding applications, e.g. under very low temperature conditions or
for heavy duty packaging polyolefins used for these purposes often lack
mechanical strength and heat resistance. Therefore, non-polymer
reinforcement materials like mineral fillers, glass, or mineral fibres are
incorporated in polyolefin compositions as modifiers. However, when using
such mineral fillers the mechanical performance of such polyolefin
compositions is often limited due to a low adhesion between the polymeric
matrix and the filler. Especially the toughness, impact strength and
elongation at break is severely lowered in such applications.
It is known in the prior art to use glass fibre reinforcements where the
reinforcement takes place by chemical coupling via surface modification of
the fibre with e.g. organosilicon compounds and the addition of a
compatibiliser to the polymeric phase. An example for this technology is
US 5,910,523 where an aminosilane functionalised filler (e.g. silica) is

reacted with carboxyl groups of a carboxylated or maleated polyolefin to
form a partially or fully polyolefin functionalised filler. However, such an
approach requires specific chemistry and the results in mechanical strength
are still poor.
JP-A-2138353 discloses a polymer composition comprising a propylene
homopolymer or an ethylene-propylene copolymer, a silane coupling agent
and an inorganic filler.
It is also known to use a non-treated filler with a polymeric compatibiliser
to improve the properties of a polymer, especially polyolefin composition.
J. Duchet et al report in J.Appl.Polym.Sci. 65 (1997) 2481-2492 on
polyethylene grafting on glass surfaces wherein chlorosilane-terminated
polyethylenes with different molar masses were provided to obtain semi-
crystalline polymers able to crystallise with the free chains of the
polyethylene matrix and polymer chains could react with the glass surface.
The technique was used for coating of silicon wafer surfaces.
Another approach in JP2004-051722 disclosing a polyolefin composite
resin composition obtained by melt kneading a composition comprising (A)
a phyllosilicate, (B) an interlayer dilating agent, and (C) a silane compound
having an unsaturated bond and/or a reactive functional group with (D) a
polyolefin resin. The melt tension and mouldability is improved by mixing
such a specific filler to the polyolefin resin (D).
However, even in such cases of using surface modified or unmodified
fillers mixed into polyolefin resin matrices, problems regarding a highly
homogeneous dispersion are still experienced. Moreover, exfoliation is not
prevented sufficiently to reach the theoretical potential of the materials.
Moreover, the prior art has experienced severe problems when the final
polymeric composition is put under mechanical load and/or deformation

resulting in debonding and cavitation at the particle surface causing stress
whitening and finally fracture of the composition.
Therefore, it is one object of the present invention to overcome the above
problems and to provide a polyolefin composition having improved
mechanical characteristics, in particular having improved toughness,
impact strength and elongation at break, and improved bonding of the filler
particles to the polyolefin matrix or parts thereof.
The present invention resides in the finding that a mineral filler can easily
and safely be bonded to a polymeric matrix so that adhesion between filler
and polymer is sharply improved. This can be achieved by chemically
binding an inorganic mineral filler containing on its surface silanol groups
or precursors thereof to polymer chains of a hydrolysable silicon group-
containing polyolefin. Thus, a polyolefin composition improved in
mechanical strength, especially toughness, impact strength and elongation
at break can be obtained.
According to a first aspect of the present invention, a polyolefin
composition is provided, comprising:
- a polyolefin base resin comprising an olefin homo- or
copolymer (A) having hydrolysable silicon-containing groups,
and
- an inorganic mineral filler (B) containing on its surface silanol
groups or precursors thereof.
The term polyolefin denotes an olefin homo- or copolymer of a mixture of
such olefin homo- or copolymers.

The polyolefin composition according to the present invention preferably
comprises a silanol condensation catalyst capable of cross-linking the
hydrolysable silicon group-containing polyolefin (A). Thus, the cross-
linking reaction may be preferably carried out at a temperature of not more
than 40 °C, more preferably not more than 30 °C, even more preferred at
about room temperature. The cross-linking reaction may but need not be
conducted in the presence of moisture.
Basically, the hydrolysable silicon-group containing polyolefin (A) may
form a matrix in which the particulate filler is dispersed. As the polyolefin
(A) contained in or forming the base resin an ethylene or propylene homo-
or copolymer may be used.
Preferably, filler (B) is substantially encapsulated by the hydrolysable
silicon-group containing polyolefin (A). Thus, the adhesion between filler
and polyolefin is guaranteed and the homogeneity of the total composition
is improved.
According to another aspect a heterophasic olefin polymer composition
may be provided.
Thus, according to a preferred embodiment of the present invention the
base resin comprises a propylene homo- or copolymer (C) which forms a
matrix phase, and a disperse phase which is distributed in said matrix phase
and comprises the polyolefin (A) having hydrolysable silicon-containing
groups.
If such a heterophasic olefin polymer composition is provided, it is more
preferred that the inorganic mineral filler (B) is present only in the
dispersed phase.

An elastomer is usually and preferably contained in the disperse phase of
the heterophasic olefin polymer. Such an elastomer may be any which is
typically contained in heterophasic polypropylenes such as an ethylene-
propylene copolymer and optionally other alpha-olefin copolymer.
Suitable elastomers include ethylene-butene rubber, copolymer rubber
such as ethylene-propylene rubber (EPR) or metallocene-catalyst based
ethylene plastomers. Elastomer may also be added in the form of
ethylene-propylene-diene monomer (EPDM) or styrene-based elastomers
(e.g. SEBS). These elastomers can be prepared by conventional
processes and blended into the heterophasic polymers of the invention by
standard mixing techniques.
While elastomer and polyolefin (A) may be different polymers, in an
embodiment of the invention the olefin homo- or copolymer (A)
comprising hydrolysable silicon-containing groups is an elastomer.
According to this aspect of the present invention, a cross-linked
heterophasic polypropylene composition may be provided which is
obtainable by a process comprising the steps of:
(i) blending (A), (B) and (C) as defined above, together with a silanol
condensation catalyst,
(ii) granulation of the blend of step (i) in a water bath, and
afterwards
(iii) cross-linking the obtained heterophasic polypropylene
composition at 10 to 40°C under a humidity of below 85 % to a cross-
linking degree of at least 30 %, based on the total polyolefin (A).

Preferably, step (i) is carried out at a temperature of 180 to 230 °C and
in step (ii) the residence time of the blend of step (i) in the water bath for
granulation preferably is less than 30 seconds.
The selective cross-linking of the polyolefin phase allows stabilising of
the phase morphology of the heterophasic polypropylene composition.
The resulting heterophasic polypropylene compositions according to the
present

invention are additionally characterised by high heat deflection
temperatures and improved scratch resistance resulting from the continuous
matrix phase as well as a reduced shrinkage and improved surface quality
resulting from the cross-linked polyolefin phase.
Such a heterophasic polypropylene composition preferably has a weight
ratio of propylene homo- or copolymer (C) to polyolefin (A) from 97:3 to
45:55, more preferably from 95:5 to 45:55, still more preferably from 90:10
to 50:50, even more preferably from 85:15 to 60:40, and most preferably
from 85:15 to 80:20.
Furthermore, such a heterophasic polypropylene composition preferably
has a weight ratio of propylene homo- or copolymer matrix (C) to the
dispersed phase of 95:5 to 45:55, more preferably from 90:10 to 50:50,
even more preferably from 85:15 to 60:40.
Preferably, the inorganic mineral filler (B) is present in the composition in
an amount of from 0.5 to 30 wt.%, more preferably from 1 to 25 wt.%, and
most preferably from 1.5 to 15 wt.%.
In the embodiment where polyolefin base resin comprises a matrix and a
dispersed phase, preferably at least 90 wt.% of inorganic filler (B) is
present in the disperse phase, more preferably at least 95 wt.% and most
preferably 100 wt.%.
The hydrolysable silicon-containing groups can be introduced e.g. by
grafting the silicon compound into the polyolefin or by copolymerisation of
the olefin monomers and silicon groups containing monomers. Such
techniques are known e.g. from US 4,413,066, US 4,297,310, US
4,351,876, US 4,397,981, US 4,446,283 and US 4,456,704.

In the case the silicon group containing polyolefin (A) has been obtained by
copolymerisation, the copolymerisation is preferably carried out with an
unsaturated silicon compound represented by the formula

wherein
R1 is an ethylenically unsaturated hydrocarbyl, hydrocarbyloxy or
(meth)acryloxy hydrocarbyl group,
R2 is an aliphatic saturated hydrocarbyl group,
Y which may be the same or different, is a hydrolysable organic group and
q is 0, 1 or 2.
Special examples of the unsaturated silicon compound are those wherein R1
is vinyl, allyl, isopropenyl, butenyl, cyclohexanyl or gamma-
(meth)acryloxy propyl; Y is methoxy, ethoxy, formyloxy, acetoxy,
propionyloxy or an alkyl-or arylamino group; and R2 , if present, is a
methyl, ethyl, propyl, decyl or phenyl group.
A preferred unsaturated silicon compound is represented by the formula

wherein A is a hydrocarbyl group having 1-8 carbon atoms, preferably 1-4
carbon atoms.
The most preferred compounds are vinyl trimethoxysilane, vinyl
bismethoxyethoxysilane, vinyl triethoxysilane, gamma-(meth)acryl-
oxypropyltrimethoxysilane, gamma(meth)acryloxypropyltriethoxysilane,
and vinyl triacetoxysilane.

The copolymerisation of the olefin and the unsaturated silane compound
may be earned out under any suitable conditions resulting in the
copolymerisation of the two monomers.
Moreover, the copolymerisation may be implemented in the presence of
one or more other comonomers which can be copolymerised with the two
monomers. Such comonomers include (a) vinyl carboxylate esters, such as
vinyl acetate and vinyl pivalate, (b) alpha-olefins, such as propene, 1-
butene, 1-hexane, 1-oetene and 4-methyl-1-pentene, (c) (meth)acrylates,
such as methyl(meth)acrylate, ethyl(meth)acrylate and butyl(meth)acrylate,
(d) olefinically unsaturated carboxylic acids, such as (meth)acrylic acid,
maleic acid and fumaric acid, (e) (meth)acrylic acid derivativs, such as
(meth)acrylonitrile and (meth)acrylic amide, (f) vinyl ethers, such as vinyl
methyl ether and vinyl phenyl ether, and (g) aromatic vinyl compounds,
such as styrene and alpha-ethyl styrene.
Amongst these comonomers, vinyl esters of monocarboxylic acids having
1-4 carbon atoms, such as vinyl acetate, and (meth)acrylate of alcohols
having 1-4 carbon atoms, such as methyl(meth)-acrylate, are preferred.
Especially preferred comonomers are butyl acrylate, ethyl acrylate and
methyl acrylate.
Two or more such olefinically unsaturated compounds may be used in
combination. The term "(meth)acrylic acid" is intended to embrace both
acrylic acid and methacrylic acid. The comonomer content of the
copolymer may amount to 70 wt% of the copolymer, preferably about 0.5
to 35 wt%, most preferably about 1 to 30 wt%.
The grafted polyolefin (A) may be produced e.g. by any of the two methods
described in US 3,646,155 and US 4,117,195, respectively.

The silicon group containing polyolefin (A) according to the invention
preferably comprises 0.1 to about 10 wt% of the silicon compound, more
preferably 0.5 to 7 wt%, most preferably 1.0 to 4 wt% by weight, based on
the total polyolefin (A).
The silanol content can be adjusted by blending the grafted or
copolymerised polyolefin with a non-modified polyolefin.
If the silicon groups are introduced in the polyolefin (A) by polymerisation,
as described above, it is preferred that the silicon group containing
polyolefin (A) has a density of 900 to 940 kg/m3, more preferred of 910 to
935 kg/m3, most preferred of 915 to 930 kg/m3.
Furthermore, it is preferred that the silicon-grafted polyolefin (A) has a
density of 920 to 960 kg/m3, more preferred of 925 to 955 kg/m3, most
preferred of 930 to 950 kg/m3.
Moreover, the used polyolefin (A) preferably is an ethylene homo- or
copolymer, as a high density polyethylene, low density polyethylene, linear
low density polyethylene or their like.
According to another preferred embodiment a further olefin homo- or
copolymer (D) may be present in the disperse phase which is compatible
with the elastomer and the polyolefin (A) having hydrolysable silicon-
containing groups. Such a further olefin polymer may be a high pressure
polyethylene, e.g. a low density polyethylene, or ethylene copolymers like
linear low density polyethylene, very low density polyethylene or
metallocene-based ethylene plastomer. Addition of said component (D) will
further increase toughness and impact strength, especially at temperatures
below 0°C, and it will increase the extensibility expressed by the
elongation at break.

The cross-linking reaction may preferably be carried out by any known
silanol condensation catalyst. However, it is preferred that the silanol
condensation catalyst is typically selected from the group comprising
Lewis acids, inorganic acids such as sulphuric acid and hydrochloric acid,
and organic acids such as citric acid, stearic acid, acetic acid, sulfonic acid
and alkanoic acids as dodecanoic acid, organic bases, carboxylic acids and
organometallic compounds including organic titanates and complexes or
carboxylates of lead, cobalt, iron, nickel, zinc and tin or a precursor of any
of the compounds mentioned.
Further preferred, the aromatic organic sulfonic acid comprises the
structural element:

with Ar being an aryl group which may be substituted or non-substituted,
and x being at least 1.
The organic aromatic sulfonic acid silanol condensation catalyst may
comprise the structural unit according to formula (III) one or several times,
e.g. two or three times. For example, two structural units according to
formula (III) may be linked to each other via a bridging group such as an
alkylene group.
Preferably, Ar is a aryl group which is substituted with at least one C4- to
C30-hydrocarbyl group, more preferably C4- to C30-alkyl group.
Aryl group Ar preferably is a phenyl group, a naphthalene group or an
aromatic group comprising three fused rings such as phenantrene and
anthracene.

Preferably, in formula (III) x is 1, 2 or 3, and more preferably x is 1 or 2.
Furthermore, preferably the compound used as organic aromatic sulfonic
acid silanol condensation catalyst has from 10 to 200 C-atoms, more
preferably from 14 to 100 C-atoms.
In one preferred embodiment, Ar is a hydrocarbyl substituted aryl group
and the total compound containing 14 to 28 carbon atoms, and still further
preferred, the Ar group is a hydrocarbyl substituted benzene or naphthalene
ring, the hydrocarbyl radical or radicals containing 8 to 20 carbon atoms in
the benzene case and 4 to 18 atoms in the naphthalene case.
It is further preferred that the hydrocarbyl radical is an alkyl substituent
having 10 to 18 carbon atoms and still more preferred that the alkyl
substituent contains 12 carbon atoms and is selected from dodecyl and
tetrapropyl. Due to commercial availability it is most preferred that the aryl
group is a benzene substituted group with an alkyl substituent containing
12 carbon atoms.
The currently most preferred compounds are dodecyl benzene sulfonic acid
and tetrapropyl benzene sulfonic acid.
The silanol condensation catalyst may also be precursor of the sulfonic
acid compound, including all its preferred embodiments mentioned, i.e. a
compound that is converted by hydrolysis to such a compound. Such a
precursor is for example the acid anhydride of a sulfonic acid compound,
or a sulfonic acid that has been provided with a hydrolysable protective
group, as e.g. an acetyl group, which can be removed by hydrolysis.
In a second preferred embodiment, the sulfonic acid catalyst is selected
from those as described in EP 1 309 631 and EP 1 309 632, namely

a) a compound selected from the group of
(i) an alkylated naphthalene monosulfonic acid substituted with 1 to 4
alkyl groups wherein each alkyl group is a linear or branched alkyl with 5
to 40 carbons with each alkyl group being the same or different and
wherein the total number of carbons in the alkyl groups is in the range of
20 to 80 carbons;
(ii) an arylalkyl sulfonic acid wherein the aryl is phenyl or naphthyl and
is substituted with 1 to 4 alkyl groups wherein each alkyl group is a linear
or branched alkyl with 5 to 40 carbons with each alkyl group being the
same or different and wherein the total number of carbons in the alkyl
groups is in the range of 12 to 80;
(iii) a derivative of (i) or (ii) selected from the group consisting of an
anhydride, an ester, an acetylate, an epoxy blocked ester and an amine salt
thereof which is hydrolysable to the corresponding alkyl naphthalene
monosulfonic acid or the arylalkyl sulfonic acid;
(iv) a metal salt of (i) or (ii) wherein the metal ion is selected from the
group consisting of copper, aluminium, tin and zinc; and
b) a compound selected from the group of
(i) an alkylated aryl disulfonic acid selected from the group consisting
of the structure (IV):

and the structure (V):


wherein each of R1 and R2 is the same or different and is a linear or
branched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 with the
proviso that y + z is 1 to 4, n is 0 to 3, X is a divalent moiety selected from
the group consisting of -C(R3)(R4)-, wherein each of R3 and R4 is H or
independently a linear or branched alkyl group of 1 to 4 carbons and n is 1;
-C(=O)-, wherein n is 1; -S-, wherein n is 1 to 3 and -S(O)2-, wherein n is
1; and
(ii) a derivative of (i) selected from the group consisting of the
anhydrides, esters, epoxy blocked sulfonic acid esters, acetylates, and
amine salts thereof which is a hydrolysable to the alkylated aryl disulfonic
acid,
together with all preferred embodiments of those sulfonic acids as
described in the mentioned European Patents.
Preferably, in the polyolefin composition the silanol condensation catalyst
is present in an amount of 0.0001 to 6 wt%, more preferably of 0.001 to
2 wt%, and most preferably 0.02 to 0.5 wt%. It may also be used in an
amount of from 0.05 to 1 wt%.
Preferably, the cross-linkable polyolefin (A) comprises, still more
preferably consists of, a polyethylene containing hydrolysable silicon
groups.
The hydrolysable silicon groups may be introduced into the polyolefin by
copolymerisation of e.g. ethylene monomers with silicon group containing

comonomers or by grafting, i.e. by chemical modification of the polymer
by addition of silicon groups mostly in a radical reaction. Both techniques
are well known in the art.
Moreover, the polyolefin composition according to the invention may
further contain various additives, such as miscible thermoplastics, further
stabilizers, lubricants, fillers, colouring agents and foaming agents, which
can be added before during or after the blending step (i) to the composition.
As the silanol group-containing inorganic mineral filler (B) any type may
be used. However, it is preferred to use a particulate or plate-like filler
selected from the group consisting of the group talc, mica, montmorillonite,
wollastonite, bentonite, silica, halloysite, kaolinite and other
phyllosilicates.
In contrast to organically modified filler particles combined with a
compatibiliser, the inventive polyolefin compositions include an inorganic
mineral filler with silanol groups on their surfaces. Instead a group
hydrolysable to such a silanol group may be present on the surface of the
filler. Such groups are referred herein as "precursors" of silanol groups.
These may be coupled by a suitable condensation reaction to hydrolysable
silicon groups on the polymer chains of polyolefin (A), preferably with the
use of a suitable silanol condensation catalyst as specified above. The
reaction may but need not be conducted in the presence of moisture.
Fig. 1 and Fig. 2 exemplify the difference between the localisation of a
filler in a conventional polypropylene impact copolymer where a low
density polyethylene forms the disperse phase. It is evident from Fig. 1 that
a discrete dispersion separate from the polymeric phases is formed showing
that the filler particles are not homogeneously included in the polymeric
phase which leads to the above discussed disadvantages.

On the other hand, Fig. 2 shows a reinforced heterophasic polypropylene
composition according to a specifically preferred embodiment of the
present invention where the filler particles are homogeneously and
completely encapsulated in the dispersed phase which is formed by a
polyethylene composition in which silicon functional groups are cross-
linked with silanol groups on the surface of the particulate filler. It can be
further seen that the filler is present only in the dispersed phase. This
specifically preferred structure of the inventive heterophasic polyolefin
composition is schematically illustrated in Fig. 3.
It will be shown in the example section below that the reinforced polyolefin
compositions according to the present invention show highly improved
mechanical properties such as Charpy notched impact strength, scratch
resistance and elongation at break. It was further surprisingly found that the
inventive polyolefm compositions showed a significantly reduced gloss
achieving an aesthetically attractive surface appearance.
Thus, the reinforced polyolefm compositions according to the present
invention preferably have an impact strength at +23°C of at least 5.5 kJ/m2
and at -20°C of at least 2.0 kJ/m2 in a Charpy notched impact strength test
according to ISO 179 leA.
Moreover, the inventive polyolefm compositions preferably have a flexural
modulus of not less than 950 MPa, preferably not less than 1000 MPa and
even more preferably not less than 1200 MPa, measured according to
ISO 178.
The inventive polyolefm compositions preferably further show an
elongation at break of at least 10%, preferably at least 20%, even more
preferably at least 50%, measured according to ISO 527.

The inventive polyolefin compositions preferably show a gloss at 20° of
not more than 50%, preferably not more than 40%, even more preferred not
more than 30%, measured according to ISO 2813.
The inventive polyolefin compositions are further improved in scratch
resistance. They preferably show a scratch resistance, expressed as delta
(L) of at least 3.5, preferably at least 4.0, even more preferred at least 4.5.
Scratch resistance is expressed as delta (L) and measured according to the
following procedure: A cross hatch grid is cut on the grained surface of an
injection-moulded specimen using a steel ball tip tool. The difference in
light reflection - delta (L) - is then measured with a spectral photometer.
The present invention will now be further described by means of the
following non-limiting examples and comparative examples, and with
reference to the figures.
Fig. 1 shows a conventional polypropylene impact copolymer with a
discrete dispersion of a mineral filler separate from the disperse phase.
Fig. 2 shows an embodiment of the polyolefin composition according to the
present invention where the mineral filler particles are encapsulated in the
disperse phase made of a silicon group containing ethylene vinyl-silane
copolymer.
Fig. 3 is a schematic illustration of the embodiment according to Fig. 2.

Examples
1. Definitions
a) Melt Flow Rate
The melt flow rate (MFR) is determined according to ISO 1133 and is
indicated in g/10 min. The MFR is an indication of the flowability, and
hence the processability, of the polymer. The higher the melt flow rate, the
lower the viscosity of the polymer. The MFR2 of polypropylene is
determined at a temperature of 230 °C and a load of 2.16 kg, the MFR5 of
polyethylene is measured at a temperature 190 °C and a load of 5 kg and
the MFR2 of polyethylene at a temperature 190 °C and a load of 2.16 kg.
b) Xylene insolubles
The content of xylene hot insolubles is determined by extracting 1 g of
finely cut polymer sample with 500 ml xylene in a Soxleth extractor for 48
hours at the boiling temperature. The remaining solid amount is dried at 90
°C and weighed for determining the insolubles amount.
c) Charpy notched impact test
The impact strength is determined as Charpy Impact Strength according to
ISO 179 1 eA at +23°C and at -20 °C on injection moulded specimens of
80x10x4 mm3.
d) Tensile test
Tensile tests are performed according to ISO 527 using injection moulded
specimen as described in EN ISO 1873-2 (dog bone shape, 4 mm
thickness).

Tensile modulus (E-modulus) was also determined according to ISO 527
and calculated from the linear part of the tensile test results.
e) Flexural Modulus
The flexural modulus is measured according ISO 178 using injection
moulded specimens of 80 x 10x4 mm3.
f) Density
The density is measured according to ISO 1183.
g) Elongation at break
The elongation at break was also determined according to ISO 527.
h) Gloss
Gloss was determined on injection moulded specimens of 60 x 60 x 2 mm3
according to ISO 2813.
i) Scratch resistance
A plate of 3 mm thickness with a fine-grained surface (type N111) is
produced by injection moulding. With an Erichsen Cross Hatch Cutter
model 420p, a cross hatch grid of 40 x 40 mm2 (line distance 2 mm in both
directions) is cut on the grained surface using the standardised Erichsen
steel ball tip tool (1 mm diameter) with a force of 10 N and a cutting speed
of 1000 mm/min. The difference in light reflection - delta (L) - is then
measured with a spectral photometer. Better scratch resistance is expressed
by lower scratch visibility and correspondingly a smaller delta(L) value

2. Materials
The components - propylene homo- or copolymer, polyethylene-
vinylsilane-copolymer or grafting product and the catalyst master batch
(Borealis polyethylene CAT-MB50 or CAT-MB 25 with dibutyltin
dilaurate as catalytically active substance), were combined in a twin screw
extruder (PRISM TSE24, L/D ratio 40) with two high intensity mixing
segments at temperatures between 190 and 220°C at a through put off of 10
kg/h and a screw speed of 50 rpm. The material was extruded to two
circular dies of 3mm diameter into water base with a residence time of at
least 30 sec for solidifying the melt standard, which was consequently
granulated. For the period until melt processing, the resulting compound
was stored at an ambient temperature of + 23 ± 2 °C and normal humidity
(50 ± 5%).
Masterbatch compositions were produced as follows:
(a) 50 wt.% of an ethylene-propylene random copolymer with MFR
(230°C/2.16 kg) of 8 g / 10 min, an ethylene content of 6 wt% and
a density of 905 kg/m3. were blended with 47.5 wt% silicon group
containing polyethylene LE4481 and 2.5 wt% CAT-MB50, or
(b) 75 wt.% of the same ethylene-propylene random copolymer were
blended with 23.75 wt % silicon group containing polyethylene
LE4481 and 1.25 wt% CAT-MB25,
to obtain two masterbatch compositions containing (a) 50 wt.% and (b) 25
wt% of the silicon group-containing polyethylene.

Compounds:
All used polymers are commercially available by Borealis Polyolefine
GmbH:
PPX104 is a heterophasic propylene-ethylene copolymer with MFR
(230°C/2.16 kg) of 31 g / 10 min, an EPR content of 20 wt% and a density
of 905 kg/m3.
BG055A1 is a heterophasic propylene-ethylene impact copolymer with
MFR (230°C/2.16 kg) of 22 g / 10 min, an EPR content of 18 wt% and a
density of 905 kg/m3.
FB5150 is a linear low density polyethylene (LLDPE) with MFR
(190°C/2.16 kg) of 1.5 g / 10 min , and a density of 915 kg/m3.
FT7239 is a low density polyethylene (LDPE) with MFR (190°C/2.16 kg)
of 3 g / 10 min, and a density of 929 kg/m3.
HE2545 is a silane-grafted high density polyethylene (HDPE) with MFR
(190°C/2.16kg) of 6 g / 10 min, a density of 955 kg/m3 and a silanol
content of 1.5 wt%.
Visico LE4481 is a high-pressure low density ethylene copolymer with
vinyl silane content for cable insulation with MFR (190°C/2.16 kg) of 5 g /
10 min , a silanol content of 1.75 wt% and a density of 927 kg/m3.
Visico LE4423 is a high-pressure low density ethylene copolymer with
vinyl silane content for cable insulation with MFR (190°C/2.16 kg) of 1 g /
10 min , a silanol content of 1.35 wt% and a density of 923 kg/m3.
"Talc" is Tital 15, manufactured by Ankerpoort NV having a top-cut
particle size of 7 µm (95% of particles below that size, according to ISO

787-7) and a weight average particle size of 2 µm as determined according
to ISO 13317-1.
Example 1:
87.75 wt% PPX104 as matrix phase, 2.0 wt% LE4481 as silane-
copolymerised polyethylene, 10.0 wt.% talc and 0.25 wt% catalyst master
batch CAT-MB50 are used.
Example 2:
87.75 wt% PPX104 as matrix phase, 2.0 wt% LE4423 as silane-
copolymerised polyethylene, 10.0 wt.% talc and 0.25 wt% catalyst master
batch CAT-MB50 are used.
Example 3:
84.75 wt% PPX104 as matrix phase, 5.0 wt% LE4423 as silane-
copolymerised polyethylene, 10.0 wt.% talc and 0.25 wt% catalyst master
batch CAT-MB50 are used.
Example 4:
79.75 wt% PPX104 as matrix phase, 10.0 wt% LE4423 as silane-
copolymerised polyethylene, 10.0 wt.% talc and 0.25 wt% catalyst master
batch CAT-MB50 are used.
Example 5:
79.75 wt% PPX104 as matrix phase, 5.0 wt.% FB5150, 5.0 wt% LE4423 as
silane-copolymerised polyethylene, 10.0 wt.% talc and 0.25 wt% catalyst
master batch CAT-MB50 are used.
Example 6:

79.75 wt% BG055A1 as matrix phase, 10.0 wt% HE2545 as si lane-grafted
polyethylene, 2.5 wt.% talc and 0.25 wt% catalyst master batch CAT-MB50
are used.
Comparative Example 1:
Only PPX104 is used.
Comparative Example 2:
90.0 wt% PPX104 without additional dispersed phase, and 10.0 wt.% talc
are used.
Comparative Example 3:
80.0 wt% PPX104 as matrix phase, 10.0 wt% FT7239 as a dispersed
polyethylene without silane groups, and 10.0 wt.% talc are used.
Comparative Example 4:
90.0 wt% BG055A1 and 10.0 wt.% talc are used.
The results are shown in Table 1 below.



Claims
1. A polyolefin composition comprising:
a polyolefin base resin comprising an olefin homo- or
copolymer (A) having hydrolysable silicon-containing groups,
and
an inorganic mineral filler (B) containing on its surface silanol
groups or precursors thereof,
wherein the amount of the silicon-containing groups is from 0.1 to
about 10 wt%, based on the total olefin homo- or copolymer (A).
2. The polyolefin composition according to claim 1, wherein said
composition further comprises a silanol condensation catalyst.
3. The polyolefin composition according to claim 2, wherein the
silanol condensation catalyst is selected from the group consisting
of inorganic acids such as sulphuric acid and hydrochloric acid,
organic acids such as citric acid, stearic acid, acetic acid,
sulphonic acid and alkanoic acids as dodecanoic acid, organic
bases, carboxylic acids, organometallic compounds including
organic titanates and complexes or carboxylates of lead, cobalt,
iron, nickel, zinc and tin or a precursor of these compounds.
4. The polyolefin composition according to any of claims 1 to 3,
wherein the hydrolysable silicon group-containing olefin homo- or
copolymer (A) is an ethylene homo- or copolymer.
5. The polyolefin composition according to any of the preceding
claims, wherein the polyolefin base resin further comprises a
propylene homo- or copolymer (C) which forms a matrix phase,

and a disperse phase which is dispersed in said matrix phase and
comprises the olefin homo- or copolymer (A) having hydrolysable
silicon-containing groups.
6. The polyolefin composition according to claim 5, wherein the
disperse phase further comprises an elastomer, different from the
olefin homo- or copolymer (A).
7. The polyolefin composition according to claim 5 or 6, wherein the
inorganic mineral filler (B) is present only in the disperse phase.
8. The polyolefin composition according to any of claims 5 to 7,
wherein the composition is obtainable by a process for the
preparation of a crosslinked heterophasic polypropylene
composition, comprising the steps of:
i. blending (A) and (C) together with a silanol condensation
catalyst,
ii. granulation of the blend of step (i) in a water bath, and
afterwards
iii. cross-linking the obtained heterophasic polypropylene
composition at 10 to 40 °C under a humidity of below 85 % to
a cross-linking degree of at least 30 %, based on the total
olefin homo- or copolymer (A).
9. The polyolefin composition according to claim 8, wherein step (i) is
carried out at a temperature of 180 to 230 °C.
10. The polyolefin composition according to claim 8, wherein for
granulation the residence time of the blend of step (i) in the water
bath is less than 30 seconds.

11. The polyolefin composition according to any of claims 5 to 10,
wherein the weight ratio of propylene homo- or copolymer (C) to
olefin homo- or copolymer (A) is from 95:5 to 45:55.
12. The polyolefin composition according to any of the preceding
claims, wherein olefin homo- or copolymer (A) is silicon-grafted and
has a density of 920 to 960 kg/m3.
13. The polyolefin composition according to any of claims 1 to 12,
wherein olefin homo- or copolymer (A) is obtained by a
polymerisation of olefin monomers and silicon group-containing
monomers and has a density of 900 to 940 kg/m3.
14. The polyolefin composition according to any of the preceding
claims, wherein the inorganic mineral filler (B) is selected from the
group consisting of talc, mica, montmorillonite, wollastonite,
bentonite, silica, and phyllosilicate.
15. The polyolefin composition according to any of claims 5 to 14,
wherein the disperse phase comprises a further olefin homo- or
copolymer (D) compatible with the olefin homo- or copolymer (A),
the olefin homo- or copolymer (D) being selected from high
pressure polyethylenes or metallocene-based ethylene plastomers.
16. The polyolefin composition according to any of the preceding
claims, wherein the hydrolysable silicon-containing groups are
introduced into the olefin homo- or copolymer (A) by
copolymerisation with an unsaturated silicon-compound
represented by the formula:

wherein

R1 is an ethylenically unsaturated hydrocarbyl, hydrocarbyloxy or
(meth)acryloxy hydrocarbyl group,
R2 is an aliphatic saturated hydrocarbyl group,
Y which may be the same or different, is a hydrolysable organic
group and
q is 0, 1 or 2.
17. The polyolefin composition according to any of the preceding
claims, wherein the composition has been subjected to the
presence of moisture.
18. The polyolefin composition according to any of the preceding
claims, wherein the composition has an impact strength at + 23 °C
of at least 5.5 kJ/m2 in a Charpy notched test according to ISO 179
1eA.
19. The polyolefin composition according to any of the preceding
claims, wherein the composition has an impact strength at -20 °C
of at least 2.0 kJ/m2, in a Charpy notched test according to ISO 179
1eA.
20. The polyolefin composition according to any of the preceding
claims, wherein the composition has a flexural modulus of not less
than 950 MPa, measured according to ISO 178.
21. The polyolefin composition according to any of the preceding
claims, wherein the composition has an elongation at break of at
least 10%, measured according to ISO 527.
22. The polyolefin composition according to claim 21, wherein the
composition has an elongation at break of at least 20%, measured
according to ISO 527.

23. The polyolefin composition according to any of the preceding
claims, wherein the composition has a scratch resistance,
expressed as delta (L) of at least 3.5, preferably at least 4.0.
24. An article made of the polyolefin composition according to any of
claims 1 to 23.
25. Use of the polyolefin composition according to any of claims 1 to
23 for the production of an article.

The present invention relates to a polyolefin composition comprising a polyolefin base resin comprising an olefin homo- or copolymer (A) having hydrolysable silicon-containing groups, and an inorganic mineral filler (B) containing on its surface silanol groups or precursors thereof.

Documents:

1403-KOLNP-2009-(17-09-2012)-ABSTRACT.pdf

1403-KOLNP-2009-(17-09-2012)-ANNEXURE TO FORM 3.pdf

1403-KOLNP-2009-(17-09-2012)-CLAIMS.pdf

1403-KOLNP-2009-(17-09-2012)-CORRESPONDENCE.pdf

1403-KOLNP-2009-(17-09-2012)-DESCRIPTION (COMPLETE).pdf

1403-KOLNP-2009-(17-09-2012)-DRAWINGS.pdf

1403-KOLNP-2009-(17-09-2012)-FORM-1.pdf

1403-KOLNP-2009-(17-09-2012)-FORM-13.pdf

1403-KOLNP-2009-(17-09-2012)-FORM-2.pdf

1403-KOLNP-2009-(17-09-2012)-OTHERS.pdf

1403-KOLNP-2009-(17-09-2012)-PA.pdf

1403-kolnp-2009-abstract.pdf

1403-KOLNP-2009-ASSIGNMENT.pdf

1403-KOLNP-2009-CANCELLED PAGES.pdf

1403-kolnp-2009-claims.pdf

1403-KOLNP-2009-CORRESPONDENCE-1.1.pdf

1403-kolnp-2009-correspondence.pdf

1403-kolnp-2009-description (complete).pdf

1403-kolnp-2009-drawings.pdf

1403-KOLNP-2009-EXAMINATION REPORT.pdf

1403-kolnp-2009-form 1.pdf

1403-kolnp-2009-form 18.pdf

1403-kolnp-2009-form 3.pdf

1403-kolnp-2009-form 5.pdf

1403-KOLNP-2009-GPA 1.1.pdf

1403-kolnp-2009-gpa.pdf

1403-KOLNP-2009-GRANTED-ABSTRACT.pdf

1403-KOLNP-2009-GRANTED-CLAIMS.pdf

1403-KOLNP-2009-GRANTED-DESCRIPTION (COMPLETE).pdf

1403-KOLNP-2009-GRANTED-DRAWINGS.pdf

1403-KOLNP-2009-GRANTED-FORM 1.pdf

1403-KOLNP-2009-GRANTED-FORM 2.pdf

1403-KOLNP-2009-GRANTED-FORM 3.pdf

1403-KOLNP-2009-GRANTED-FORM 5.pdf

1403-KOLNP-2009-GRANTED-SPECIFICATION-COMPLETE.pdf

1403-kolnp-2009-international preliminary examination report.pdf

1403-kolnp-2009-international publication.pdf

1403-KOLNP-2009-INTERNATIONAL SEARCH REPORT & OTHERS.pdf

1403-kolnp-2009-others.pdf

1403-KOLNP-2009-PA.pdf

1403-kolnp-2009-pct priority document notification.pdf

1403-kolnp-2009-pct request form.pdf

1403-KOLNP-2009-REPLY TO EXAMINATION REPORT.pdf

1403-kolnp-2009-specification.pdf

1403-KOLNP-2009-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-1403-kolnp-2009.jpg


Patent Number 257616
Indian Patent Application Number 1403/KOLNP/2009
PG Journal Number 43/2013
Publication Date 25-Oct-2013
Grant Date 21-Oct-2013
Date of Filing 16-Apr-2009
Name of Patentee BOREALIS TECHNOLOGY OY
Applicant Address P.O. BOX 330, FIN-06101 PORVOO, FINLAND
Inventors:
# Inventor's Name Inventor's Address
1 GAHLEITNER, MARKUS KOHLWINKEL 4, A-4501 NEUHOFEN/KREMS, AUSTRIA
2 MACHL, DORIS GRABNERSTRASSE 25, A-4020 LINZ, AUSTRIA
3 PHAM, TUNG GOGLERFELDGASSE 9, A-4040 LINZ, AUSTRIA
4 MOTHA, KSHAMA VEDENOTTAMONTIE 12 D 29, FIN-00980 HELSINKI, FINLAND
PCT International Classification Number C08K 9/04,C08K 9/08
PCT International Application Number PCT/EP2007/009654
PCT International Filing date 2007-11-07
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 06027118.6 2006-12-29 EUROPEAN UNION