U.S. patent application number 15/105506 was filed with the patent office on 2017-04-20 for a polymer composition comprising a crosslinkable polyolefin with hydrolysable silane groups, catalyst and a surfactant interacting additive.
The applicant listed for this patent is BOREALIS AG. Invention is credited to Martin ANKER, Roger CARLSSON, Kristian DAHLEN, Ola FAGRELL, Stefan HELLSTROM, Perry NYLANDER, Bernt-Ake SULTAN.
Application Number | 20170107356 15/105506 |
Document ID | / |
Family ID | 49886660 |
Filed Date | 2017-04-20 |
United States Patent
Application |
20170107356 |
Kind Code |
A2 |
ANKER; Martin ; et
al. |
April 20, 2017 |
A POLYMER COMPOSITION COMPRISING A CROSSLINKABLE POLYOLEFIN WITH
HYDROLYSABLE SILANE GROUPS, CATALYST AND A SURFACTANT INTERACTING
ADDITIVE
Abstract
The present invention relates to a polymer composition
comprising a surfactant interacting additive, and wherein the
polymer composition further comprises at least one silanol
condensation catalyst, wherein each catalyst is selected from: i) a
compound of formula I ArSO.sub.3H (I) or a precursor thereof,
wherein Ar is an 1 to 4 alkyl groups substituted aryl, wherein the
aryl is phenyl or naphthyl, and wherein each alkyl group,
independently, is a linear or branched alkyl with 10 to 30 carbons,
wherein the total number of carbons in the alkyl groups is in the
range of 20 to 80 carbons; ii) a derivative of i) 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 compound of formula I; and iii) a metal salt of
i) wherein the metal ion is selected from the group consisting of
copper, aluminum, tin and zinc; an article, for example, a coating,
a wire or a cable, comprising the polymer composition, a process
for producing an article and use of the polymer composition.
Inventors: |
ANKER; Martin; (Hisings
Karra, SE) ; NYLANDER; Perry; (Goteborg, SE) ;
CARLSSON; Roger; (Save, SE) ; SULTAN; Bernt-Ake;
(Stenungsund, SE) ; HELLSTROM; Stefan; (Kungalv,
SE) ; DAHLEN; Kristian; (Stora Hoga, US) ;
FAGRELL; Ola; (Stenungsund, SE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BOREALIS AG |
Vienna |
|
AT |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20160312012 A1 |
October 27, 2016 |
|
|
Family ID: |
49886660 |
Appl. No.: |
15/105506 |
Filed: |
December 17, 2014 |
PCT Filed: |
December 17, 2014 |
PCT NO: |
PCT/EP2014/078321 PCKC 00 |
371 Date: |
June 16, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 3/013 20180101;
C08K 3/26 20130101; H01B 3/441 20130101; C08L 2203/18 20130101;
C08K 3/20 20130101; C08K 5/005 20130101; C08K 5/005 20130101; C08L
23/0853 20130101; C08L 23/08 20130101; C08L 23/0892 20130101; C08L
43/04 20130101; C08L 23/08 20130101; C08K 13/02 20130101; C08L
23/0869 20130101; C08K 3/26 20130101; C08L 23/08 20130101; C08K
3/013 20180101; C08L 23/08 20130101; C08L 2666/78 20130101; C08L
23/08 20130101; C08L 23/08 20130101; C08L 43/04 20130101; C08K 3/20
20130101 |
International
Class: |
C08K 13/02 20060101
C08K013/02 |
Claims
1-16. (canceled)
17. A polymer composition comprising a surfactant interacting
additive, and characterized by that the polymer composition further
comprises at least one silanol condensation catalyst, wherein each
catalyst is selected from: i) a compound of formula I ArSO.sub.3H
(I) or a precursor thereof, wherein Ar is an 1 to 4 alkyl groups
substituted aryl, wherein the aryl is phenyl or naphthyl, and
wherein each alkyl group, independently, is a linear or branched
alkyl with 10 to 30 carbons, wherein the total number of carbons in
the alkyl groups is in the range of 20 to 80 carbons; ii) a
derivative of i) 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
compound of formula I; and iii) a metal salt of i) wherein the
metal ion is selected from the group consisting of copper,
aluminum, tin and zinc.
18. A polymer composition according to claim 17, wherein the
polymer composition is a silanol condensation catalyst masterbatch
which further comprises a polymer matrix.
19. A polymer composition according to claim 17, wherein the
polymer composition further comprises a crosslinkable polyolefin
with hydrolysable silane groups.
20. A polymer composition according to claim 17, wherein Ar, of the
compound of formula I, is naphthyl.
21. A polymer composition according to claim 17, wherein each
catalyst is selected from a) C.sub.12-alkylated naphthyl sulfonic
acids; b) a derivative of a) 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
compound a); and/or c) a metal salt of a) wherein the metal ion is
selected from the group consisting of copper, aluminum, tin and
zinc.
22. A polymer composition according to claim 17, wherein the
polymer composition comprises the "at least one" silanol
condensation catalyst in an amount of 0.0001 to 8 wt %.
23. A polymer composition according to claim 17, wherein the
surfactant interacting additive comprises a colour master
batch.
24. A polymer composition according to claim 17, wherein the
surfactant interacting additive comprises TiO.sub.2, CaCO.sub.3
and/or carbon black, e.g. a UV black.
25. A polymer composition according to claim 17, wherein the
surfactant interacting additive comprises hindered-amine light
stabilizers (HALS).
26. A polymer composition according to claim 17, wherein the
crosslinkable polyolefin with hydrolysable silane groups comprises
a polyethylene with hydrolysable silane groups.
27. A polymer composition according to claim 17, wherein the
polyolefin with hydrolysable silane groups comprises 0.001 to 15%
by weight of silane compound.
28. A polymer composition according to claim 17, which comprises a
crosslinked polyolefin, wherein the crosslinked polyolefin is
produced by crosslinking the crosslinkable polyolefin comprised in
the polymer composition according to claim 1.
29. A polymer composition according to claim 28, which polymer
composition has a hot set elongation of less than 175% when
measured according to method EN60811-2-1:1999.
30. An article, for example, a coating, a wire or a cable,
comprising the polymer composition, according to claim 17.
31. A process for producing an article, wherein said process
comprises use, for example extrusion, of a polymer composition
according to claim 17.
Description
FIELD OF INVENTION
[0001] The present invention relates to a new polymer composition,
an article, for example, a coating, a wire or a cable, comprising
the polymer composition, a process for producing an article and use
of the polymer composition.
BACKGROUND
[0002] It is known to crosslink polymers by means of additives.
Crosslinking improves properties of the polymer such as mechanical
strength and heat resistance. Polymers normally considered to be
thermoplastics, and not crosslinkable, can also be made
crosslinkable by introducing crosslinkable groups in the polymer.
Examples thereof are polymer compositions comprising polyolefins,
such as polyethylenes, where silane compounds have been introduced
as crosslinkable groups, e.g. by grafting silane compounds onto a
prepared polyolefin, or by copolymerisation of an olefin and a
silane compound. Such techniques are known e.g. from U.S. Pat. No.
4,413,066, U.S. Pat. No. 4,297,310, U.S. Pat. No. 4,351,876, U.S.
Pat. No. 4,397,981, U.S. Pat. No. 4,446,283 and U.S. Pat. No.
4,456,704.
[0003] The crosslinking of polymer compositions comprising
hydrolysable silane groups with catalysts is known in the art, see
e.g. EP0736065. It is further known that the crosslinking process
may advantageously be carried out in the presence of acidic silanol
condensation catalysts. The acidic silanol condensation catalysts
permit crosslinking of silane-containing polymer compositions
already at room temperature (about 20 to 25.degree. C.). Examples
of such acidic silanol condensation catalysts which are organic
sulphonic acids, or precursors of such acids, are disclosed in, for
example, WO95/17463, EP1309631, EP1309632 and EP1849816, which
documents, and the contents therein, are enclosed herein by
reference.
[0004] It is also known to use various additives in polymer
compositions. The particular type and amount of the additive to be
used is dependent on the particular application a polymer
composition is designed for.
[0005] Further, some important groups of additives are surfactant
interacting additives which may be represented by, for example,
pigments, and important pigments are pigments which comprise
titanium dioxide, i.e. TiO.sub.2, and/or calcium carbonate, i.e.
CaCO.sub.3, as the main component. The pigments which comprise
titanium dioxide, and/or calcium carbonate, are used to improve
colour coverage of processed articles. The pigments, comprising
titanium dioxide, and/or calcium carbonate, are, e.g., used to make
processed articles more opaque.
[0006] Furthermore, uses of pigments comprising titanium dioxide,
and/or calcium carbonate, in polymer compositions comprising
polyolefins with hydrolysable silane groups and conventional
silanol condensation catalysts are also known in the art. Moreover,
it has further been shown that surfactant interacting additives,
such as pigments comprising titanium dioxide, and/or calcium
carbonate, are to some extent deactivating the crosslinking ability
of silanol condensation catalysts of the Bronstedt acid type.
Therefore, generally speaking, pigments comprising titanium
dioxide, and/or calcium carbonate, are not compatible with the
technology of crosslinking polyolefins containing hydrolysable
silane groups with the silanol condensation catalysts of the
Bronstedt acid type. Thus, there is a need of polymer compositions
comprising a specific silanol condensation catalyst and a
surfactant interacting additive, for example pigments comprising
titanium dioxide, and/or calcium carbonate, wherein the polymer
compositions effectively promote the crosslinking performance of
the silanol condensation catalysts of the Bronstedt acid type.
DESCRIPTION OF THE INVENTION
[0007] It has now surprisingly been found that the object to
provide a polymer composition which effectively promotes the
desired crosslinking performance is achieved by a new polymer
composition in accordance to the present invention, wherein the
polymer composition comprises a surfactant interacting additive,
and a specific silanol condensation catalyst of the Bronstedt acid
type, wherein the catalyst is: [0008] i) a compound of formula
I
[0008] ArSO.sub.3H (I) [0009] or a precursor thereof, wherein
[0010] Ar is an 1 to 4 alkyl groups substituted aryl, wherein the
aryl is phenyl or naphthyl, and wherein each alkyl group,
independently, is a linear or branched alkyl with 10 to 30 carbons,
wherein the total number of carbons in the alkyl groups is in the
range of 20 to 80 carbons; [0011] ii) a derivative of i) 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 compound of formula I; and [0012]
iii) a metal salt of i) wherein the metal ion is selected from the
group consisting of copper, aluminum, tin and zinc.
[0013] Thus, the present invention provides a polymer composition
comprising a surfactant interacting additive, wherein the polymer
composition further comprises at least one silanol condensation
catalyst, and each catalyst is selected from: [0014] i) a compound
of formula I
[0014] ArSO.sub.3H (I) [0015] or a precursor thereof, wherein
[0016] Ar is an 1 to 4 alkyl groups substituted aryl, wherein the
aryl is phenyl or naphthyl, and wherein each alkyl group,
independently, is a linear or branched alkyl with 10 to 30 carbons,
wherein the total number of carbons in the alkyl groups is in the
range of 20 to 80 carbons; [0017] ii) a derivative of i) 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 compound of formula I; and [0018]
iii) a metal salt of i) wherein the metal ion is selected from the
group consisting of copper, aluminum, tin and zinc.
[0019] In accordance with the present invention, by using the
polymer composition as described herein comprising a surfactant
interacting additive, and a specific silanol condensation catalyst
of the Bronstedt acid type, (which catalyst comprises an aryl
substituted with one or more alkyl groups), it has surprisingly now
been possible to achieve an efficient crosslinking reaction, i.e.
hydrolysis and condensation of silane groups, in presence of a
surfactant interacting additive. This is especially significant
when polymer article is crosslinked in hot water bath. The
surfactant interacting additive may for instance be a colour
masterbatch. Colour masterbatches comprising titanium dioxide
and/or calcium carbonate will usually interact with the Bronstedt
acid. If the presence of titanium dioxide and/or calcium carbonate
is significantly high relative to the catalyst concentration, the
result will be inefficient crosslinking of silane groups. Thus, the
present invention relates to the use of a specific silanol
condensation catalyst of the Bronstedt acid type having a
lipophilic nature. Consequently, the catalyst has shown to have an
improved compatibility with the, usually non-polar, polymer matrix
of a polymer composition. Thus, accordingly, the catalyst also has
less driving force to lower its energy by interacting with an
additive surface. Hence, the catalyst stays longer times in the
polymer matrix and is more available for catalysis of silane
hydrolysation and condensation reactions.
[0020] The polymer composition according to the present invention
comprises the surfactant interacting additive which surfactant
interacting additive may comprise solid substances with polar
surface groups, for example, one or more selected from fillers,
different kind of pigments, TiO.sub.2, CaCO.sub.3, carbon black
(e.g. "UV black", i.e. a carbon black that absorbs ultraviolet
radiation), huntite, mica, kaolin, aluminium hydroxide (ATH),
magnesium dihydroxide (MDH), and SiO.sub.2.
[0021] Further, in accordance with the present invention the
expression "a polymer composition comprises a surfactant
interacting additive, wherein the polymer composition further
comprises at least one silanol condensation catalyst" shall also be
understood to include embodiments of a polymer composition where a
surfactant interacting additive is comprised in a skin, which skin
is outside, and in contact with, an inner polymer composition
comprising said "at least one" silanol condensation catalyst. Thus,
in such embodiments the polymer composition of the present
invention comprises said skin, comprising a surfactant interacting
additive, as well as said inner polymer composition comprising said
"at least one" silanol condensation catalyst. Further, said inner
polymer composition may, optionally, also comprise a surfactant
interacting additive.
[0022] Furthermore, in accordance with the present invention the
expression "a polymer composition comprises a surfactant
interacting additive, wherein the polymer composition further
comprises at least one silanol condensation catalyst" shall also be
understood to include embodiments of a polymer composition
comprising a surfactant interacting additive, wherein the polymer
composition has been sprayed with the at least one silanol
condensation catalyst.
[0023] The polymer composition of the present invention do also
comprise the "at least one" silanol condensation catalyst, wherein
each catalyst is selected from: [0024] i) a compound of formula
I
[0024] ArSO.sub.3H (I) [0025] or a precursor thereof, wherein
[0026] Ar is an 1 to 4 alkyl groups substituted aryl, wherein the
aryl is phenyl or naphthyl, and wherein each alkyl group,
independently, is a linear or branched alkyl with 10 to 30 carbons,
wherein the total number of carbons in the alkyl groups is in the
range of 20 to 80 carbons; [0027] ii) a derivative of i) 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 compound of formula I; and [0028]
iii) a metal salt of i) wherein the metal ion is selected from the
group consisting of copper, aluminum, tin and zinc.
[0029] Ar of the compound of formula I, may, besides the "1 to 4
alkyl groups"-substituents, also, optionally, comprise further
suitable substituents.
[0030] An embodiment of the present invention provides a polymer
composition, as described herein, wherein said each silanol
condensation catalyst is selected from a) C.sub.12-alkylated
naphthyl sulfonic acids;
[0031] b) a derivative of a) 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
compound a); and/or
[0032] c) a metal salt of a) wherein the metal ion is selected from
the group consisting of copper, aluminum, tin and zinc.
[0033] A further embodiment of the present invention provides a
polymer composition, as described herein, wherein said each silanol
condensation catalyst is selected from C.sub.12-alkylated naphthyl
sulfonic acids.
[0034] In a further embodiment of the present invention, the
polymer composition is a silanol condensation catalyst masterbatch
which further comprises a polymer matrix.
[0035] When the polymer composition in accordance with the present
invention is a silanol condensation catalyst masterbatch, said
silanol condensation catalyst masterbatch may be a mixture which
may comprise both the surfactant interacting additive and the "at
least one" silanol condensation catalyst, i.e. the compound of
formula I, both in a concentrated form in said polymer matrix.
[0036] Further, when the polymer composition in accordance with the
present invention is a silanol condensation catalyst masterbatch,
said silanol condensation catalyst masterbatch may be produced by
compounding the surfactant interacting additive, the "at least one"
silanol condensation catalyst and, optionally, any further
additives with a polymer resin (i.e. a carrier resin), whereby the
polymer resin forms the polymer matrix.
[0037] The further, optional, additives may, for example, be
miscible thermoplastics, antioxidants, stabilizers, lubricants,
fillers, peroxides, silanes and/or foaming agents.
[0038] The silanol condensation catalyst masterbatch in accordance
with the present invention may be in a liquid form or a solid form
suitably formed into, for example, a powder and/or granular shaped
solids, e.g. pellets or granules.
[0039] Furthermore, prior to a crosslinking of a polymer, handling
of the "at least one" silanol condensation catalyst, i.e. the
compound of formula I, and the surfactant interacting additive may
be facilitated when added in concentrated form as the silanol
condensation catalyst masterbatch.
[0040] The polymer matrix may comprise, for example, a polyolefin,
e.g., a polyethylene, which may be a homo- or copolymer of
ethylene, e.g. low density polyethylene, or a ethylene-acrylate
where the acrylate comonomer is selected from methyl acrylate,
methyl methacrylate, ethyl acrylate, butyl acrylate, and tert-butyl
acrylate, or a copolymer containing 1 to 50 percent by weight of
the acrylate comonomer, or any mixtures thereof. Furthermore, the
polymer matrix may comprise a high density or medium density
polyethylene. Further, the polymer matrix may comprise a bimodal
polymer.
[0041] In still a further embodiment of the present invention, the
polymer composition further comprises a crosslinkable polyolefin
with hydrolysable silane groups.
[0042] The crosslinkable polyolefin of the polymer composition may,
for example, comprise a polyethylene with hydrolysable silane
groups, or the crosslinkable polyolefin may, e.g., consist of a
polyethylene with hydrolysable silane groups.
[0043] The hydrolysable silane groups may be introduced into the
polyolefin by copolymerisation of, e.g., ethylene and silane group
containing comonomers or by grafting, i.e. by chemical modification
of the polyolefin by addition of silane-containing compounds mostly
in a radical reaction. Both techniques are well known in the
art.
[0044] Moreover, the crosslinkable polyolefin with hydrolysable
silane groups may be obtained by copolymerisation. In the case of
polyolefin being, for example, polyethylene, the copolymerisation
may be carried out with an unsaturated silane compound represented
by the formula II
R.sup.1SiR.sup.2.sub.qY.sub.3-q (II)
wherein
[0045] R.sup.1 is an ethylenically unsaturated alkyl, alkyloxy or
(meth)acryloxy alkyl group,
[0046] R.sup.2 is an aliphatic saturated alkyl group,
[0047] Y which may be the same or different, is a hydrolysable
organic group and
[0048] q is 0, 1 or 2.
[0049] Special examples of the unsaturated silane compound are
those wherein R.sup.1 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 R.sup.2, if present, is a methyl, ethyl, propyl, decyl or
phenyl group.
[0050] In even a further embodiment the unsaturated silane compound
may be represented by the formula III
CH.sub.2.dbd.CHSi(OA).sub.3 (III)
wherein A is a alkyl group having 1 to 8 carbon atoms, e.g. 1 to 4
carbon atoms.
[0051] In further embodiments of the present invention the silane
compound may be, e.g., vinyl trimethoxysilane, vinyl
bismethoxyethoxysilane, vinyl triethoxysilane,
gamma-(meth)acryloxypropyltrimethoxysilane,
gamma(meth)acryloxypropyltriethoxysilane, or vinyl
triacetoxysilane.
[0052] Said copolymerisation may be carried out under any suitable
conditions resulting in the copolymerisation of two monomers.
[0053] 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, for example, vinyl
carboxylate esters, such as vinyl acetate and vinyl pivalate,
alpha-olefins, such as propene, 1-butene, 1-hexane, 1-octene and
4-methyl-1-pentene, (meth)acrylates, such as methyl(meth)acrylate,
ethyl(meth)acrylate and butyl(meth)acrylate, olefinically
unsaturated carboxylic acids, such as (meth)acrylic acid, maleic
acid and fumaric acid, (meth)acrylic acid derivatives, such as
(meth)acrylonitrile and (meth)acrylic amide, vinyl ethers, such as
vinyl methyl ether and vinyl phenyl ether, and aromatic vinyl
compounds, such as styrene and alpha-ethyl styrene.
[0054] In still further embodiments of the present invention, said
comonomers may be vinyl esters of monocarboxylic acids having 1-4
carbon atoms, such as vinyl acetate, and/or (meth)acrylate of
alcohols having 1-4 carbon atoms, such as
methyl(meth)-acrylate.
[0055] In even further embodiments of the present invention, the
comonomers: butyl acrylate, ethyl acrylate and/or methyl acrylate
are disclosed.
[0056] Two or more comonomers, such as any of the olefinically
unsaturated compounds disclosed herein, 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% by weight of the copolymer, for example, about
0.5 to 35% by weight, e.g., about 1 to 30% by weight.
[0057] If a graft polymer is used, it may have been produced e.g.
by any of the two methods described in U.S. Pat. No. 3,646,155 and
U.S. Pat. No. 4,117,195, respectively.
[0058] The polyolefin with hydrolysable silane groups, which is
comprised in the polymer composition of the present invention, may
comprise 0.001 to 15% by weight of silane compound, for example,
0.01 to 5% by weight, e.g., 0.1 to 2% by weight.
[0059] In further embodiments of the present invention, Ar of the
compound of formula I, is a 1, 2, 3 or 4 alkyl groups substituted
aryl, for example, a 2 to 3 alkyl groups substituted aryl, or,
e.g., a 2 alkyl groups substituted aryl. Further, said aryl is
phenyl or naphthyl, e.g. naphthyl.
[0060] In an embodiment of the present invention, Ar is naphthyl
being substituted by, e.g. 2 alkyl groups.
[0061] Furthermore, each alkyl group, independently, is a linear or
branched alkyl with 10 to 30 carbons, wherein the total number of
carbons in the alkyl groups is in the range of 20 to 80
carbons.
[0062] In a further embodiment of the present invention, each alkyl
group, independently, is a linear alkyl with 10 to 15 carbons,
wherein the total number of carbons in the alkyl groups is in the
range of 20 to 60 carbons.
[0063] In still a further embodiment of the present invention, any
two of said alkyl groups may be linked to each other via a bridging
group such as an alkylene group.
[0064] The silanol condensation catalyst may also be a derivative
of the compound of formula I as described herein, wherein said
derivative may be converted by hydrolysis to the compound of
formula I. The derivative may, for example, be a corresponding acid
anhydride of the compound of formula I. Alternatively, the
derivative may be a compound of formula I which has been provided
with a hydrolysable protective group, as, e.g., an acetyl group.
The hydrolysable protective group can be removed by hydrolysis.
[0065] In an embodiment the polymer composition according to the
present invention comprises the surfactant interacting additive in
an amount of, for example, 0.01 to 5% by weight, or, e.g., 0.01 to
2% by weight.
[0066] In a further embodiment the polymer composition according to
the present invention comprises the "at least one" silanol
condensation catalyst in an amount of, for example, 0.0001 to 8% by
weight, 0.0001 to 6% by weight, 0.001 to 2% by weight, 0.05 to 1%
by weight, 1 to 8% by weight or 1 to 6% by weight.
[0067] In even a further embodiment wherein the polymer composition
is the silanol condensation catalyst masterbatch according to the
present invention, the silanol condensation catalyst masterbatch
comprises the surfactant interacting additive in an amount of, for
example, 0.2 to 40 wt %, or, e.g., 1 to 35 wt %.
[0068] In still a further embodiment wherein the polymer
composition is the silanol condensation catalyst masterbatch
according to the present invention, the silanol condensation
catalyst masterbatch comprises the "at least one" silanol
condensation catalyst in an amount of, for example, 0.7 to 8% by
weight, 0.7 to 6% by, 1 to 8% by weight or 1 to 6% by weight.
[0069] The polymer composition according to the invention may
further comprise various additives, for example, miscible
thermoplastics, antioxidants, stabilizers, lubricants, fillers,
peroxides, silanes and/or foaming agents.
[0070] As antioxidant, a compound, or a mixture of compounds, may,
for example, be used. The antioxidant may, suitably, be neutral or
acidic compounds, and which compounds may, suitably, comprise a
sterically hindered phenol group or aliphatic sulphur groups. Such
compounds are disclosed in EP1254923 and these are suitable
antioxidants for stabilisation of polyolefins containing
hydrolysable silane groups which are crosslinked with a silanol
condensation catalyst, e.g., an acidic silanol condensation
catalyst. Other exemplified antioxidants are disclosed in
WO2005003199.
[0071] Moreover, the antioxidant may be present in the polymer
composition in an amount of from 0.01 to 3 wt %, e.g., 0.05 to 2 wt
%, or, e.g., 0.08 to 1.5 wt %.
[0072] In accordance with the present invention the "at least one"
silanol condensation catalyst, the surfactant interacting additive
and the crosslinkable polyolefin may suitably be mixed to produce
the polymer composition of the present invention, by compounding a
crosslinkable polyolefin together with one or more additive
masterbatches. The one or more additive masterbatches may suitably
include the silanol condensation catalyst masterbatch of the
present invention as described herein.
[0073] Said compounding may be performed by any known compounding
process, including extruding the final product with a screw
extruder or a kneader.
[0074] Further, the one or more additive masterbatches comprise
said "at least one" catalyst, said surfactant interacting additive
and/or, optionally, further additives, respectively, in
concentrated form in their polymer matrices, e.g. polyolefin
matrices.
[0075] Alternatively, one or more of the "at least one" silanol
condensation catalyst, the surfactant interacting additive and the,
optional, further additives. need not to be added as comprised in
masterbatches but may instead be added, e.g. in liquid form,
directly to a system for production of the polymer composition of
the present invention.
[0076] The further, optional, additives may be as already described
herein.
[0077] The polymer matrix or matrices of the one or more additive
masterbatches may suitably be as the polymer matrix of the silanol
condensation catalyst as described herein.
[0078] Further, the silanol condensation catalyst masterbatch, the
additive masterbatch or masterbatches comprise said "at least one"
catalyst, said surfactant interacting additive and, optionally,
further additives, in concentrated form. The wording "concentrated
form" means herein that said "at least one" catalyst, said
surfactant interacting additive and the optional further additives
have higher concentration in said masterbatches as compared with
their concentration in the final crosslinkable polymer
composition.
[0079] In further embodiments of the present invention a silanol
condensation catalyst masterbatch or an additive masterbatch, as
described herein, may, for example, comprise the "at least one"
silanol condensation catalyst in an amount of, for example, 0.7 to
8% by weight, 0.7 to 6% by, 1 to 8% by weight or 1 to 6% by
weight.
[0080] Further in accordance with the present invention, when a
silanol condensation catalyst masterbatch or an additive
masterbatch, as described herein, is compounded with said polymer
composition comprising said crosslinkable polyolefin, the silanol
condensation catalyst masterbatch or the additive masterbatch may
be present in an amount of 1 to 10 wt %, for example, 2 to 8 wt
%.
[0081] In an even further embodiment of the present invention, the
surfactant interacting additive may be comprised in, or,
alternatively, comprises an additive masterbatch which is a colour
master batch.
[0082] In a further embodiment of the present invention, the
surfactant interacting additive comprises TiO.sub.2, CaCO.sub.3
and/or carbon black, e.g. a UV black.
[0083] In still a further embodiment of the present invention, the
surfactant interacting additive comprises hindered-amine light
stabilizers (HALS).
[0084] The present invention do also relate to a process for
producing an article, wherein said process comprises use, for
example extrusion, of a polymer composition as described herein.
Said extrusion may be performed at a temperature of, for example,
140 to 280.degree. C.
[0085] In a further embodiment of the present invention a polymer
composition is disclosed, wherein the polymer composition comprises
a crosslinked polyolefin, wherein the crosslinked polyolefin is
produced by crosslinking the crosslinkable polyolefin comprised in
the polymer composition as described herein.
[0086] In an even further embodiment of the present invention a
polymer composition is disclosed, wherein the polymer composition
comprises a crosslinked polyolefin, as described herein, and
wherein the polymer composition has a hot set elongation of less
than 175% when measured according to method EN60811-2-1:1999.
[0087] In even further embodiments of the present invention a
polymer composition is disclosed, wherein the polymer composition
comprises a crosslinked polyolefin, as described herein, and
wherein the polymer composition has a hot set elongation of less
than 150, 130 or 100%
[0088] A further embodiment of the invention relates to an article,
for example, a coating, a wire or a cable, which article comprises
the polymer composition as described herein.
[0089] Still a further embodiment of the present invention relates
to use of the polymer composition as described herein.
[0090] The following examples illustrate, but intend not to limit,
the present invention.
EXAMPLES
[0091] 1. Methods
[0092] a. Melt Flow Rate
[0093] The melt flow rate (MFR) is determined according to ISO 1133
and is indicated in g/10 min. The MFR for ethylene polymers is
determined at 190.degree. C. and with a 2.16 kg load
(MFR.sub.2).
[0094] b. Hot Set Elongation
[0095] The crosslinking of the polymer composition was determined
according to IEC-60811-2-1 (hot set method and permanent set) by
measuring the thermal deformation at 200.degree. C. and a load of
0.2 MPa after various times of crosslinking at 23.degree. C. and
50% R.H.
[0096] 2. Materials
[0097] Base resin, which is comprised in the polymer composition,
is in the examples herein an ethylene vinylsilane copolymer Visico
LE4423.TM., i.e. a crosslinkable polyolefin with hydrolysable
silane groups, supplied by Borealis having a density of 923
kg/m.sup.3 and an MFR.sub.2.16 of 1.0 g/10 min.
[0098] Catalyst masterbatches are composed as described Table 1
below. DBSA (dodecylbenzenesulfonic acid), i.e. Ufacid K from Unger
Fabrikker. Nacure.RTM. CD-2180, i.e. a highly hydrophobic mixture
of C.sub.12-alkylated naphthyl sulfonic acids (i.e. silanol
condensation catalysts selected from the compound of formula I, as
described herein), from King Industries, having an active content
of 80%. Catalyst masterbatches were prepared having an equimolar
amount of sulfonic acid groups. Amounts are given in weight
percentages of the total catalyst masterbatch.
[0099] The catalyst carrier is BAR717, i.e. ethylene butylacrylate
copolymer, which is supplied by Special Polymers Antwerp. The
BAR717 has a butyl acrylate content of 17 weight % and an
MRF.sub.2.16 of 7.5 g/10 min.
[0100] The stabiliser is Lowinox CPL, a phenolic stabilizer from
Chemtura, and the drying agent is Dynasylan 9116, HDTMS,
hexadecyltrimethoxysilane produced by Evonic.
[0101] The surfactant interacting additive used in the tests is
2000-WT-50, a white colour masterbatch supplied by PolyOne.
2000-WT-50 contains by weight: 30-60% TiO.sub.2, 10-30% CaCO.sub.3,
1-5% Amorphous Silica, 1-5% Al.sub.2O.sub.3, 0.1-1% Quartz.
TABLE-US-00001 TABLE 1 Catalyst Catalyst masterbatch A masterbatch
B BAR717 (catalyst carrier) 86.1 83.3 DBSA 3.5 Nacure CD-2180 6.3
Stabilizers 6.4 6.4 Drying agent 3 3
[0102] 3. Sample Preparation
[0103] Catalyst masterbatches may be prepared by mixing the
components in a Banbury kneader at 130.degree. C. for 8 minutes.
The compounds may afterwards be pelletized on a Buss kneader. Tapes
of 1.8 mm may be extruded using a Collin tape extruder operating at
50 rpm with a temperature profile of 150/160/170 degrees Celsius of
the extrusion zones.
TABLE-US-00002 TABLE 2 Composition of the tapes. Comparative
Comparative Comparative Innovative Example 1 Example 2 Example 3
Example 1 LE4423 95 95 94 94 Catalyst MB A 5 5 Catalyst MB B 5 5
2000-WT-50 1 1
[0104] The tapes were treated in 90.degree. C. water bath or
ambient conditions (23.degree. C., 50% RH) and hot-set elongation
were measured at 200.degree. C. after 15 minutes applying a load of
0.2 MPa. Amounts are given in weight percentages of the total
composition.
[0105] The results from the hot-set elongation tests are given in
Table 3. The standard requirements for LV cable insulation are a
hot-set elongation of <175% as given in e.g. IEC60502-1 Ed. 2
and HD603 A1.
TABLE-US-00003 TABLE 3 Hot-set elongation. Hot-set Comparative
Comparative Comparative Innovative elongation after: Example 1
Example 2 Example 3 Example 1 4 h in water bath <100% <100%
Fail <150% 8 h in water bath <100% <100% Fail <150% 24
h in water bath <60% <60% Fail <150% 14 days in <100%
<100% <150% <150% ambient condition 21 days in <100%
<100% <150% <150% ambient condition Total result Pass Pass
Fail Pass
[0106] The comparative examples 1 and 2, without colour masterbatch
meet all hot set and crosslinking requirements. The comparative
example 3 comprising a highly hydrophilic alkyl benzene sulphonic
acid catalyst with, comparably, fewer carbons and a TiO.sub.2
colour masterbatch the sample crosslinks in ambient condition but
not in hot water bath (the sample 3 broke within one minute in the
hot set oven). The innovative example 1, comprising a highly
hydrophobic mixture of alkylated naphthyl sulfonic acids with,
comparably, more carbons and a TiO.sub.2 colour masterbatch the
sample meet all hot set requirements both when crosslinking in
Ambient condition and in the hot water bath.
* * * * *