Title of Invention

STABILIZED MEDIUM AND HIGH VOLTAGE CABLE INSULATION COMPOSITION

Abstract Abstract The invention relates to a polyethylene composition for use as insulation for wire and cable that has improved scorch resistance comprising (a) a polyethylene (b) a scorch inhibitor having a melting point below 50 °C at atmospheric pressure, and (c) an organic peroxide.
Full Text

Stabilized medium and high voltage cable insulation composition
The invention relates to a polyethylene composition for use as insulation for wire and cable that has improved scorch resistance, the stabilized composition is suitable for use as cable insulation of medium and high voltage power cables.
Insulation compositions generally include a polyethylene, a peroxide crosslinking agent and a stabilizer. Polymers containing peroxides are vulnerable to scorch, i.e. to premature crosslinking occurring during the extrusion process.
There are several key factors which must be considered when making the choice of an appropriate stabilizing system. These factors include the crosslinking speed and the degree of crosslinking, resistance to scorch at extrusion temperatures, efficient retention of mechanical properties before and after high temperature aging, no exudation to the polymer surface and a high degree of cleanliness.
US Patent 6,191,230 described a polyethylene composition containing as scorch inhibitor a substituted hydroquinone, 4,4'-thiobis(2-methyl-6 -tert.-butylphenol); 4,4'-thiobis(2 -tert.-butyl-5-methylphenol); or mixtures thereof.
In order to remove electroconductive impurities the European Patent Application EP-A-613154 describes a process to prepare a polyethylene composition whereby the crosslinking agent and/or the stabilizer are blended into a low density polyethylene after being subjected to a purification process.
Cleanliness is a critical parameter and there is still a need to provide clean insulating material containing polyethylene crosslinkable compositions which can be extruded with a minimum of premature crosslinking and yet showing a sufficient crosslinking speed.
It has now been found that an improved insulation material can be obtained by using a liquid stabilizing system.

Thus, the invention relates to a composition comprising
(a) a polyethylene
(b) a scorch inhibitor having a melting point below 50 °C at atmospheric pressure, and
(c) an organic peroxide.
Scorch inhibitors having a melting point below 50 °C at atmospheric pressure are e.g.
phenols as described in US 4,759, 862 and US 4,857,572,
phenols as described in US 5,008,459 or mixtures of said phenols;
mixtures containing an aromatic amine and a phenol as described in US 5,091,099.
The term "scorch inhibitor" also includes mixtures as described in US 5,091,099 containing
in addition a phenol as described in US 4,759, 862, US 4,857,572 or US 5,008,459.
Referring to US 4,759, 862 and US 4,857,572 the scorch inhibitor is a compound of formula
wherein
R1 is d-zoalkyl or Chalky! which is substituted by phenyl, C2.2oalkenyl, Cwoalkinyl,
Cs-gcycloalkyl, phenyl or tolyl; R2 and R3 each independently of the other are:
C1-.2oalkyl or C^oalkyl which is substituted by the following radicals: phenyl, one or two hydroxyl, cyano, formyl, acetyl, -O-COR3; R5 is C^oalkyl; C2-2oalkenyl or C3.20alkinyl;
C5.7cycloalkyl or C5.7cycloalkyl which is substituted by hydroxyl;
phenyl, 4-chlorophenyl, 2-methoxycarbonylphenyl, p-tolyl,
1,3-benzthiazol-2-yl, or
-(CHR8)nCOOR7 or -(CHR6)nCONRBR9 with
n is 1 or 2,
R8 is hydrogen or C^alkyl,
R7 is C1-.20alkyl, Chalky! which is interrupted by one to five O or S,
C5.7cycloalkyl, phenyl, benzyl, tolyl,
R8 and R9 are hydrogen or C^alkyl;
R4 is hydrogen or methyl.

C1--2oalkyl radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, 1,1-dimethylbutyl, n-octyl, 2-ethylhexyl, isooctyl (isomeric mixture of primary octyl), n-nonyl, tert.-nonyl (isomeric mixture), n-decyl, 1,1,3,3-tetramethylbutyl (t-octyl), n-dodecyl, tert.-dodecyl (mixture containing as main component 1,1,3,3,5,5-hexamethylhexyl and 1,1,4,6,6-pentamethylhept-4-yl), n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.
Cwoalkenyl radicals are, for example, vinyl, allyl (prop-2-enyl), but-3-enyl, pent-4-enyl, hex-5-enyl, oct-7-enyl, dec-9-enyl ordodec-11-enyl. Allyl is preferred.
CMoalkinyl radicals are, for example, propargyl, but-3-inyl, hex-5-inyl, oct-7-inyl, dec-9-inyl, dodec-11-inyl, tetradec-13-inyl, hexadec-15-inyl, octadec-17-inyl oreicos-19-inyl. Propargyl is preferred.
C5.9cycloalkyl radicals are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and in particular cyclohexyl.
C1-.20alkyl radicals substituted by phenyl are, for example, benzyl, phenethyl, cc-methylbenzyl, a.a-dimethylbenzyl, phenylbutyl, phenyl-a,a-dimethylpropyl, phenylhexyl, phenyl-a,a-di-methylbutyl, phenyloctyl or phenyl-a,a-dimethylhexyl. Benzyl, a-methylbenzyl and a,a-dimethylbenzyl are preferred.
C,.20alkyl radicals substituted by one or two hydroxyl groups are, for example, 2-hydroxy-ethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxyhexyl, 2-hydroxyoctyl, 2-hydroxydecyl, 2-hydroxydodecyl, 2-hydroxytetradecyl, 2-hydroxyhexadecyl, 2-hydroxyoctadecyl, 2-hydroxy-eicosyl or 2,3-dihydroxypropyl. Preferred is 2-hydroxyethyl, 2-hydroxypropyl and 2,3-dihydroxypropyl.
C,.20alkyl radicals substituted by phenyl and hydroxy are, for ex. 1-phenyl-2-hydroxyethyl.
d.20alkyl radicals substituted by cyano are, for example, 2-cyanoethyl.

C^oalkyl interrupted by one to five O or S are, for example, 3-oxapropyl, 3-thiapropyl, 3-oxabutyl, 3-thiabutyl, 3-oxapentyl, 3-thiapentyl, 3,6-dioxaheptyl, 3,6,9-trioxadecyl or 3,6,9,12,15,18 hexaoxanonadecyl.
The group R1 is preferably C1-^alkyl, more preferably methyl or tert.-butyl, most preferably methyl and the groups R2 and R3 are preferably identical and are C1-.20alkyl or Chalky! substituted by one or two hydroxyl, preferably Cs-ualkyl, and in particular n-octyl, tert.-nonyl, n-dodecyl or tert.-dodecyl, 2-hydroxyethyl or 2,3-dihydroxypropyl.
The substances listed below may be regarded as examples of representatives of
compounds of the formula I:
a) Compounds of formula I with
R1 =alkyl (methyl, tert.-butyl, isopropyl, 2-ethylhexyl, 1,1-dimethylpropyl or 1,1-dimethylbutyl)
2,4-bis(2'-hydroxyethylthiomethyl)-6-methylphenol,
2f4-bis(2',3'-dihydroxypropylthiomethyl)-3,6-dimethylphenol,
2,4-bis(2'-acetyloxyethylthiomethyl)-3,6-dimethyl phenol,
2,4-bis(2'-n-decanoyloxyethylthiomethyl)-6-methylphenol,
2,4-bis(n-octylthiomethyl)-6-methylphenol,
2,4-bis(n-dodecylthiomethyl)-6-methylphenol,
2,4-bis(tert.-dodecylthiomethyl)-6-methylphenol,
2,4-bis(benzylthiomethyl)-6-methylphenol,
2,4-bis(2'-ethylhexyloxycarbonylmethylthiomethyl)-6-methylphenol,
2,4-bis(n-octadecyloxycarbonylmethylthiomethyl)-3,6-dimethylphenoll
2,4-bis(methylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(ethylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-propylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-butylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-hexylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-octylthibmethyl)-6-tert.-butylphenol,
2,4-bis-(n-decylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-dodecylthiomethy))-6-tert.-butylphenol,
2,4-bis-(n-tetradecylthiomethyl)-6-tert.-butylphenol,

2,4-bis-(n-hexadecylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(n-octadecylthlomethyl)-6-tert.-butylphenol,
2,4-bis-(n-eicosylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(isopropylthiomethyl)-6-tert.-butylphenol,
2f4-bis-(sec.-butylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(tert.-butylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(2-ethylhexylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(1,1,3,3-tetramethylbutylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(1l1I3l3,5,5-hexamethylhexylthiomethyl)-6-tert.-butylphenoll
2,4-bis-[4-(2,2l4,6,6-pentamethylheptyl)-thiomethyl]-6-tert.-butylphenol,
2,4-bis-(prop-2-enylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(prop-2-inylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(cyclohexylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(2-hydroxycyclohexylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(phenylthiomethyl)-6-tert.-butylphenol,
2,4-bis(phenylthiomethyl)-3-methyl-6-tert.-butylphenol,
2,4-bis-(benzylthiomethyl)-6-tert.-butylphenol,
2,4-bis-(p-toly lthiomethyl)-6-tert.-butylphenol,
2,4-bis[2'-(2"-ethylhexyloxycarbonyl)ethylthiomethyl]-3-methyl-6-tert.-butyl phenol,
the dimethyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the dibutyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the dioctyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the didodecyl ester of 2,4;bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the monomethyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the dimethyl ester of 2,4-bis-(4 -carboxy-2-thiabutyl)-6-tert.-butylphenol,
the dioctyl ester of 2,4-bis-(4-carboxy-2-thiabutyl)-6-tert.-butylphenol,
the di-(2-ethylhexyl) ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the dimethyl ester of 2,4-bis-(3-carboxy-2-thiabutyl)-6-tert.-butylphenol,
the dimethyl ester of 2,4-bis-(4-carboxy-3-methyl-2-thiapentyl)-6-tert.-butylphenol
the N,N-dimethylamide of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the N,N-dihexylamide of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the N,N-didodecylamide of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the N,N-dimethylamide of 2,4-bis-(4-carboxy-2-thiabutyl)-6-tert.-butylphenol,

the N,N-dimethylamide of 2,4-bis-[3-carboxy-2-thiabutyl]-6-tert.-butylphenol,
the N,N-dibutylamide of 2,4-bis-(4-carboxy-3-methyl-2-thiapentyl)-6-tert.-butylphenol,
the dicyclohexyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the diphenyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the dibenzyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the di-p-tolyl ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the di-(3-thiabutyl) ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the di-(3-oxabutyl) ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
the di-(N,N-dimethylamino-2-ethyl) ester of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert-
butylphenol,
the diamide of 2,4-bis-(3-carboxy-2-thiapropyl)-6-tert.-butylphenol,
2,4-bis-
2,4-bis-
2,4-bis
2,4-bis
2,4-bis
2,4-bis-l
2,4 -bis
2,4-bis-
2,4-bis-
2,4-bis-
2,4-bis-
2,4-bis-
2,4-bis-|
2,4-bis-
2,4-bis-2,4-bis-
2,4-bis-2,4-bis-
the diamide of 2,4-bis-(4-carboxy-2-thiabutyl)-6-tert.~butylphenol,
prop-2-enylthiomethyl)-6-tert.-butylphenol,
prop-2-inylthiomethyl)-6-tert.-butylphenol,
2-hydroxyethylthiomethyl]-6-tert.-butyiphenol,
2-cyanoethylthiomethyl]-6-tert.-butylphenol,
(4-methoxyphenyl)-thiomethyl]-6-tert.-butylphenol,
(4-chlorophenyl)-thiomethyl]-6-tert.-butylphenol,
[(2-methoxycarbonylphenyl)-thiomethyl]-6-tert.-butylphenol,
(1,3-benzthiazol-2-yl)-thiomethy l]-6-tert.-butylphenol,
2,3-dihydroxypropylthiomethyl]-6-tert.-butylphenol,
(3,5-di-tert.-butyl-4-hydroxyphenyl)thiomethyl]-6-tert.-butylphenol,
4-(3,5-di-tert.-butyl-4-hydroxyphenyl)-2-thiabutyl]-6-tert.-butyl phenol,
4-acetoxy-2-thiabutyl]-6-tert.-butylphenol,
3-formyl-2-thiabutyl]-6-tert.-butylphenol and
3-acetyl-2-thiabutyl]-6-tert.-butylphenol.
n-octylthiomethyl)-6-isopropylphenol, n-dodecylthiomethyl)-6-isopropylphenol,
n-octylthiomethyl)-6-(2-ethylhexyl)-phenol, n-dodecylthiomethyl)-6-(2-ethylhexyl)-phenol,
2,4-bis-(n-dodecylthiomethyl)-6-(1,1-dimethylpropyl)-phenol,

2,4-bis-(n-octylthiomethyl)-6-(1,1-dimethylbutyl)-phenol, 2,4-bis-(n-dodecylthiomethyl)-6-(1,1-dimethylbutyl)-phenol,
b) compounds of formula I with R1 = cycloalkyl (cyclohexyl)
2,4-bis-(n-octylthiomethyl)-6-cyclohexylphenol, 2,4-bis-(n-dodecylthiomethyl)-6-cyclohexylphenol.
c) compounds of formula I with R1 = phenyl or tolyl
2,4-bis-(n-octylthiomethyl)-6-phenylphenol, 2,4-bis-(n-dodecylthiomethyl)-6-phenylphenol, 2,4-bis-(n-octylthiomethyl)-6-p-tolylphenol, 2,4-bis-(n-dodecylthiomethyl)-6-p-tolylphenol.
d) compounds of formula I with R1 = alkyl substituted by phenyl (benzyl, a.oc-dimethylbenzyl)
2,4-bis-(n-octylthiomethyl)-6-benzylphenol,
2,4-bis-(n-dodecylthiomethyl)-6-benzylphenol,
2,4-bis-(n-dodecylthiomethyl)-6-(a,a-dimethylbenzyl)-phenol.
e) compounds of formula I with R1 = alkenyl (prop-2-enyl) or alkinyl (prop-2-inyl)
2,4-bis-(n-octylthiomethyl)-6-prop-2-enylphenol, 2,4-bis-(n-dodecylthiomethyl)-6-prop-2-enylphenol. 2,4-bis-(n-dodecylthiomethyl)-6-prop-2-inylphenol.


The most preferred liquid scorch inhibitor of formula I is 2,4-bis(n-octylthiomethyl)-6-methylphenol and 2,4-bis(n-dodecylthiomethyl)-6-methylphenol.


The substances listed below may be regarded as examples of representatives of
compounds of the formula II:
2,6-bis-(2,-hydroxyethylthiomethyl)-4-methylphenol,
2,6-bis-(2\3' 2,6-bis-(2'-methylamlnocarbonylethylthfomethyl)-4-phenylphenQl,
2,6-bis-(N,N-diethylamlnocarbonyl-ethylthiomethyl)-4-allylphenol,
2,6-bls-(n-octylthiomethyl)-4-methylphenol,
2,6-bls-(n-dodecylthiomethyl)-4-methylphenol
2,6-bis-(n-octy(thiomethyl)-4 -tert.-butylphenol,
2,6-bl$-(n-dodecylthiomethyl)-4 -tert.-butylphenol,
a.e-bis-^'OCtyltbiomethylJ^^lM'.S'^'-tetramethylbutyOphenol,
2,6-bls-(t-nonylthiomethyl)-4 -tert.-butylphenol,
2,6-bis-(t-dodecylth1omethyI)-4 -tert.-octyl-phenol,
2,6-bis-(benzylthiomethyl)-6-methylphenol,
2,6-bis-(phenylthiomethyl)-4 -tert.-butyl-phenol,
2.6-bis-(2'-ethylhexyloxycarbonylmethyl-thiomethyl)-4-cyclohexylphenol,
2,6-bis-(2'-isoociyloxycarbonylmethyl-thiomethyl)-4-cyclohexylphenol,
2,6-bis-(n-octadecyloxycarbonylmethyl-thiomethyl)-4-propargylphenol,
2,6-bis-[2'-(2"-ethylhexyloxycarbonyl)-ethylthiomethylJ-4-tert.-butylphenol.
The substances listed below may be regarded as examples of representatives of
compounds of the formula III.
2,2-bis-[4' ,4"-dihydroxy-3' ,3", 5", 5"-tetrakis-(n-octy Ithiomethy l)-phenyl]-propane,
2,2-bis-[4',4"-dihydroxy-3',3")5',5"-tetrakis-(n-dodecylthiomethyl)-phenyl]-propane,
bis-[4,4'-dihydroxy-3,3',5,5'-tetrakis-(n-octylthiomethyl)-phenyl3-methane,
bis-[4,4'.dihydroxy-3,3',5,5'-tetrakis-(n-dodecylthiomethyl)-phenyl]-methane,

2,2-bis-[4,l4',-dihydroxy-3,,3",5',5"-tetrakis- 212-bis-[4',4"-dihydroxy-3'13,,,5'15"-tetrakis-(2-isooctyloxycarbonyl-methylthiomethyl)-phenyl) propane.
With reference to US 5,091,099 the scorch inhibitor is a mixture containing an amine selected from diphenylamine, 4-tert.-butyldiphenylamine, 4-tert.-octyldipenylamine, 4,4'-di-tert.-butyldiphenylamine, 214,4'-tris-tert.-butyldiphenylamine, 4-tert.-butyl-4'-tert.-octyldi-phenylamine, o.o'-, m,m'- or p,p'-di-tert.-octyldiphenylamine, 214-di-tert.-butyl-4'-tert.-octyl-diphenylamine^^'-di-tert.-octyldiphenylamine, 2,4-di-tert.-octyl-4'-tert.-butyldiphenylamine, and



The amounts of the aromatic amines in the mixture are: not more than 5% by weight of diphenylamine (a), 8-15% by weight of 4-tert.-dibutyl-diphenylamine (b), 24 to 32% by weight of compounds selected from group (c),
(c)(i) 4-tert.-octyldiphenylamine ,
(c)(ii)4,4'-di-tert.-butyldiphenylamine
(c)(iii) 2,4,4'-tris-tert.-butyldiphenylamine 23 to 34% by weight of compounds selected from group (d),
(d)(i) 4-tert.-butyl-4'-tert.-octyldiphenylamine
(d)(ii) o,o'-, m,m'- or p,p'-di-tert.-octyldiphenylamine
(d)(iii) 2,4-di-tert.-butyl-4'-tert.-octyldiphenylamine; and 21 to 34% by weight of compounds selected from group (e)
(e)(i)4,4,-di-tert.-octyldiphenylamine
(e)(ii)2,4-di-tert.-octyl-4'-tert.-butyldiphenylamine, based in each case on the total amount of amines.
A preferred amine is 4,4'-di-tert.-oc.tyldiphenylamine or Amine (A) which is a mixture of: |
3wt% diphenylamine, 14wt% 4-tert-butyldiphenylamine, 30wt% (4-tert.-octyldiphenylamine 4,4'-di-tert.-butyldiphenylamine and 214,4'-tris-tert.-butyldiphenylamine)1 29wt% (4-tert.-butyl-

4'-tert -octyldiphenylamine, o,o', m.rn' or p(p'-di-tert.-octyldiphenylamine and 2,4-di-tert-butyW-tert.-octyldiphenylamine), 18wt% 4,4,-dMert.-octyldiphenylamine and 6wt% 2,4-di-tert.-octyl-4'-tert.-butyldiphenylamine.
Examples of mixtures suitable as scorch inhibitor are: Amine (A) and Phenol (P) 4.4'-di-tert.-octyldiphenylamine and Phenol (P) 4,4'-dkert.-octyidiphenylamine and Phenol (S) Amine (A) and Phenol (U) Amine (A) and Phenol (V) Amine (A) and Phenol (W) Amine (A) and Phenol (X)
The weight ratio of amine to Phenol is 4 to 5:1,
Especially suitable as liquid scorch inhibitor is a mixture of 80wt% 4,4'-di-tert-octyldiphenylamine and 20wt% of Phenol P.
The compounds of the formulae I, II and III are prepared by processes which are known per se and described in US 4,759, 862 and US 4,857,572 (formula I) or in US 5,008,459 (formula II and III).
Polyethylene, as that term is used herein, is a homopolymer of ethylene or a copolymer of ethylene and a minor proportion of one or more alpha-olefins having 3 to 12 carbon atoms, and preferably 4 to 8 carbon atoms, and, optionally, a diene, or a mixture or blend of such homopolymers and copolymers. The mixture can be a mechanical blend or an in situ blend. Examples of the alpha-olefins are propylene, 1-butene, 1-hexene, 4-methyM-pentene, and 1-octene. The polyethylene can also be a copolymer of ethylene and an unsaturated ester such as a vinyl ester, e.g., vinyl acetate or an acrylic or methacrylic acid ester
Suitable polyethylenes are so-called high pressure polyethylenes. A variety of such polymers are commercially available. The high pressure polyethylenes are preferably homopolymers of ethylene having a density in the range of 0.910 to 0.930g/cm'. The homopolymer can also have a melt index in the range of about 1 to about 5 g per 10 minutes, and preferably has a

melt index in the range of about 0.75 to about 3 g per 10 minutes. Melt index is determined under ASTMD-1238.
The crosslinking agent is an organic peroxide including dialkyl peroxides such as dicumyl peroxide, di -tert.-butyl peroxide, tert.-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)-hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)-hexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane-3, 2,5-dimethyl-2,5-di(t*amylperoxy)hexyne-3, The organic peroxides have a decomposition temperature in the range of 100 to 200°C. Especially preferred is dicumyl peroxide, having a decomposition temperature of 150°C.
The organic peroxide and the scorch inhibitor are incorporated into the polyethylene by known methods, for example by melt blending in a roll mill, a kneading extruder or a mixer at a temperature lower than the decomposition temperature of the peroxide or by a soaking method whereby the liquid scorch inhibitor/peroxide blend is mixed until the whole liquid phase is soaked into the polymer.
The scorch inhibitor and/or the peroxide can be added to the polyethylene either before or during processing.
The amount of the scorch inhibitor is in the range from 0.01 to 1wt%, preferably 0.1 to 0.5wt%,
The amount of the peroxide is in the range from 0.5 to 5 wt% preferably 1 to 3wt%.
Optionally epoxidized soya bean oil can be added in an amount 1 to 3wt%, preferably 2wt% to the polymer to stabilize the polymer against color degradation.

In a preferred embodiment the process is carried out in an extruder. The polyethylene or the polyethylene/peroxide blend is introduced into the extruder and the scorch inhibitor having a melting point below 50 °C or the scorch inhibitor and the peroxide is added, for example, through a side feed to said extruder, optionally after being filtered.
The extrudate is then crosslinked by exposing it to a temperature greater than the decomposition temperature of which the organic peroxide decomposes. The extrusion can be done around one or more electrical conductors to form a medium voltage or high voltage cable. The conductor is either a bare conductor or the conductor is surrounded by primary insulation and /or semicon layer. The cable is then exposed to crosslinking temperatures.
The crosslinking may be carried out in any conventional fashion such as in an oven or in a continuous vulcanization tube, optionally, but not necessarily under nitrogen atmosphere and increased pressure.
The stabilized composition is suitable for use as cable insulation of medium and high voltage power cables. A range for medium voltage is 1 kV to 40 kV. "High voltage" relates to a valve voltage exceeding about 40 kV, especially 40-110kV.
Advantages of the inventionjs a surprisingly high resistance to scorch at extrusion temperature^hile_majntaining a satisfactory_crosslinking speed and crosslinking density The mechanical properties before and after heat aging meet the industrial standard requirements.
The following examples illustrate the invention in detail.
Compound preparation
A low density polyethylene (d=0.923g/cm3), type Escorene LD 100 MED from Exxon Mobil Chemical, is heated up to 90°C in a static oven. The stabilizer and the peroxide are heated up to 70°C by exposure to a water bath. The clear stabilizer/peroxide melt is added to the warm polymer granulate and kept in the oven for approximately 60min. Every ten minutes

the mixture is quickly removed and thoroughly shaken. The procedure is repeated until the whole liquid phase was soaked into the polymer.
Examples of laboratory results:
Scorch resistance
In order to simulate cable extrusion condition's, 43 g of each compound are weighed and stir melted at 30 rpm in a lab kneader, type Brabender Plasticorder 814 300, at an initial mass temperature of 120°C. The material is kneaded under a constant load of 2.0 kg until the minimum torque is obtained and a subsequent remarkable increase in torque could be observed. The scorch time is determined as the period between minimum torque and an increase by 1Nm starting from the minimum torque. A longer scorch time means fewer problems occur due to premature crosslinking during extrusion. Tab. 1 shows the results.
Crosslinking procedure
The production of crosslinked PE-LD plaques (thickness: 1.5 mm) is carried out in three compression molders atdifferent temperatures: In the first mold a defined weight of material is spread out in a frame and heated up to 120"C for six minutes. During that time the pressure is increased stepwise from 0 to 150 bar. In the next step the frame with the plaques is transferred to a second compression molder and left at 180°C for 15 min for completion of crosslinking. Finally, the plaques are cooled down from 180°C to room temperature within ten minutes.
Crosslinking Speed In the Rheometer
5g of each sample are heated up to 180°C in a Moving Die Rheometer (Monsanto MDR
2000). At test temperature the samples are exposed to a periodical alternating stress at
constant amplitude (3° torsion at 1.66 Hz) until the maximum torque is obtained. The
criterion is the constant crossliijiking speed, which is a measure of the interaction between
i crosslinking agent and antioxidant.


Gel Content
The amount of insolubles is generally a measure of the degree of crosslinking obtained A defined weight of the crosslinked plaques is exposed to a solvent (toluene, xylene or decaline) at 90°C for 24h. The soluble parts are filtered through a sieve and both sieve and sample are washed with the corresponding solvent. Afterwards both are dried in a vacujm dryer until a constant weight is obtained.
The Gel content was determined according to the formula: Get content (%) = 100 (W, - W 2)/W3 W, « Weight of Sieve and insolubles after vacuum drying WH = Weight of the annealed, empty sieve before filtration W2 = Weight of the polymer sample
All results (Table 2) are in the typical range expected for this kind of application.


Thermal Aging and Mechanical Tests
Tensile bars (dimensions according to DIN 53-504-82) are punched from the crosslinked
plaques and split into four sets for oven aging at 150°C for 0, 3, 10 and 14 days. The tensile
bars are evaluated for retention of tensile strength and elongation (yield; break).
All results (Tables 3 and 4) are within the standard range of results expected for this
application.



Reduced Exudation of Stabilizers
It is examined how the liquid systems behave in comparison to the solid ones. A high
tendency for migration of stabilizers to the polymer surface can cause various problems,
such as loss of active radical scavengers and a sticky surface lumping together the granules
during storage. Exudation of stabilizers and peroxides is also known to have a negative
impact on the extrusion process and the cable product and exudation dust may foul filters
and cause slippage and instability in the extrusion process.
The example compares the sweat out or exudation behavior of the different systems after conditioning at 55°C. Both Invention A and Invention B show an impressive improvement in terms of compatibility with the polymer. This offers a further opportunity for the converter to

increase the additive loadings if appropriate, especially where higher scorch resistance is desired, without expecting severe problems with exudation..
Each formulation is kept in the oven at 55°C in order to simulate antioxidant plate out. At the appropriate recall interval, an aliquot is extracted from the oven and measured for surface exudation. The samples are washed with methylene chloride (about 15 seconds contact with polymer) and the solution is then transferred to a round bottom flask and evaporated to dryness. The resultant residue is reconstituted with a standard solution and analyzed quantitatively via liquid chromatography.






' We claim, 1. A composition comprising
(a) a polyethylene,
(b) a scorch inhibitor having a melting point below 50°C at atmospheric pressure and is a compound of the formula 1

wherein
R' is C1-2oalkyl or C1-2oalkyl, which is substituted by phenyl, C2.2oalkyl, C3.2oalkinyl, C5-9cycloalkyl, phenyl or tolyl;
R^ and R^ each independently of the other are: C1-2oalkyl or C1-2oalkyl which is
substituted by the following radicals: phenyl, one or two hydroxyl, cyano, formyl,
acetyl, -0-COR^; R^ is C1-2oalkyl; Cz-aoalkenyl; C3.2oalkinyl;C5.7cycloalkyl or
C5.7cycloalkyl which is substituted by hydroxyl; phenyl, 4-chlorophenyl,
2-methoxycarbonylphenyl, p-tolyl, l,3-benzthazol-2-yI, or -(CHR^)nCOOR' or -
(CHR*)nCOOR*R^ with n is 1 or 2,
R^ is hydrogen or Ci-ealkyl,
R^ is Ci-2oalkyl, C1-2oalkyl which is interrupted by one to five O or S, Cs-Tcycloalkyl,
phenyl, benzyl, tolyl,
R^ and R^ are hydrogen or Ci-galkyl;
R' is hydrogen or methyl; and
(c) an organic peroxide; and which is free of a sterically hindered amine and a
phenolic antioxidant other than a compound of the formula 1.
2. The composition as claimed in claim 1, wherein
R' is C1-2oalkyI, and
R^ and R^ are identical and are C1-2oalkyl or C1-2oalky substituted by one or two
hydroxyl.
3. The composition as claimed in claim 1, wherein the scorch inhibitor of formula 1 is 2, 4-bis(n-octylthiomethyl)-6-methylphenol or 2,4-bis(n-dodecylthiomethyl)-6-methylphenol.
4. The composition as claimed in claim 1, additionally comprising (an mine ielected from the group consisting of diphenyl amine, 4-tert-butyldipiienylamine, 4-tert-octyldipenylamine, 4.4'-di-tert-butyldiphenylamine, 2,4,4'-tris-tert-butyldiphenylamine, 4-tert-butyl-4'-tert-octyldi-phenylamine, o,o'-, m,m'-or p.p'-di-tert-octyldiphenylamine, 2,4-di-tert-butyl-4 '-tert-octyl-diphenylamine, 4,4 '-di-tert-octyldiphenylamine, 2,4-di-tert-butyldiphenylamine.

5. The composition as claimed in claim 4, wherein the amine is 4,4'-di-tert-
octyldiphenylamine or Amine (A) which is a mixture of: 3wt% diphenylamine, 14wt%
4-tert-butyldiphenylamine, 30%wt 4-tert-octyldiphenylamine 4,4'-di-tert-
butyldiphenylamine and 2,4,4'-tris-tert-butyldiphenylaraine, 29wt% 4-tert.-butyl-4'-tert-
octyldiphenylamine, o,o'm,m' or p,p'-di-tert-octyldiphenylamine and 2,4-di-tert-butyl-
4'-tert-octyldiphenylamine, 18wt% 4,4'-di-tert-octyl-diphenylamine and 6wt% 2,4-di-
tert-octyl-4'-tert-butyldiphenylamine.
6. The composition as claimed in claim 1, wherein the amount of scorch inhibitor is in the
range from 0.01 to lwt% and the amount of the peroxide is in the range from 0.5 to
5 wt%.
7. A process for preparing a crosslinked polyethylene composition wherein a polyethylene
or a polyethylene/peroxide blend is introduced into an extruder with a scorch inhibitor
according to claim 1 having a melting point below 50C; or wherein a polyethylene is
introduced into an extruder with a scorch inhibitor and a peroxide, whereby the
extrudate is then crosslinked by exposing it to a temperature greater than the
decomposition temperature of which the organic peroxide decomposes.


Documents:

0261-mas-2002 abstract.pdf

0261-mas-2002 claims-duplicate.pdf

0261-mas-2002 claims.pdf

0261-mas-2002 correspondence-others.pdf

0261-mas-2002 correspondence-po.pdf

0261-mas-2002 description (complete)-duplicate.pdf

0261-mas-2002 description (complete).pdf

0261-mas-2002 form-1.pdf

0261-mas-2002 form-13.pdf

0261-mas-2002 form-18.pdf

0261-mas-2002 form-26.pdf

0261-mas-2002 form-3.pdf

0261-mas-2002 form-5.pdf

0261-mas-2002 form-6.pdf

0261-mas-2002 others.pdf


Patent Number 228824
Indian Patent Application Number 261/MAS/2002
PG Journal Number 12/2009
Publication Date 20-Mar-2009
Grant Date 11-Feb-2009
Date of Filing 09-Apr-2002
Name of Patentee CIBA HOLDING INC
Applicant Address KLYBECKSTRASSE 141, 4057 BASEL,
Inventors:
# Inventor's Name Inventor's Address
1 WOLFGANG VOIGT IM FELDLI 7, 79541 LORRACH,
2 JOHN KENNY IM REINACHERHOF 189, 4153 REINACH,
PCT International Classification Number H01B3/18
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 01810511.4 2001-05-23 EUROPEAN UNION
2 01810356.4 2001-04-10 EUROPEAN UNION