阅读说明：本技术 用于柔性电缆的湿气可固化聚合物 (Moisture curable polymers for flexible cables ) 是由 K·福苏姆 S·赫尔斯特罗姆 B·A·苏丹 于 2020-04-29 设计创作，主要内容包括：本发明涉及聚乙烯组合物用于改善包括该聚乙烯组合物的电缆层与聚氨酯树脂之间的粘结性的用途,该聚乙烯组合物包含：一种或多种乙烯共聚物,其中该乙烯共聚物是包含带有极性基团的单体单元和带有可水解硅烷基团的单体单元的三元共聚物,其中,基于总的聚乙烯组合物,该带有极性基团的单体单元的存在量大于5mol.％；和硅烷醇缩合催化剂,基于总的聚乙烯组合物,该硅烷醇缩合催化剂的量为0.0001wt.％至5wt.％。(The present invention relates to the use of a polyethylene composition for improving the adhesion between a cable layer comprising the polyethylene composition and a polyurethane resin, the polyethylene composition comprising: one or more ethylene copolymers, wherein the ethylene copolymer is a terpolymer comprising polar group-bearing monomer units and hydrolysable silane group-bearing monomer units, wherein the polar group-bearing monomer units are present in an amount of greater than 5 mol.%, based on the total polyethylene composition; and a silanol condensation catalyst in an amount of 0.0001 wt.% to 5 wt.%, based on the total polyethylene composition.)

1. Use of a polyethylene composition for improving the adhesion between a cable layer comprising the polyethylene composition and a polyurethane resin, the polyethylene composition comprising:

a) one or more ethylene copolymers, wherein the ethylene copolymer is a terpolymer comprising polar group-bearing monomer units and hydrolysable silane group-bearing monomer units, wherein the polar group-bearing monomer units are present in an amount of greater than 5 mol.%, based on the total polyethylene composition, and

b) a silanol condensation catalyst in an amount of from 0.0001 wt.% to 5 wt.%, based on the total polyethylene composition.

2. Use according to claim 1, wherein the monomer units bearing polar groups are butyl acrylate, ethyl acrylate, methyl acrylate and/or methyl methacrylate.

3. Cable according to any one of the preceding claims, wherein the polar group-bearing monomer units are present in an amount of not more than 25 mol%, based on the total polyethylene composition.

4. Use according to any one of the preceding claims, wherein the monomer units bearing hydrolysable silane groups comprise vinyltrimethoxysilane, vinylbismethoxyethoxysilane, vinyltriethoxysilane, gamma- (meth) acryloxypropyltrimethoxysilane, gamma- (meth) acryloxypropyltriethoxysilane, vinyltriacetoxysilane, and mixtures thereof.

5. Use according to any of the preceding claims, wherein the hydrolysable silane group-bearing monomer units are present in an amount of from 0.001 to 15 wt.%, based on the total polyethylene composition.

6. Use according to any preceding claim wherein the silanol condensation catalyst b) comprises a sulphonic acid based catalyst or a tin based catalyst.

7. Use according to claim 6, wherein the sulfonic acid based catalyst comprises dodecylbenzene sulfonic acid, tetrapropylbenzene sulfonic acid, alkylated naphthalene sulfonic acid, aralkyl sulfonic acid, alkylated aryl disulfonic acid, or mixtures thereof.

8. Use according to any of the preceding claims, wherein the polyethylene composition further comprises c) a scorch retarder additive.

9. Use according to claim 8, wherein the scorch retarder additive c) is present in an amount of from 0.0003mole per 1000g of polyethylene composition to 0.6mole per 1000g of polyethylene composition.

10. Use according to claim 8 or 9, wherein the scorch inhibiting additive c) comprises an alkoxysilane.

11. Use according to any of the preceding claims, wherein the polyethylene composition has an MFR, determined according to ISO1133, of from 0.1g/10min to 50g/10min₂(2.16kg)。

12. Use according to any one of the preceding claims, wherein the layer is an insulating or sheathing layer.

13. Use according to any one of the preceding claims, wherein the cable further comprises a skin layer.

Technical Field

The invention relates to a cable comprising at least one layer comprising a polyethylene composition comprising one or more ethylene copolymers comprising monomeric units carrying polar groups and monomeric units carrying hydrolysable silane groups; and to the use of a polyethylene composition comprising one or more ethylene copolymers, said polyethylene composition comprising monomer units carrying polar groups and monomer units carrying hydrolysable groups, for improving the adhesion between a cable layer comprising said polyethylene composition and a polyurethane resin.

Background

Power cables for low voltages, i.e. voltages below 6kV, usually comprise an electrical conductor covered with an insulating layer. Such a cable will be referred to as a single wire cable hereinafter. Optionally, two or more such single-wire cables are surrounded by a common outermost jacket layer, jacket (jack).

The insulation layer of low voltage power cables is usually made of a polymer composition comprising a polymer base resin, such as a polyolefin. A material commonly used as a base resin is polyethylene. Furthermore, in the final cable, the polymer base resin is typically crosslinked.

For this and other applications, such as welding cables or charging cables for electric vehicles, peroxide crosslinked EPR (ethylene propylene rubber) is mainly used today. However, the manufacturing process of these cables is very complicated, since it is necessary to cross-link the insulation layer in a vulcanization tube, then to put on the jacket, and then to let it pass through the vulcanization tube to cross-link the jacket. Thus, for such flexible cables, it is most common that both the insulation and the jacket are crosslinked. For standard non-flexible cables, only the insulation is crosslinked.

On the other hand, the cable joint between the low-voltage power cables is preferably formed in such a manner that after a part of the insulation at the ends of the two cables to be connected is stripped and the electrical conductors are connected, a new insulation layer covering the joint conductors is usually formed of a polyurethane polymer. It is therefore important that the polymer composition of the original insulation layer exhibits good adhesion to the polyurethane polymer used to repair the insulation layer so that the layer does not crack even under mechanical stress at the cable joint.

On the other hand, certain applications require the flexibility of the cable. Therefore, as described in the EN 50525 standard, materials for flexible cables should generally have a flexural modulus of 30MPa or less.

EP1528574 relates to a composition comprising a density of 1100kg/m³Low voltage power cable of an insulation layer comprising a polyolefin comprising 0.02 to 4 mol.% of a compound bearing polar groups.

Disclosure of Invention

Accordingly, it is an object of the present invention to provide a polyethylene composition useful for improving adhesion between a cable layer comprising the polyethylene composition and a polyurethane resin.

It is another object of the present invention to provide a polyethylene composition as a layer in a cable which cures or crosslinks under ambient conditions and does not require further crosslinking, for example in a vulcanised tube.

The present invention is based on the surprising finding that improved adhesion between a cable layer comprising the polyethylene composition and a polyurethane resin cable can be achieved by using an ethylene copolymer having monomer units with polar groups present in an amount of more than 5 mol.%.

Accordingly, the present invention provides the use of a polyethylene composition for improving the adhesion between a cable layer comprising the polyethylene composition and a polyurethane resin, the polyethylene composition comprising:

a) one or more ethylene copolymers, wherein the ethylene copolymer is a terpolymer comprising monomer units with polar groups and monomer units with hydrolysable silane groups, wherein the monomer units with polar groups are present in an amount of more than 5 mol.%, based on the total polyethylene composition, and

b) a silanol condensation catalyst in an amount of from 0.0001 wt.% to 5 wt.%, based on the total polyethylene composition.

It has surprisingly been found that a polyethylene composition comprising one or more ethylene copolymers comprising monomeric units carrying polar groups and monomeric units carrying hydrolysable silane groups, wherein the monomeric units carrying polar groups are present in an amount of more than 5 mol.%, based on the total polyethylene composition, can be used to improve adhesion to polyurethane casting resins, so that durable joints between cables can be made with polyurethane casting resins.

At the same time, the cable layer meets the demanding requirements on the mechanical properties of the cable, in particular of Low Voltage (LV) power cables. In particular, elongation at break and flexural modulus are improved simultaneously. LV cables are typically installed in buildings. Single wire cables are typically installed in a conduit and during installation, the single wire cable is pulled through a long conduit. Sharp corners, especially other devices, may damage the insulation of the cable. The low voltage power cable according to the present invention effectively prevents such damage during installation due to its improved elongation at break, while having high flexibility.

Furthermore, the layer can rapidly crosslink under ambient conditions. In fact, the crosslinking speed of the ethylene copolymers of the present invention increases with increasing acrylate content, and therefore the crosslinking speed of these high acrylate content ethylene copolymers is very fast.

Another advantage of the present invention is that scorch problems can be reduced or even eliminated by adding a scorch retarder to the inventive polyethylene composition.

The polyethylene composition comprises one or more ethylene copolymers a). Preferably, the polyethylene composition comprises or consists of two ethylene copolymers a) different from each other, more preferably the polyethylene composition comprises or consists of an ethylene copolymer a).

The ethylene copolymer or copolymers a) containing monomer units with polar groups can be prepared, for example, by grafting polyolefins with polar-group-containing compounds, i.e.the ethylene polymers are chemically modified, mostly in a free-radical reaction, by addition of polar-group-containing compounds. Grafting is described, for example, in US 3,646,155 and US 4,117,195.

Preferably, however, the one or more ethylene copolymers a) are prepared by copolymerization of ethylene in the presence of monomer units bearing polar groups and monomer units bearing hydrolysable silane groups.

In the case of copolymerization, the entire monomer unit having a polar group is expressed as "monomer unit having a polar group". Therefore, the weight fraction of the polar group-carrying monomer unit in the ethylene copolymer obtained by the copolymerization can be simply calculated from the weight ratio of the polar group-carrying monomer unit polymerized into the ethylene copolymer. For example, when an ethylene copolymer containing a polar group is prepared by copolymerizing an ethylene monomer with a polar group-containing vinyl compound, the vinyl moiety forming the backbone of the polymer moiety after polymerization contributes to the weight fraction of the "polar group-bearing monomer units".

Preferably, the monomer units bearing polar groups are selected from siloxane, amide, anhydride, carboxylic acid, carbonyl, hydroxyl, ester and/or epoxy groups.

As examples of monomer units carrying polar groups there may be mentioned the following: (a) vinyl carboxylates, such as vinyl acetate and vinyl pivalate; (b) (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and hydroxyethyl (meth) acrylate; (c) ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid; (d) (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide; and (e) vinyl ethers such as vinyl methyl ether and vinyl phenyl ether.

Among these monomers, vinyl esters of monocarboxylic acids having 1 to 4 carbon atoms, such as vinyl acetate, and (meth) acrylic esters of alcohols having 1 to 4 carbon atoms, such as methyl (meth) acrylate, are preferred.

Particularly preferred monomers are butyl acrylate, ethyl acrylate, methyl methacrylate and/or methyl acrylate. Two or more of such ethylenically unsaturated compounds may be used in combination. The term "(meth) acrylic" is intended to include both acrylic and methacrylic.

Preferably, the monomer units bearing polar groups are butyl acrylate, ethyl acrylate, methyl acrylate and/or methyl methacrylate, more preferably butyl acrylate and/or methyl acrylate, more preferably methyl acrylate.

Preferably, the polar group-bearing monomer units are present in an amount of more than 6 mol.%, more preferably more than 7 mol.%, most preferably more than 8 mol.%, based on the total polyethylene composition.

Preferably, the polar group-bearing monomer units are present in an amount of not more than 25 mol.%, more preferably not more than 20 mol.%, more preferably not more than 17.5 mol.%, more preferably not more than 15 mol.%, more preferably not more than 13.5 mol.%, more preferably not more than 11 mol.%, most preferably not more than 9.5 mol.%, based on the total polyethylene composition

The one or more ethylene copolymers a) comprise, in addition to the monomer units bearing polar groups, monomer units bearing hydrolysable silane groups. These silane groups may be introduced into the polymer by grafting, for example as described in US 3,646,155 and US 4,117,195, or preferably by ethylene copolymerization in the presence of monomer units bearing polar groups and monomer units bearing hydrolysable silane groups.

Where copolymerization is used, the complete silane group-bearing monomer is expressed as a "hydrolysable silane group-bearing monomer unit".

Preferably, the ethylene copolymer a) is obtained by copolymerization. In the case of polyethylene, the copolymerization is preferably carried out with a monomer unit having a hydrolyzable silane group represented by the following formula

R¹SiR² _qY_3-q (I)

Wherein the content of the first and second substances,

R¹is an ethylenically unsaturated hydrocarbon radical, an alkoxy radical or (A)A group) an acryloyloxy hydrocarbon group,

R²is an aliphatic saturated hydrocarbon group, and is,

y, which may be identical or different, is a hydrolyzable organic radical and

q is 0, 1 or 2.

Specific examples of monomeric units bearing hydrolysable silane groups are those wherein R is¹Is vinyl, allyl, isopropenyl, butenyl, cyclohexyl or gamma- (meth) acryloxypropyl; y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or alkyl-or arylamino; and if present, R²Is methyl, ethyl, propyl, decyl or phenyl.

Preferred hydrolyzable silane group-bearing monomer units are represented by the formula

CH₂＝CHSi(OA)₃ (II)

Wherein A is a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

The most preferred monomeric units bearing hydrolyzable silane groups are vinyltrimethoxysilane, vinylbismethoxyethoxysilane, vinyltriethoxysilane, gamma- (meth) acryloxypropyltrimethoxysilane, gamma- (meth) acryloxypropyltriethoxysilane, and vinyltriacetoxysilane.

The copolymerization of ethylene in the presence of the polar group-bearing monomer unit and the hydrolysable silane group-bearing monomer unit may be carried out under any suitable conditions that result in the copolymerization of ethylene and both monomer units. The resulting ethylene copolymer or copolymers a) can thus also be labelled as terpolymer or terpolymers.

Preferably, the hydrolysable silane group-bearing monomer units comprise or consist of: vinyltrimethoxysilane, vinylbismethoxyethoxysilane, vinyltriethoxysilane, gamma- (meth) acryloxypropyltrimethoxysilane, gamma (meth) acryloxypropyltriethoxysilane, vinyltriacetoxysilane, and mixtures thereof, more preferably vinyltrimethoxysilane.

Preferably, the monomer units bearing hydrolysable groups are present in an amount of from 0.001 to 15 wt.%, more preferably from 0.01 to 5 wt.%, more preferably from 0.1 to 2.5 wt.%, more preferably from 0.1 to 2 wt.%, most preferably from 1 to 2 wt.%, based on the total polyethylene composition.

The polyethylene composition for the cable layer comprises a silanol condensation catalyst b) in an amount of 0.0001 to 5 wt.%, based on the total polyethylene composition. The silanol condensation catalyst b) is preferably present in an amount of from 0.0005 wt.% to 4 wt.%, more preferably from 0.001 wt.% to 3 wt.%, more preferably from 0.005 wt.% to 2 wt.%, and most preferably from 0.05 wt.% to 1 wt.%, based on the total polyethylene composition.

Preferably, the silanol condensation catalyst b) comprises a lewis acid; inorganic acids such as sulfuric acid and hydrochloric acid; and organic acids such as citric acid, stearic acid, acetic acid, sulfonic acids, and alkanoic acids such as dodecanoic acid.

Preferably, the silanol condensing catalyst b) comprises or consists of a sulfonic acid based catalyst or a tin based catalyst.

Preferably, the silanol condensation catalyst b) is a sulphonic acid based catalyst according to formula (III) or a precursor thereof

ArSO₃H (III)

Ar is a hydrocarbyl-substituted aryl group and the total compound contains 14 to 28 carbon atoms.

Preferably, the Ar group is a hydrocarbyl-substituted benzene or naphthalene ring, in the case of benzene the hydrocarbyl radical or radicals containing from 8 to 20 carbon atoms, and in the case of naphthalene the hydrocarbyl radical or radicals containing from 4 to 18 atoms.

Further preferably, the hydrocarbyl radical is an alkyl substituent having from 10 to 18 carbon atoms, more preferably the alkyl substituent contains 12 carbon atoms and is selected from dodecyl and tetrapropyl. The most preferred aryl group, because of commercial availability, is a benzene substituent bearing an alkyl substituent containing 12 carbon atoms.

Preferably, the sulfonic acid group catalyst comprises dodecylbenzene sulfonic acid, tetrapropylbenzene sulfonic acid, alkylated naphthalene sulfonic acid, aralkyl sulfonic acid, alkylated aryl disulfonic acid, or mixtures thereof, preferably consisting of dodecylbenzene sulfonic acid or tetrapropylbenzene sulfonic acid.

The silanol condensation catalyst b) may also be a precursor of the compound of formula (III), i.e. a compound which is converted by hydrolysis into the compound of formula (III). Such precursors are, for example, anhydrides of sulfonic acid compounds of the formula (III). Another example is a sulfonic acid of formula (III) having a hydrolyzable protecting group (e.g., acetyl) which can be removed by hydrolysis to give a sulfonic acid of formula (III).

Preferably, the tin-based catalyst is one or more selected from the group consisting of dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dibutyltin diacetate, stannous acetate, stannous octoate. More preferably, condensation catalyst (B) is dibutyltin dilaurate, dioctyltin dilaurate, or a mixture thereof, and most preferably, condensation catalyst (B) is dioctyltin dilaurate (DOTDL).

The silanol condensation catalyst b) is preferably added to the one or more ethylene copolymers a) as a crosslinking Catalyst Masterbatch (CM). The masterbatch preferably comprises a silanol condensation catalyst b) and a polymeric carrier, and optionally other additives such as antioxidants. The polymeric carrier is preferably an ethylene copolymer, more preferably a copolymer of ethylene and a monomer containing alkyl acrylate groups, and most preferably an ethylene butyl acrylate copolymer.

Preferably, the polyethylene composition further comprises c) a scorch retarder additive.

Preferably, the scorch retarder c) is present in an amount of 0.0003mole/1000g of polyethylene composition to 0.6mole/1000g of polyethylene composition, more preferably 0.003mole/1000g of polyethylene composition to 0.3mole/1000g of polyethylene composition, more preferably 0.03mole/1000g of polyethylene composition to 0.24mole/1000g of polyethylene composition, more preferably 0.045mole/1000g of polyethylene composition to 0.18mole/1000g of polyethylene composition, most preferably 0.06mole/1000g of polyethylene composition to 0.12mole/1000g of polyethylene composition.

Scorch inhibiting additives c) may be added to the polyethylene composition to reduce or even eliminate scorch without any negative impact on the full crosslinking performance.

Preferably, the scorch retarder c) comprises an alkoxysilane.

Preferably, the alkoxysilane comprises hexadecyltrimethoxysilane, octyltriethoxysilane, or mixtures thereof, more preferably the alkoxysilane comprises hexadecyltrimethoxysilane, and most preferably the alkoxysilane consists of hexadecyltrimethoxysilane.

Preferably, the MFR of the polyethylene composition determined according to ISO1133₂(2.16kg) is from 0.1g/10min to 50g/10min, more preferably from 0.5g/10min to 25g/10min, and most preferably from 1.5g/10min to 15g/10 min.

The polyethylene composition according to the invention may be crosslinked. Preferably, the polyethylene composition according to the invention is crosslinked. The crosslinking of the polyethylene composition of the invention is preferably carried out by so-called moisture curing as known in the art. Reference is made, for example, to WO 95/17463 and WO 00/36612. In a first step, the silane groups of one or more ethylene copolymers are hydrolyzed under the influence of water or steam, resulting in the separation of the alcohol and the formation of silanol groups. In a second step, the silanol groups are crosslinked by condensation reactions which separate out water. In both steps, a silanol condensation catalyst b) as described herein is used as catalyst.

Crosslinking may be carried out at ambient conditions, preferably at a relative humidity of 45% to 65% and a temperature of 20 ℃ to 25 ℃, most preferably at a relative humidity of 55% and a temperature of 23 ℃. Crosslinking can also be carried out at elevated temperature, preferably in water at from 70 ℃ to 90 ℃.

Preferably, the layer is an insulating layer or a sheathing layer.

Preferably, the cable further comprises a skin. The skin is the outermost layer of the cable. The skin layer is preferably adjacent to the insulation or jacket layer. The thickness of the skin layer is preferably 0.01mm to 0.2 mm.

The skin layer is different from the layer comprising the polyethylene composition of the invention as described above. The skin layer preferably comprises or consists of a thermoplastic polyolefin or a crosslinked polyolefin. The polyolefin may be an ethylene copolymer, high density polyethylene, linear low density polyethylene, medium density polyethylene or polypropylene comprising monomer units bearing hydrolysable silane groups.

The high-density polyethylene preferably has a density of 940kg/m³To 970kg/m³The density of (2), the medium density polyethylene preferably has 925kg/m³To 940kg/m³The following densities.

The ethylene copolymer comprising monomer units bearing hydrolysable silane groups for use in the skin layers preferably does not comprise monomer units bearing polar groups.

Applying such a skin layer to a cable according to the invention has the advantage of improving the wear resistance and mechanical strength of the cable.

The cable preferably further comprises an inner insulation layer. By inner insulation layer is meant that this layer is the innermost layer of the cable. In other words, the inner insulation layer is in direct contact with the electrical conductor of the cable. Preferably, the inner insulation layer is between the electrical conductor of the cable and the layer comprising the polyethylene composition of the present invention.

The inner insulation layer is different from the cable layer as described above. The inner insulating layer preferably comprises or consists of a thermoplastic polyolefin or a crosslinked polyolefin. As mentioned above, the polyolefin may be an ethylene copolymer comprising monomer units bearing hydrolysable silane groups, a high density polyethylene, a linear low density polyethylene, a medium density polyethylene or a polypropylene. Such an inner insulation improves the electrical properties of the cable, especially for Medium Voltage (MV) cables. Preferably, the cable is a low voltage cable or a medium voltage cable. Low voltage means a voltage below 6kV and medium voltage means a voltage between 6kV and 68 kV.

Detailed Description

Examples

1. Measurement method

a) Melt Flow Rate (MFR)

The Melt Flow Rate (MFR) is determined according to ISO1133 and is expressed in g/10 min. MFR is an indication of the flowability and thus the processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.

MFR of polyethylene (co) Polymer₂Measured at a temperature of 190 ℃ and under a load of 2.16 kg.

b) Density of

The density of the polymer is determined according to ISO 1183-1:2004 method A on compression-shaped samples prepared according to EN ISO 1872-2 in kg/m³。

c)FTIR

The amount of the polar group-bearing monomer unit and the hydrolyzable silane group-bearing monomer unit can be determined using Fourier transform Infrared Spectroscopy (FTIR).

In particular, the amount of Butyl Acrylate (BA) in the polymer was determined by fourier transform infrared spectroscopy (FTIR). Wt.%/mole.% of butyl acrylate at 3450cm from butyl acrylate^-1The peak at (A) was determined to be 2020cm from polyethylene^-1The peaks at (a) are compared.

The amount of vinyltrimethoxysilane in the polymer was determined by Fourier transform Infrared Spectroscopy (FTIR). Weight% of vinyltrimethoxysilane from silane at 945cm^-1The peak at (A) was determined to be 2665cm from polyethylene^-1The peaks at (a) are compared.

d) Adhesive strength

The adhesive strength was determined according to standard HD 603S1/A3:2008 (see chapter G, part 5). The standard specifies a minimum adhesive strength between the cable insulation and the joint casting resin (typically polyurethane, but epoxy-based resins are also present) of 1N per mm of width of cable sample.

The data in the present invention are based on adhesion to a strip sample having a thickness of 0.5mm and a length of 30 cm. The strands were prepared at 30rpm on a Collin Teachline E20T strand extruder with a 4.2:1, 20D compression screw, D ═ 20mm, temperature profile 135/165/755 ℃. The tape samples were then treated at 23 ℃ and 59% relative humidity for at least 24 hours and then cleaned with isopropanol.

The treated strip was placed on a plate made of HDPE. The plate contained openings having a width of 10mm, a length of 150mm and a depth of 15 mm. The strip sample is placed over the opening. The strip is secured over the opening by another HDPE plate. The polyurethane resin (PUR) is mixed with the hardener and poured into the opening. The mold was then treated for 24 hours. During this time, the PUR crosslinks and hardens. The tape and PUR samples were removed from the jig and adhesion was determined in a tensile tester with a special sample jig as described in VDE 0472-.

The crosslinking catalyst masterbatch was dry blended with the polymers/compounds listed in table 2. Then, 1.8mm thick strips were extruded at a temperature profile of 135/165/755 ℃ and at 30rpm on a Collin Teachline E20T strip extruder with a 4.2:1, 20D compression screw, D ═ 20 mm.

e) Rate of crosslinking

5 wt.% of a crosslinking catalyst was added to the formulation given below and after storage at 23 ℃ and 55% relative humidity for 4 days, 7 days and 14 days, the heat-set elongation (%) of the 1mm strip was evaluated.

f) Mechanical hardness Shore A and Shore D

The mechanical hardness Shore A and Shore D were measured on type B specimens of 80X 10X 4 according to ISO 868. For vinyl polymers, the test specimens were shaped according to EN ISO 1872-2. For Shore D, indentation was performed using a 30 ° cone. For the measurement of Shore A and Shore D, values 1 second after indentation were taken.

g) Flexural modulus

Flexural modulus was determined according to ISO 178. The test sample was an extruded strip 2mm thick. The span length between the supporting objects is 64mm, the testing speed is 2mm/min, and the weighing sensor is 100N. The apparatus used was Alwetron TCT 25. Samples were treated at 23+/-2 ℃ and 50% relative humidity for a minimum of 16 hours prior to testing.

h) Heat-set elongation (%)

To confirm that the crosslinkable polyethylene composition was properly cured, it was prepared according to IEC 60811-²Heat deformation under load determines the heat set elongation and permanent set. Three dumbbell test specimens were prepared from a strip consisting of the polyethylene composition to be tested by cutting the test specimen from the strip. Each test specimen was vertically fixed in an oven from the upper end thereof and 20N/cm was attached to the lower end of each test specimen²The load of (2). After 15min in an oven at 200 ℃, pre-calibration is measuredThe distance between the lines is noted and the percentage of heat set elongation is calculated and expressed as heat set elongation in%.

For% permanent set, the tensile force (weight) was removed from the test specimen and recovered at 200 ℃ for 5min, then cooled to ambient temperature at room temperature. The% permanent set is calculated from the distance between the marked lines.

i) Tensile Strength at Break and tensile Strain at Break (elongation at Break)

Tensile strength at break and tensile strain at break were determined according to ISO 527-1:2012 at 23 ℃ and 50% relative humidity on an Alwedron TCT 10 tensile tester at a speed of 250 mm/min. The extensometer used MFE-900. The test sample was an extruded strip 2mm thick. Samples were treated at 23+/-2 ℃ and 50% relative humidity for a minimum of 16 hours prior to testing. The average values were obtained here from 6 to 10 samples.

j) Appearance of the strip

The appearance of the tape was evaluated visually. Extruded strips were prepared as described above. The grade in which many gels appeared on the band was designated as (-), the grade in which some gels appeared was designated as (-), the grade for good appearance was designated as (+), and the grade for good appearance was designated as (+ +).

2. Experimental methods

The formulations containing the crosslinking catalyst masterbatch were crosslinked in water at 90 ℃ for 24h before being processed for adhesion testing. The crosslinking Catalyst Masterbatch (CM) is dry blended into the particular formulation selected prior to the ribbon extrusion step.

3. Material

a) Ethylene copolymers

The ethylene copolymers used in the present invention with the indicated types and amounts of comonomers are given in table 1 below. In table 1 below, polymers B and C are terpolymers.

Polymers A, B and C were produced in a 660m long split-feed high pressure tubular reactor (Union Carbide type A-1). The diameter of the inner wall is 32 mm. Chain transfer agent (propylene), initiator (t-butylperoxy 2-ethylhexanoate (Luperox 26) and air) and comonomer were fed to the reactor in a conventional manner. The polymerization pressure of both polymers was 230 MPa. The maximum polymerization temperature for polymer A was 310 ℃ and the maximum polymerization temperatures for polymers B and C were 285 ℃.

Table 1: ethylene copolymers

Material	Polymer A	Polymer B	Polymer C
				MFR2，g/10min	1	0.5	3.5
Density, kg/m3	923	930	945
				VTMS content, wt. -%)	1.1	1.05	1.4
Polar group	-	BA	MA
				Polar group content, wt.%/mol%	0	9.5/2.3	22.5/8.7

BA: acrylic acid butyl ester

MA: acrylic acid methyl ester

VTMS: vinyl trimethoxy silane

The Scorch Retarder (SRA) was Hexadecyltrimethoxysilane (HDTMS) and was added to polymers a through C in the amounts shown by preheating the pellets to 60 ℃ for 12 hours. Thereafter, the pellets were conveyed to a drum mixer where they were impregnated with a given amount of HDTMS and mixed for 20 minutes. The impregnated pellets were then held at 60 ℃ for an additional 24 hours. Thus, seven formulations as shown in table 2 below were obtained.

Table 2: formulation of

Formulation of	1	2	3	4	5	6	7
								Material	Polymer A	Polymer A	Polymer B	Polymer C	Polymer C	Polymer C	Polymer C
SRA,wt.％	0.35	0.35	1	0	1	2	3

b) Crosslinking catalyst masterbatch CM-A

CM-A consists of 1.7 wt.% dodecylbenzene sulfonic acid and stabilizer, 2 wt.% Irganox 1010 and 3 wt.% HDTMS, compounded into an ethylene Butyl Acrylate (BA) copolymer with a BA content of 17 wt.% and an MFR₂＝8g/10min。

c) Crosslinking catalyst masterbatch CM-B

CM-B consists of 3.6 wt.% dioctyltin dilaurate (DOTDL) and stabilizer, 2 wt.% Irganox 1010 and 1 wt.% HDTMS, compounded to an ethylene Butyl Acrylate (BA) copolymer with a BA content of 17 wt.% and an MFR₂＝8g/10min。

d) Polyurethane resin (PUR)

The polyurethane resin (PUR) used as the cable joint casting resin in the present invention is Protolin 2000, commercially available from Lovink-Enertech. It is a two-component non-filled and non-pigmented two-component casting resin.

4. Results

Comparative (CE) and Inventive (IE) examples were prepared by dry blending the masterbatch of crosslinked silanol condensation catalyst shown to formulations 1 to 7 prior to extrusion. The amount and type of catalyst added is given in table 3 below.

Table 3: composition of comparative and inventive examples

CE1

CE2

CE3

IE1

IE2

IE3

IE4

Formulation of

1

2

3

4

5

6

7

Catalyst, wt. -%)

CM-A,5

CM-B,5

CM-A,5

CM-A,5

CM-A,5

CM-A,5

CM-A,5

Formulations 1-7 were crosslinked for 10 days at ambient conditions (23 ℃, 55% relative humidity). The results after crosslinking the examples are shown in table 4 below.

Table 4: example Properties after crosslinking

	CE1	CE2	CE3	IE1	IE2	IE3	IE4
								SRA，wt.％	0.35	0.35	1	0	1	2	3
And (3) scorching test: appearance of the strip	++	++	++	--	-	+	++
								Shore D	52	52	46			25
Shore A			82			93
								Flexural modulus, MPa	170	236	100	22	26	24	25
Tensile strength at break, MPa	21	16	19	14	15	15	19
								Tensile strain at break,%	439	526	224	344	375	390	565
Heat-set elongation percentage%	82	448	32	29	23	25	26

Appearance of the tape: excellent (+ +), good (+), gel (-), numerous gels (- -)

The mechanical properties and heat-set data, such as tensile strength at break and elongation at break, of the examples of the invention far exceed the requirements for flexible cables, as expressed in terms of tensile strength in EN 506363-1 (insulation) and EN50363-2-1 (jacket). The insulation requirements for different EPR or EVA types are between 5-7 MPa. The flexural modulus of the inventive examples was significantly improved compared to the comparative examples. The inventive examples also show high tensile strain at break (elongation at break) in excess of 200% and tensile strength in excess of 6 MPa.

The inventive examples simultaneously meet the EN 50525 standard with a typical flexural modulus of less than 30 MPa.

Furthermore, all inventive examples IE1 to IE4 showed a high degree of crosslinking, as demonstrated by the heat-set elongation after 15 minutes in table 4. The amount of SRA had little effect on the heat-set results of the inventive examples. Increasing the amount of SRA (IE2 to IE4) reduced the heat-set value compared to the inventive example without SRA (IE 1).

Table 5 shows the results of the crosslinking speed for comparative examples CE1 and CE3 compared to IE4 after addition of 5 wt.% crosslinking catalyst CM-a.

Table 5: rate of crosslinking

Days at ambient conditions (23 ℃, 55% relative humidity)	4	7	14
				CE1，％	140	94	67
CE3，％	37	31	30
				IE4，％	27	26	25

The terpolymer IE4 of the invention showed excellent crosslinking speed and was fully crosslinked after 4 days. The final heat-set level also decreased with increasing acrylate concentration, as can be seen from a comparison of example CE3 with IE 4.

Table 6 shows the results of the adhesion of comparative examples CE1 and CE3 to PUR casting resin Protolin 2000 compared to IE4 after addition of 5 wt.% of crosslinking catalyst CM-a.

Table 6: adhesion to PUR joint casting resins

	Adhesion, N/mm
		CE1	0.1
CE3	0.5
		IE4	>10

The bond strength between the insulation of the cable and the PUR casting resin requires at least 1N/mm according to the HD 603S1/A3:2008 standard. As can be seen from Table 6, the adhesion of IE4 to PUR is significantly higher than the lower limit.