US20100041817A1 - Method of cross-linking a filled polymer based on polyethylene - Google Patents
Method of cross-linking a filled polymer based on polyethylene Download PDFInfo
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- US20100041817A1 US20100041817A1 US12/604,399 US60439909A US2010041817A1 US 20100041817 A1 US20100041817 A1 US 20100041817A1 US 60439909 A US60439909 A US 60439909A US 2010041817 A1 US2010041817 A1 US 2010041817A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
- Y10T428/12514—One component Cu-based
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a method of cross-linking a composition associating a polyethylene-based silane-grafted polymer with a filler of any kind.
- a particularly advantageous, but non-exclusive application of the invention lies in the field of insulating materials for power and/or telecommunications cables.
- Polyethylene is known for presenting excellent dielectric properties, and also low cost price. That is why it is nowadays in widespread use for making insulating layers of power and/or telecommunications cables.
- polyethylene is generally used in a cross-linked form. It is known that establishing a lattice of chemical bonds extending in all three dimensions serves to increase the high temperature behavior of this particular type of insulating material.
- Cross-linked polyethylene is usually fabricated by silane cross-linking. That now-conventional technique consists initially in grafting the base polyethylene with a silane, by adding radicals using a peroxide. Thereafter, the compound as grafted in that way is subjected to cross-linking by hydrolysis and then to condensation, which requires the presence of water and a condensation catalyst. It should be observed that the catalyst is commonly constituted either by dibutyl tin laurate (DBTL) or by dibutyl tin dilaurate (DBTDL).
- DBTL dibutyl tin laurate
- DBTDL dibutyl tin dilaurate
- the silane cross-linking technique nevertheless presents the drawback of being unsuitable for being implemented directly in ambient air if said polyethylene is filled.
- insulating materials it is extremely common practice for insulating materials to include fillers. This applies in particular to flame-retardant fillers for improving the behavior of power cables and/or telecommunications cables in the event of fire.
- the only solutions presently in use consist in implementing the second cross-linking step of the silane technique either in a pool for 24 hours (h) at 63° C., or else in a sauna for 15 h at 90° C.
- the technical problem to be solved by the subject matter of the present invention is to propose a method of cross-linking a composition comprising both a polyethylene-based silane-grafted polymer and a filler, which cross-linking method makes it possible to avoid prior art problems, in particular by being substantially less complicated to implement and thus implicitly being less expensive.
- the solution to the technical problem posed lies in the fact that the cross-linking method consists in mixing the composition with a condensation catalyst constituted by lauryl stannoxane having the following formula
- silane-grafted polymer conventionally designates a polymer on which a silane type compound has previously been grafted.
- polyethylene-based polymer relates to any low, medium, or high density polyethylene, and also any polyethylene-octene elastomer (POE), and regardless of the polymerization system involved.
- the invention as defined presents the advantage of enabling a filled polyethylene to be cross-linked in ambient air and in a few days, with complete cross-linking being achieved within a period of less than 45 days. It is thus entirely appropriate to speak of self-cross-linking.
- the invention makes it possible to abandon the expensive and complicated step of passing through a pool or a sauna, and thus to eliminate the corresponding equipment. Independently of the purely monetary financial advantage associated with such omission, the resulting saving in time that results also serves to improve productivity.
- cables can advantageously be marked continuously, directly at the outlet from an extruder. This also leads to a gain in productivity.
- the use of a new catalyst does not require significant change to the overall industrial process of cable fabrication, and thus does not require significant change to the installations presently in use.
- the condensation catalyst is packaged in the form of a master batch.
- Packaging the lauryl stannoxane in the form of a master batch also makes it possible to measure out accurately the quantity of catalyst that is really necessary, which can be particularly advantageous given that the catalyst is liquid and is for use in very small quantities.
- the master batch comprises a polymer matrix having the lauryl stannoxane dispersed therein.
- the polymer matrix of the master batch is preferably identical in nature with the base polymer of the composition.
- This characteristic makes it possible in particular to avoid modifying the mechanical and dielectric properties of the final material.
- the composition contains 0.0036% to 0.0108% of condensation catalyst.
- the composition contains 90 pcr to 190 pcr of filler.
- the composition is also provided with at least one additive selected from a processing agent, an anti-oxidant, a colorant, an anti-UV agent, an anti-copper agent.
- the composition contains less than 3 pcr of processing agent.
- the composition includes 0.5 pcr to 5 pcr of anti-oxidant.
- the cross-linking method is implemented at ambient temperature.
- the cross-linking method is implemented in ambient air.
- the invention also relates to any power and/or telecommunications cable including at least one insulating covering that is made from a composition cross-linked in application of the above-described method.
- each of these Examples I and II is to compare the level of cross-linking in two identical filled polymer materials when left to cross-link in the open air, one of the materials including a condensation catalyst in accordance with the invention, and the other having only a prior art catalyst.
- Two samples of materials A and B were prepared from two compositions that thus differed from each other solely in the nature of their respective condensation catalysts.
- compositions A and B were mixed, the resulting mixture was extruded, and the corresponding extruded sample was allowed to cross-link in the open air. It should be observed that in each case the condensation catalyst was added during extrusion, in the form of a master batch.
- Table 1 below gives the respective compositions of the two material samples A and B.
- silane-grafted polymer in this first example was constituted by a linear low-density polyethylene grafted to 1% with a silane cocktail, which cocktail associated a peroxide and silane. Specifically, it was the composition sold under the name “CLDO” by the supplier Polimeri Europa.
- the filler was of the flame-retardant type, being constituted by aluminum trihydroxide (ATH).
- the DBTL used in sample A was as sold by the supplier Goldschmidt, under the reference Tegokat 218.
- the lauryl stannoxane used in its sample B was as sold by the supplier Goldschmidt, under the reference Tegokat 225.
- That type of test is governed by the standard NF EN 60811-2-1. Specifically, it consists in loading one end of a dumbbell-H2 type test piece with a mass corresponding to applying stress equivalent to 0.2 megapascals (MPa), and in placing the assembly in an oven that is heated to a given reference temperature to within ⁇ 2° C. for a duration of 15 minutes (min). After that time, the elongation of the test piece while hot and under stress is measured as a percentage. The suspended mass is then removed, and the test piece is kept in the oven for five more minutes. The permanent elongation that remains, also known as remanence, is then measured and expressed in percentage.
- MPa megapascals
- sample A was not capable of passing the hot-set test at 200° C. successfully, even after 36 days. This confirms the known fact that a typical prior art catalyst is not capable of generating fast cross-linking in a filled polyethylene.
- the two material samples C and D of the second example were prepared in a manner analogous to that described above for Example I.
- Table 3 specifies the respective compositions of the samples in question.
- the major difference compared with the first example comes from the specific nature of the silane-grafted polymer common to samples C and D. Specifically, it was a polyethylene octene grafted to 3% with a silane cocktail, which in this example likewise associated a peroxide and a silane. Specifically, the composition sold under the name “Exact8203/LL4004(70/30)” from the supplier Exxon was used.
- the filler was still of the flame-retardant type, and specifically was still constituted by aluminum trihydroxide (ATH).
- the DBTL and the lauryl stannoxane used respectively in samples C and D were identical in kind to those used respectively in samples A and B.
- sample C was not capable of passing the hot-set test at 200° C. successfully, even after 27 days. This is further proof that a typical catalyst of the prior art cannot lead to rapid self-cross-linking of a filled polyethylene.
Abstract
A method of cross-linking a composition comprising firstly a polyethylene-based silane-grafted polymer, and secondly a filler. The invention is remarkable in that the cross-linking method consists in mixing the composition with a condensation catalyst constituted by lauryl stannoxane of formula [(C4H9)2Sn(OOCC11H23)]2O.
Description
- This application is a divisional application from U.S. patent application Ser. No. 11/582,853, filed on Oct. 18, 2006, which in turn claims the benefit of priority from French Patent Application No. 06 50030, filed on Jan. 4, 2006, the entirety of which are incorporated herein by reference.
- The present invention relates to a method of cross-linking a composition associating a polyethylene-based silane-grafted polymer with a filler of any kind.
- A particularly advantageous, but non-exclusive application of the invention lies in the field of insulating materials for power and/or telecommunications cables.
- Polyethylene is known for presenting excellent dielectric properties, and also low cost price. That is why it is nowadays in widespread use for making insulating layers of power and/or telecommunications cables.
- In order to provide improved thermomechanical properties, polyethylene is generally used in a cross-linked form. It is known that establishing a lattice of chemical bonds extending in all three dimensions serves to increase the high temperature behavior of this particular type of insulating material.
- Cross-linked polyethylene is usually fabricated by silane cross-linking. That now-conventional technique consists initially in grafting the base polyethylene with a silane, by adding radicals using a peroxide. Thereafter, the compound as grafted in that way is subjected to cross-linking by hydrolysis and then to condensation, which requires the presence of water and a condensation catalyst. It should be observed that the catalyst is commonly constituted either by dibutyl tin laurate (DBTL) or by dibutyl tin dilaurate (DBTDL).
- With a polyethylene, the silane cross-linking technique nevertheless presents the drawback of being unsuitable for being implemented directly in ambient air if said polyethylene is filled. Unfortunately, in cable making, it is extremely common practice for insulating materials to include fillers. This applies in particular to flame-retardant fillers for improving the behavior of power cables and/or telecommunications cables in the event of fire.
- In order to remedy that difficulty, the only solutions presently in use consist in implementing the second cross-linking step of the silane technique either in a pool for 24 hours (h) at 63° C., or else in a sauna for 15 h at 90° C.
- Nevertheless, both of those solutions are particularly expensive because of the cost of the extra equipment that is needed, because of the cost of the energy required for operation, and because of the cost of maintaining the installation.
- Furthermore, since marking inks do not withstand passing through a pool or a sauna, it is not possible to mark each cable directly on leaving an extruder, and the marking operation must necessarily be performed as an extra operation on leaving the bath of liquid water or of steam. Thus, a consequence of using a pool or a sauna is to complicate quite considerably the industrial fabrication method in terms of logistics, and that again constitutes more extra costs.
- Thus, the technical problem to be solved by the subject matter of the present invention is to propose a method of cross-linking a composition comprising both a polyethylene-based silane-grafted polymer and a filler, which cross-linking method makes it possible to avoid prior art problems, in particular by being substantially less complicated to implement and thus implicitly being less expensive.
- According to the present invention, the solution to the technical problem posed lies in the fact that the cross-linking method consists in mixing the composition with a condensation catalyst constituted by lauryl stannoxane having the following formula
-
[(C4H9)2Sn(OOCC11H23)]2O. - It should be understood that the term “silane-grafted polymer” conventionally designates a polymer on which a silane type compound has previously been grafted.
- The concept of a “polyethylene-based polymer” relates to any low, medium, or high density polyethylene, and also any polyethylene-octene elastomer (POE), and regardless of the polymerization system involved.
- Furthermore, it should be observed that the filler could, a priori, be of absolutely any kind.
- The invention as defined presents the advantage of enabling a filled polyethylene to be cross-linked in ambient air and in a few days, with complete cross-linking being achieved within a period of less than 45 days. It is thus entirely appropriate to speak of self-cross-linking.
- Consequently, the invention makes it possible to abandon the expensive and complicated step of passing through a pool or a sauna, and thus to eliminate the corresponding equipment. Independently of the purely monetary financial advantage associated with such omission, the resulting saving in time that results also serves to improve productivity.
- Because of the self-cross-linking, cables can advantageously be marked continuously, directly at the outlet from an extruder. This also leads to a gain in productivity.
- Furthermore, the use of a new catalyst does not require significant change to the overall industrial process of cable fabrication, and thus does not require significant change to the installations presently in use. In other words, this means that the cross-linking method of the invention can be implemented very easily using existing fabrication equipment.
- According to a feature of the invention, the condensation catalyst is packaged in the form of a master batch.
- This characteristic enables the lauryl stannoxane to be better dispersed within the batch, thereby achieving significantly greater effectiveness. For equivalent effect, it is consequently possible to use significantly less catalyst, thus implying a significant saving in terms of cost.
- Packaging the lauryl stannoxane in the form of a master batch also makes it possible to measure out accurately the quantity of catalyst that is really necessary, which can be particularly advantageous given that the catalyst is liquid and is for use in very small quantities.
- In particularly advantageous manner, the master batch comprises a polymer matrix having the lauryl stannoxane dispersed therein.
- This naturally assumes that the polymer matrix of the catalyst master batch is compatible with the base polymer of the composition.
- The polymer matrix of the master batch is preferably identical in nature with the base polymer of the composition.
- This characteristic makes it possible in particular to avoid modifying the mechanical and dielectric properties of the final material.
- In accordance with another advantageous feature, the composition contains 0.0036% to 0.0108% of condensation catalyst.
- According to another advantageous characteristic, the composition contains 90 pcr to 190 pcr of filler.
- In this respect, it should be understood that throughout this specification, the abbreviation “pcr” has the conventional meaning of percent of resin. Consequently, it designates the percentage by weight of a compound in question relative to the weight of the base polymer set arbitrarily as being 100.
- According to another feature of the invention, the composition is also provided with at least one additive selected from a processing agent, an anti-oxidant, a colorant, an anti-UV agent, an anti-copper agent.
- In particularly advantageous manner, the composition contains less than 3 pcr of processing agent.
- According to another advantageous characteristic, the composition includes 0.5 pcr to 5 pcr of anti-oxidant.
- According to another feature of the invention, the cross-linking method is implemented at ambient temperature.
- According to another advantageous characteristic of the invention, the cross-linking method is implemented in ambient air.
- Naturally, the invention also relates to any power and/or telecommunications cable including at least one insulating covering that is made from a composition cross-linked in application of the above-described method.
- Other characteristics and advantages of the present invention appear from the following description of two comparative examples, said examples being given by way of non-limiting illustration.
- The object of each of these Examples I and II is to compare the level of cross-linking in two identical filled polymer materials when left to cross-link in the open air, one of the materials including a condensation catalyst in accordance with the invention, and the other having only a prior art catalyst.
- Two samples of materials A and B were prepared from two compositions that thus differed from each other solely in the nature of their respective condensation catalysts.
- Specifically, the various ingredients for each of the compositions A and B were mixed, the resulting mixture was extruded, and the corresponding extruded sample was allowed to cross-link in the open air. It should be observed that in each case the condensation catalyst was added during extrusion, in the form of a master batch.
- Table 1 below gives the respective compositions of the two material samples A and B.
-
TABLE 1 Sample A B Silane-grafted polymer (pcr) 100 100 Filler (pcr) 110 110 Processing agent (pcr) 3 3 Anti-oxidant (pcr) 1 1 DBTL (%) 0.072 — Lauryl stannoxane (%) — 0.072 - It should be observed that the silane-grafted polymer in this first example was constituted by a linear low-density polyethylene grafted to 1% with a silane cocktail, which cocktail associated a peroxide and silane. Specifically, it was the composition sold under the name “CLDO” by the supplier Polimeri Europa.
- The filler was of the flame-retardant type, being constituted by aluminum trihydroxide (ATH).
- The DBTL used in sample A was as sold by the supplier Goldschmidt, under the reference Tegokat 218.
- The lauryl stannoxane used in its sample B was as sold by the supplier Goldschmidt, under the reference Tegokat 225.
- In order to verify that each sample A and B had indeed cross-linked, it was subjected to a standardized hot-set test (HST) under mechanical stress.
- That type of test is governed by the standard NF EN 60811-2-1. Specifically, it consists in loading one end of a dumbbell-H2 type test piece with a mass corresponding to applying stress equivalent to 0.2 megapascals (MPa), and in placing the assembly in an oven that is heated to a given reference temperature to within ±2° C. for a duration of 15 minutes (min). After that time, the elongation of the test piece while hot and under stress is measured as a percentage. The suspended mass is then removed, and the test piece is kept in the oven for five more minutes. The permanent elongation that remains, also known as remanence, is then measured and expressed in percentage.
- The greater the extent to which a material is cross-linked, the smaller the values of elongation and of remanence. Furthermore, in the event of a test piece breaking during the test or in the event of its elongation exceeding 100%, under the combined effects of mechanical stress and temperature, then the result of the test is logically considered as being a failure.
- The results of the hot-set tests under mechanical stress at 200° C. are summarized in Table 2 below.
-
TABLE 2 Sample A B Hot-set test (200° C.) failure success Time D + 36 D + 15 Elongation (%) — 50 Remanence (%) — 10 - It should be observed firstly that only sample B was successful in passing the hot-set test at 200° C., and was capable of so doing after 15 days only. This means that only the catalyst of the invention is capable of enabling the filled polyethylene to self-cross-link in open air.
- In contrast, it can be seen that sample A was not capable of passing the hot-set test at 200° C. successfully, even after 36 days. This confirms the known fact that a typical prior art catalyst is not capable of generating fast cross-linking in a filled polyethylene.
- The two material samples C and D of the second example were prepared in a manner analogous to that described above for Example I.
- Table 3 specifies the respective compositions of the samples in question.
-
TABLE 3 Sample C D Silane-grafted polymer (pcr) 100 100 Filler (pcr) 110 110 Processing agent (pcr) 3 3 Anti-oxidant (pcr) 3 3 DBTL (%) 0.0036 — Lauryl stannoxane (%) — 0.0036 - The major difference compared with the first example comes from the specific nature of the silane-grafted polymer common to samples C and D. Specifically, it was a polyethylene octene grafted to 3% with a silane cocktail, which in this example likewise associated a peroxide and a silane. Specifically, the composition sold under the name “Exact8203/LL4004(70/30)” from the supplier Exxon was used.
- The filler was still of the flame-retardant type, and specifically was still constituted by aluminum trihydroxide (ATH).
- The DBTL and the lauryl stannoxane used respectively in samples C and D were identical in kind to those used respectively in samples A and B.
- Samples C and D were subjected to the same hot-set test under mechanical test as in Example I. The results of the various tests are summarized in Table 4 below.
-
TABLE 4 Sample C D Hot-set test (200° C.) failure success Time (days) D + 27 D + 20 Elongation (%) — 60 Remanence (%) — 0 - The conclusions are entirely similar to those formulated for Example I.
- It can thus be seen that only sample D was successful in passing the hot-set test at 200° C., and it could do so after only 20 days. This confirms the fact that only a catalyst in accordance with the invention is capable of causing a filled polyethylene to self-cross-link in the open air.
- It should also be observed that sample C was not capable of passing the hot-set test at 200° C. successfully, even after 27 days. This is further proof that a typical catalyst of the prior art cannot lead to rapid self-cross-linking of a filled polyethylene.
Claims (11)
1. A method of manufacturing a power and/or telecommunications cable, including at least one insulating covering, said method comprising the steps of:
mixing a composition comprising firstly a polyethylene-based silane-grafted polymer and secondly a filler with a condensation catalyst constituted by lauryl stannoxane of formula [(C4H9)2Sn(OOCC11H23)]2O,
extruding the composition obtained from the preceding step, and
crosslinking the extruded composition in order to form the insulating covering.
2. A method according to claim 1 , wherein the condensation catalyst is packaged in the form of a master batch.
3. A method according to claim 2 , wherein the master batch comprises a polymer matrix having lauryl stannoxane dispersed therein.
4. A method according to claim 3 , wherein the polymer matrix of the catalyst master batch is of nature identical to that of the base polymer of the composition.
5. A method according to claim 1 , wherein the composition includes 0.0036% to 0.0108% of condensation catalyst.
6. A method according to claim 1 , wherein the composition includes 90 pcr to 190 pcr of filler.
7. A method according to claim 1 , wherein the composition further includes at least one additive selected from the group consisting of a processing agent, an anti-oxidant, a colorant, an anti-UV agent, an anti-copper agent.
8. A method according to claim 1 , wherein the composition includes less than 3 pcr of processing agent.
9. A method according to claim 1 , wherein the composition includes 0.5 pcr to 5 pcr of anti-oxidant.
10. A method according to claim 1 , the crosslinking step being implemented at ambient temperature.
11. A method according to claim 1 , the crosslinking step being implemented in the open air.
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US12/604,399 US20100041817A1 (en) | 2006-01-04 | 2009-10-23 | Method of cross-linking a filled polymer based on polyethylene |
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FR0650030 | 2006-01-04 | ||
FR0650030 | 2006-01-04 | ||
US11/582,853 US7632574B2 (en) | 2006-01-04 | 2006-10-18 | Method of cross-linking a filled polymer based on polyethylene |
US12/604,399 US20100041817A1 (en) | 2006-01-04 | 2009-10-23 | Method of cross-linking a filled polymer based on polyethylene |
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US11/582,853 Continuation US7632574B2 (en) | 2006-01-04 | 2006-10-18 | Method of cross-linking a filled polymer based on polyethylene |
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US12/604,399 Abandoned US20100041817A1 (en) | 2006-01-04 | 2009-10-23 | Method of cross-linking a filled polymer based on polyethylene |
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EP (1) | EP1806379B1 (en) |
KR (1) | KR20070073614A (en) |
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---|---|---|---|---|
CN101389673B (en) * | 2005-09-13 | 2011-06-08 | 陶氏环球技术公司 | Distannoxane catalysts for silane crosslinking and condensation reactions |
EP1806379B1 (en) * | 2006-01-04 | 2010-12-22 | Nexans | Method for the crosslinking of a filled polymer based on polyethylene |
CN104736621A (en) * | 2012-08-24 | 2015-06-24 | 陶氏环球技术有限公司 | Tetramethylstannoxy compounds |
JP5972836B2 (en) * | 2013-06-14 | 2016-08-17 | 日立金属株式会社 | Non-halogen flame retardant wire cable |
NO2963654T3 (en) * | 2014-06-30 | 2018-05-12 |
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US4549041A (en) * | 1983-11-07 | 1985-10-22 | Fujikura Ltd. | Flame-retardant cross-linked composition and flame-retardant cable using same |
US20050049343A1 (en) * | 2003-09-02 | 2005-03-03 | Borke Jeffrey S. | Crosslinkable flame retardant wire and cable compositions having improved abrasion resistance |
US20060223952A1 (en) * | 2003-09-12 | 2006-10-05 | Willy Furrer | Process for crosslinking thermoplastic polymers with silanes employing peroxide blends and the resulting crosslinked thermoplastic polymers |
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IT1290854B1 (en) * | 1996-12-17 | 1998-12-14 | Pirelli Cavi Spa Ora Pirelli C | PROCEDURE AND DEVICE FOR FORMING A CROSS-LINKED POLYMER COATING AND COATING THUS OBTAINED |
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DE102004061985A1 (en) * | 2004-12-23 | 2006-07-06 | Rehau Ag + Co | TPV Alternative |
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-
2006
- 2006-10-03 EP EP20060301005 patent/EP1806379B1/en not_active Not-in-force
- 2006-10-03 AT AT06301005T patent/ATE492588T1/en not_active IP Right Cessation
- 2006-10-03 DE DE200660019047 patent/DE602006019047D1/en active Active
- 2006-10-18 US US11/582,853 patent/US7632574B2/en not_active Expired - Fee Related
-
2007
- 2007-01-02 KR KR1020070000349A patent/KR20070073614A/en not_active Application Discontinuation
-
2009
- 2009-10-23 US US12/604,399 patent/US20100041817A1/en not_active Abandoned
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US4549041A (en) * | 1983-11-07 | 1985-10-22 | Fujikura Ltd. | Flame-retardant cross-linked composition and flame-retardant cable using same |
US20050049343A1 (en) * | 2003-09-02 | 2005-03-03 | Borke Jeffrey S. | Crosslinkable flame retardant wire and cable compositions having improved abrasion resistance |
US6936655B2 (en) * | 2003-09-02 | 2005-08-30 | Equistar Chemicals, Lp | Crosslinkable flame retardant wire and cable compositions having improved abrasion resistance |
US20060223952A1 (en) * | 2003-09-12 | 2006-10-05 | Willy Furrer | Process for crosslinking thermoplastic polymers with silanes employing peroxide blends and the resulting crosslinked thermoplastic polymers |
US7632574B2 (en) * | 2006-01-04 | 2009-12-15 | Nexans | Method of cross-linking a filled polymer based on polyethylene |
Also Published As
Publication number | Publication date |
---|---|
US7632574B2 (en) | 2009-12-15 |
ATE492588T1 (en) | 2011-01-15 |
KR20070073614A (en) | 2007-07-10 |
DE602006019047D1 (en) | 2011-02-03 |
EP1806379B1 (en) | 2010-12-22 |
US20070154730A1 (en) | 2007-07-05 |
EP1806379A1 (en) | 2007-07-11 |
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