AU3320199A - Optical cable with filling material comprising an internal olefin oligomer - Google Patents
Optical cable with filling material comprising an internal olefin oligomer Download PDFInfo
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- AU3320199A AU3320199A AU33201/99A AU3320199A AU3320199A AU 3320199 A AU3320199 A AU 3320199A AU 33201/99 A AU33201/99 A AU 33201/99A AU 3320199 A AU3320199 A AU 3320199A AU 3320199 A AU3320199 A AU 3320199A
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- 238000011049 filling Methods 0.000 title claims description 67
- 239000000463 material Substances 0.000 title claims description 51
- 230000003287 optical effect Effects 0.000 title claims description 42
- 150000001336 alkenes Chemical class 0.000 title description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 90
- 229920000098 polyolefin Polymers 0.000 claims description 40
- 239000000945 filler Substances 0.000 claims description 37
- 239000013307 optical fiber Substances 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 18
- 239000002480 mineral oil Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 235000010446 mineral oil Nutrition 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Chemical group 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229920002633 Kraton (polymer) Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000009736 wetting Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 239000000539 dimer Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000013100 final test Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Our Ref: 730349 P/00/011 Regulation 3:2
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Address for Service: Invention Title: Pirelli Cavi E Sistemi S.p.A: Viale Sarca, 222 Milano 20126
ITALY
DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Optical cable with filling material The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 PC756 1 OPTICAL CABLE WITH FILLING
MATERIAL
The present invention relates to an optical fibre cable comprising a filling material and to the composition of said filling material.
The task of the filling material in an optical fibre cable is to protect the fibres throughout their lifetime. To carry out this function, the filling material is generally introduced into the structures containing the optical fibres in such a way that the optical fibres are embedded in it.
The composition of known fillers typically e.* .comprises a base oil, for example of the silicone, .e mineral (naphthenic or paraffin) or synthetic type.
This base oil typically requires the addition of a :.viscosity improver" such as an elastomeric polymer with a low glass transition point, which by imparting viscosity to the solution improves its performance as a filling material. The filler composition may also contain an antioxidant and a thickening/thixotropic *S agent, consisting of more or less silanized pyrogenic silica.
There are various known types of cable which have suitable housings for the optical fibres, filled with a filling material.
For example, the patent EP 632301 describes an optical fibre cable comprising, in a suitable housing, the optical fibres embedded in a composition capable of protecting the fibres from phenomena of attenuation, in PC756 2 which the said composition comprises a hydrocarbon compound, a catalyst and a thixotropic thickener such as silica.
Another example of a filler composition is disclosed in patent application EP 811864, which describes a composition for fillers comprising a mineral oil or a polyalphaolefin, a block copolymer, an anti-oxidant and if necessary a stabilizer of the "metal deactivator" type.
Other examples of optical cables with known fillers are disclosed in US patents 5,285,513 and *o 5,187,763 and in the patent EP 541007.
Optical fibre cables, when installed underground, *for example in leads or inside underground conduits, are subject to damage affecting their coatings, caused by mechanical abuse of various kinds, for example accidental impact by sharp tools such as spades or pickaxes, which .have a cutting action on the cable. The said conditions may lead to the ingress of water, with 20 the worst possibility that it will run longitudinally inside the cable and consequently in the proximity of the optical fibres. One of the tasks of the filler is therefore to limit or impede this passage of water inside the cable structure. Less disastrous faults, such as breaks in the outer sheaths only, may also lead to permeation of water in the liquid or vapor state, with consequent harmful effects on the optical fibres, and the development of a number of problems (for example, the delamination of the layer of plastic PC756 -3coating of the optical fibres), the final outcome of which is manifested in optical attenuation of the transmitted signals.
The applicant has observed that, in order to limit the possibility of the coating of the optical fibre coming into contact with water, it would be desirable to use a filling material with a good wetting capacity by comparison with this coating, in such a way as to make it more difficult for water to enter the interface between the fibre coating and the filling composition.
In relation to the mechanical stresses to which the optical fibres may be subjected, it should also be observed that, even if the cable does not undergo e• SC movement once it has been laid, it is inevitably 15 subject to thermal variations which cause differential dimensional deformations in the components of the cable structure, according to the different materials from which these components are formed. The applicant has observed that these deformations may cause movements of 20 the optical fibre inside the structure in which it is housed, by acting through the filling material. If this filling material is not sufficiently deformable during the passage of the optical fibre, the structure of the latter may be subject to excessively high localized pressures; this may cause the well-known phenomena of "micro-bending" in the fibre, which are one of the causes of attenuation of the optical signal.
PC756 4 The applicant has now discovered a new composition which can be used advantageously as a filling material for optical cables.
The filling composition according to the present invention not only maintains the desired characteristics of the known fillers, but also has a number of characteristics which make it possible to improve the compatibility of the fibres with the filling material and the intrinsic properties of this filler, both in terms of ease of processing and in terms of performance when the cable is in use.
o*o
S
In particular, the applicant has observed that a filling material according to the present invention has S S S• an improved capacity for wetting the coating surfaces 15 of the optical fibres with which it comes into contact, and has less resistance to the movement of the optical fibres within this filling material. For the purposes 0* of the present invention, the term "wetting" denotes the capacity of the filler to adhere to the surfaces of
S@SS
20 the optical fibres, which are generally coated with acrylic materials; the result of this improved wetting capacity is a greater resistance to water permeation, since the ingress of water into the acrylate/filler interface is made more difficult.
The applicant has also observed that the use of a filling material according to the present invention causes less resistance to the movement of the optical fibres when these move inside it.
PC756 According to the applicant's observations, the smaller resistance to the movement of the optical fibres inside the filling material makes it possible to reduce the problems associated with the mobility of the said fibres, thus reducing or eliminating "microbending" phenomena which may occur during the movement of the cable during laying or when the cable is in use.
The applicant has also observed that the composition of a filling material according to the present invention has a reduced dripping tendency when *inside the cable.
In the present description, the term dripping means the tendency of filling material to move inside the various structures forming the cable, both in a 15 longitudinal and transversal direction.
Generally, an excessive movement of filling material inside the cable is undesirable, both during manufacturing and installation of the cable as well as when the same is under exercise.
oeee "9*9 20 During manufacturing of the cable for example, the filling material runs horizontally together with the cable, and it should thus preferably have a relatively high dripping resistance in order to avoid incomplete filling of the cable.
In addition, when on exercise, the cable can be placed in locations with high slopes so that the filling material should preferably have a relatively high dripping resistance in order to avoid the flowing 0 M M PC756 6 of said filling material towards junction boxes or even towards devices connected therewith.
The flowing resistance of the material, that is strictly related to the dripping resistance, is thus a further advantageous property of the filling material according to the present invention, which can be appreciated both during manufacturing and installation of the cable.
One aspect of the present invention therefore relates to an optical cable comprising at least one optical fibre and a filling material, characterized in e that the said filler comprises an internal polyolefin.
In the present description, the term "internal polyolefin" means the product of polymerization of two 15 or more hydrocarbon monomeric units having at least one unsaturation distributed randomly along the whole hydrocarbon chain, in which a mixture of these monomeric units to be polymerized comprises a maximum of 10% of monomeric units having the double bond in the eo" 20 a position; preferably, these monomeric units are monounsaturated hydrocarbons.
A preferred aspect of the present invention relates to a cable as described previously, in which this filling composition is in contact with the said at least one optical fibre.
According to a further preferred aspect, the quantity of internal polyolefin in the filler is between 30% and 98% by weight, preferably between and 95% by weight.
PC756 7 In a preferred embodiment, this internal polyolefin is produced by polymerization of unsaturated hydrocarbon monomers, each comprising from 10 to carbon atoms.
In particular, this internal polyolefin is preferably produced by the polymerization of monomers with chains each comprising from 12 to 18 carbon atoms and even more preferably from 15 to 16 carbon atoms.
Preferably, this internal polyolefin is an oligomer comprising from 2 to 4 monomeric units as defined above.
*e *According to a preferred aspect, this internal *polyolefin is a mixture of polyolefins with different molecular weights.
15 In particular, these mixtures are mixtures of oligomers comprising from 2 to 4 monomeric units as defined above.
A further aspect of the present invention relates :i to an optical cable as described previously, in which 20 the filling composition also comprises a thickening polymer, this thickening polymer being preferably selected from block copolymers of the type which comprises styrene, propylene and ethylene units.
Another preferred aspect of the present invention relates to an optical cable as described previously, in which the internal polyolefin included in the filling composition is partially replaced by a mineral oil. In particular, the mineral oil can replace up to approximately 70% by weight of the internal polyolefin, PC756 8preferably from 20% to 60% by weight, a replacement of approximately 50% by weight of the internal polyolefin being particularly preferred.
The present invention will be more clearly understood from the following detailed description, provided by way of example and consequently without restriction, with reference to the attached drawings, in which: Figure 1 shows schematically a section through an optical fibre cable of the multiple-tube type with a .ooeei central support, according to the invention.
Figure 2 shows schematically a section through another optical fibre cable according to the invention, with a grooved core.
S 15 Figure 3 shows schematically a section through another optical fibre cable according to the invention.
Figure 4 shows schematically a section through another optical fibre cable according to the invention.
The cable shown in Figure 1 has in the radially innermost position a reinforcing element, typically made from glass-fibre reinforced plastic coated with a polymeric layer of polyethylene for example. The cable has one or more tubular elements (3) made from PE, PBT or PP, embedded in the filler comprising the optical fibres which are also embedded in the filler The tubular elements (3) are wrapped in a reinforcing layer typically made from Kevlar or glass thread, containing two sheath cutting threads disposed longitudinally with PC756 9 respect to the cable. Finally, the cable comprises a corrugated tape and an outer sheath typically made from polyethylene.
Figure 2 shows another example of an optical fibre cable.
As shown in Figure 2, the cable has in the radially innermost position a reinforcing element (1) on which is extruded the grooved core (10) in which are externally formed grooves (11) which extend either spirally or with an s-z configuration along the whole *outer surface of the said core.
*The grooves (11) are filled with a filler according to the present invention, and house the optical fibres (4) The grooved core (10) is then wrapped in a layer of filler which covers the grooves and which in turn is surrounded by a polyurethane sheath (13) and by a reinforcing tape The final layers are a twolayer corrugated tape (14) and an outer polyethylene sheath Figure 3 shows a sectional view of an optical fibre cable' comprising a central tube containing the optical fibres which are preferably disposed loosely in the filling material The central tube is wrapped, in sequence from the tube outwards, with a reinforcing layer containing two sheath cutting threads a corrugated tape and an outer polyethylene sheath (9) PC756 10 Figure 4 shows another example of an optical fibre cable comprising a central tube in which are housed optical fibre ribbons preferably embedded in the filling material The central tube is wrapped with a water swellable layer (16) and with a containing tape (17) typically made from polyester, between which tapes are contained the sheath cutting threads and the reinforcing rods (18) made from glass-fibre reinforced plastic.
The optical fibre cables as described previously solely by way of example may also comprise a water .swellable tape disposed outside the tube and in any case outside the elements containing the optical fibres, with the function of further improving the S 15 resistance of the structure to the propagation of water in the longitudinal direction inside the cable.
The filling composition according to the present ••or invention can be used advantageously as a filler in the cables illustrated in Figures 1, 2, 3 and 4, 20 particularly when this filler is in direct contact with the optical fibres.
The filling material to which the present invention relates is characterized in that it comprises an internal polyolefin.
The composition of the filler according to the present invention typically comprises from approximately 30% to approximately 98% by weight, and preferably from 45% to 95% by weight, of internal polyolefins.
PC756 11 Internal polyolefins (hereinafter also denoted by the acronym which can be used advantageously to prepare a filling composition according to the present invention, are mixtures of oligomers, typically dimers, trimers and tetramers, which can be produced, for example, by the polymerization of two or more n-olefinic monomeric units, each containing one unsaturation, this unsaturation being distributed in a statistical way along the whole chain. These n-olefinic monomeric units are preferably formed by chains each containing from 10 to 20 carbon atoms.
Preferably, the oligomeric chains are derived from e n-olefinic monomeric units, each of which contains a single unsaturation, this unsaturation being 15 distributed statistically along the whole chain.
Typically, the mixtures of initial monomers for preparing polyolefinic oligomers usable in the filling composition according to the present invention contain not more than 10% a-olefins, in other words n-olefins 20 having a double bond in the a position of the chain.
US patent No. 4,167,534 describes a suitable method of preparing these polyolefins.
According to this patent, the initial n-olefinic monomers are produced by dehydrogenation of n-paraffin by a process known as the PACOL-OLEX process.
These n-olefinic monomers are then polymerized by a catalytic autocondensation reaction.
The polymerization product is then distilled to separate the fractions having different ranges of PC756 12 molecular weight; the fractions pre-selected by the applicant allow for the requirements of the final filling composition, which should preferably have a viscosity of between 70 and 120 Pa-s (measured with a "shear rate" of 1.5 s- 1 at 25 0 compatibly with a pour point of less than -40 0
C.
The process is completed by a stabilization of the products by catalytic hydrogenation.
According to what has been stated above, in the case of monomers each containing from 10 to 20 carbon atoms the initial monomeric unit can be defined by the following formula: Cn C C Cm where: 15 0 m 17 0 n 17 8 m+n 18 Spreferably with the use of monomeric mixtures containing less than 10% a-olefins, in other words n- 20 olefins with a double bond in the a position.
The applicant has also observed preferred results when using the mixture of oligomers (dimers, trimers, tetramers, and mixtures of these) produced by polymerizing monomeric units according to the above formula where n+m is in the range from 10 to 16, in other words where chains with 12 to 18 carbon atoms are present.
PC756 13 Oligomers produced by polymerizing monomers each having 15 to 16 carbon atoms proved to be particularly advantageous.
Preferably, these mixtures of polyolefin oligomers have a weight average molecular weight in the range from approximately 400 to approximately 600.
The mixtures of oligomers used by the applicant were selected according to the effects which the various oligomers have on certain fundamental performances of the final mixture.
S. An increase of the content of tetramers with respect to the content of dimers typically causes an increase in viscosity, in the pour point and in the flash point, and also results in a reduction in vapor 15 pressure and consequently a lower volatility of the mixture.
This is because the internal polyolefins used for 9. the preparation of the invention are characterized by a high viscosity index, a limited reduction of viscosity 20 with an increase in temperature, low volatility and high thermal stability.
Preferably, these internal polyolefins have a viscosity in the range from 15 to 400 mPa-s at 40 0 C, and a viscosity in the range from 1 to 40 mPa-s at 100 0
C.
According to another advantageous characteristic, the pour point of the internal polyolefins used in the filling composition according to the invention is preferably in the range from -100 0 C to -40 0
C.
PC756 14 The term "pour point" denotes the lowest temperature at which the oil can still be made to move, when conditioned to the temperatures under investigation, according to the ASTM D97 standard (standards drawn up by the Institute of Electrical and Electronics Engineers, New York, USA).
Another advantageous characteristic of these polyolefins is an index of viscosity preferably lying in the range from approximately 120 to 160.
These internal polyolefins also preferably have a density, measured at 15 0 C, in the range from approximately 0.820 to approximately 0.835 kg/dm 3 Examples of polyolefins which can be used advantageously to prepare a filling composition 15 according to the invention are the products marketed by MixOil under the trade names MX 2104, MX 2106 and MX 2108. These products are typically mixtures of oligomers produced by polymerization of monomers having from 15 to 16 carbon atoms, whose typical distribution 20 of dimers, trimers, tetramers and higher oligomers is shown in Table I.
PC756 15 Table I. Composition of some commercially available mixtures of internal polyolefins by weight MX 2104 MX 2106 MX 2108 DIMERS 94 67 42 TRIMERS 6 26 43 TETRAMERS AND HIGHER 7
OLIGOMERS
The mixture forming the filler may comprise, in 5 addition to the internal polyolefins defined above, mineral oils, and in particular refined naphthenic oils which may advantageously partially replace the internal S* polyolefins in the filling mixture.
Preferably, these mineral oils have a viscosity in e 1 0 the range from approximately 4 to 60 mPa-s at 400C and a e viscosity in the range from approximately 1.5 to 7 mPa-s at 1000C.
These mineral oils also have a pour point which is preferably in the range from approximately -600C to 15 approximately -250C.
The abovementioned refined mineral oils primarily make it possible to produce a more economical filler, without any change in the properties of the final mixture, of which properties the fundamental one is compatibility, in the sense of chemical inertness, with the plastic materials which are contacted.
Oils suitable for the requirements are typically of the low-viscosity naphthenic type, which have a pour point below -400C; typical examples may be the products PC756 16 Nytex 800 and Nytex 810 and Nyflex 800 and Nyflex 810 manufactured by Nynas.
Typically, the proportion of mineral oil contained in the filling mixture varies from 0% to 70% by weight, and preferably from 20% to 60% by weight, a variation from 45% to 50% being particularly preferred. The total proportion of base oil, whether based on PIO only or formed by a mixture of PIO and mineral oil, within the total weight of the filling composition will typically be in the range from approximately 80% to 98% by
S
weight, and preferably from approximately 85% to 95% by weight.
A "viscosity improver", in other words an elastomeric substance capable of imparting a sufficiently high viscosity to the fluid oil base, may advantageously be added to the PIOs as such and also to mixtures of PIO and mineral distillation oils.
The viscosity imparted to the final compound is typically in the range from approximately 70 to 20 approximately 120 Pa-s, measured with a shear rate of s 1 at 250C.
The added elastomer which acts as a viscosity improver must have a high solubility in the oil, and has a very stable chemical structure, a considerable thickening capacity, even at low concentrations, and a high capacity for imparting adhesive and cohesive properties to the solution.
Among the various possible elastomers, the use of a block copolymer of the SEP type, in other words a PC756 17 block copolymer based on styrene-ethylene-propylene, was found to be particularly advantageous. Typically, these copolymers have a weight average molecular weight in the range from approximately 60,000 to approximately 200,000. The proportion of these materials in the total weight of the filling mixture is preferably in the range from 3% to 20%. The person skilled in the art is capable of selecting the quantity of these copolymers in a suitable way to obtain the desired viscosity, on the basis of the fact that, typically, a quantity of :...polymer with a high molecular weight makes it possible to obtain a higher viscosity than an equal quantity of a similar polymer having a lower molecular weight.
Examples of materials which may be used advantageously for this purpose are the commercial products Kraton G1701 and Kraton G1702 manufactured by Shell Chemical.
A further. component added to the mixture normally consists of an antioxidant, for example one of the type sold under the trade name Irganox 1010, Irganox 1076 (Ciba-Geigy), which adequately protect the filler from the thermal aging which takes place during the lifetime of the cable, as well as during the hot preparation of the filler.
The filling composition according to the invention can be used favourably to impede the longitudinal propagation of water in various cable structures. In particular, the composition can be used advantageously in direct contact with the optical fibres, for example PC756 18 when injected into the rigid coatings which contain them.
Optionally, pyrogenic silica, which can further thicken the filling mixture and make it thixotropic, may also be added to the filling composition according to the invention.
The following examples will further clarify the particularly advantageous aspects of the present invention.
10 EXAMPLE 1 Preparation of the filling composition according eto the invention and of the comparative compositions The following materials were used for the e preparation of the fillers according to the invention: MX 2106 and MX 2108 internal polyolefins; KRATON G1701 and G1702 thickener; IRGANOX 1010 antioxidant; NYFLEX 800 and 810 naphthenic oil.
The poly-a-olefins used by the applicant for the comparative tests described below are the NEXBASETM 2006 and NEXBASETM 2008 products manufactured by Nynas.
The apparatus used consists of a reactor, with a capacity from 1500 to 2000 litres, provided with a multiple-blade variable-speed agitator, capable of operating at temperatures of up to 130 0 C at least.
The base oil, in suitable measured amounts, is placed in the cold reactor together with the antioxidant, and agitation is carried out at between PC756 19 150 and 200 r.p.m. in such a way that the mixture is adequately stirred.
The elastomer, after being measured and comminuted, and preferably ground, is then added, this operation being supervised carefully in order to prevent the formation of lumps of elastomeric thickeners.
When a satisfactory dispersion has been achieved, the reactor is subjected to the experimentally 1 0 determined temperature (130 0 C in the case of the oil base consisting of MX 2108 or NEXBASETM 2008 only, 120 0
C
in the case of MX 2106 only or of NEXBASETM 2006 and mixtures of these with NYFLEX 810 oils, 105 0 C for the a.* base oil MX 2106 or NEXBASETM 2006 if mixed with NYFLEX 800 oil).
soon as the specified temperature is reached, the agitation is reduced, to match the temporary *reduction of viscosity of the mixture, and as the dissolving progresses the agitation velocity should be gradually increased again.
As regards the duration of the dissolving, this depends on the operating temperature, being longer for a lower maintained temperature.
When the elastomer has been fully dissolved, the temperature of the mixture is lowered by approximately 200C, and a vacuum is then created in the reactor, with continuing slow agitation of the mixture.
The next operation of degassing lasts for at least minutes, a vacuum of several mbar being produced.
PC756 20 At this point, the material is collected in drums at temperatures of 70-80 0 C, care being taken not to create turbulences, resulting in incorporation of air, during the operation.
A filling composition (indicated by the number 1 in Table II) was prepared by mixing 87.8 parts of MX 2016, 11.8 parts of KRATON G1701 and 0.4 part of
IRGANOX.
Similarly, another 6 compositions 3, 4, 5 and 1 0 6) were prepared, using materials and quantities as shown in Table II.
In particular, two naphthenic oils were used in the compositions indicated by 5, 6 and 7 in Table II, starting from a composition of the oily base mixture consisting of PIO and naphthenic oils in a ratio of *1:1.
Table II, which shows the composition in detail of the various components of the 7 mixtures according to the invention, shows in the last line the viscosity of the filler measured with a shear rate of s 1 at 25 0
C.
PC756 21 Table II. Composition by weight for fillers to the invention according COMPONENT 11 12 [3 14 MX 210 87. 91. 45. MX 2108 88.8 91.3 45.8 4 NYF'LEX 810 45.5 NYFLEX 800 IRGANOX 0.4 .0.4 0.4 0.4 .0.4 0.4 0.4 KRATON G1701 11.8 KRATON G1702 8.5 8.3 8 8.6 9.6 VISCOSITY 'y1.5 92 90.2 89.5 89.8 90 92.8 98 s-1 Three comparative filling compositions were 5 prepared in a similar way to that described above, using polyalphaolefins instead of internal polyolefins.
Table ha shows the details of these compositions.
PC756 22 Table IIa. Comparative compositions comprising polyalphaolefins, by weight: COMPOSITION 1 2 3 NEXBASETM 2006 88.6 91.1 NEXBASETM 2008 91.6 KRATON G1701 11 KRATON G1702 8.5 8 IRGANOX 1010 0.4 0.4 0.4 VISCOSITY y 1.5 s- 1 88.4 84.1 88 (Pa- s) a. a a a a a..
EXAMPLE 2 5 Measurement of the wetting capacity The wettability of the acrylic coating of the optical fibres by the filling composition is essentially determined by the oil component of the said composition. The thickening component has no wetting capacity for practical purposes.
In order to evaluate the tendency of the material to adhere to the walls of the optical fibres, and consequently its wetting capacity, the "angle of contact" of the oil component only was measured at 25 0
C,
and compared with the measured values for an internal polyolefin such as MX 2108 and for the similar poly-aolefin NEXBASETM 2008.
For this measurement, reference may be made to the publication by D.W. Van Krevelen, "Properties of polymers", published by Elsevier, pp. 230-231 (3rd edition).
PC756 23 Instruments made by Costech International S.r.l.
were used to measure the angle of contact.
The measurement consists in depositing, with a micro-syringe, a drop of the liquid under examination on a perfectly flat surface consisting of the material on which the interaction with the substance in question is to be evaluated, and waiting until the drop reaches a completely settled condition.
The angle of contact is defined as the angle 10 formed by the tangent to the drop, generated at the point of contact of this drop with the surface on which it is placed, and the said surface, this angle being measured externally with respect to the surface of the drop.
The wetting capacity of the filler was evaluated *according to the fact that smaller angles of contact indicate a greater wetting capacity of the liquid.
The values of the angle of contact measured relative to internal polyolefins and poly-a-olefins, at a temperature of 25 0 C, on a surface of dyed acrylates, which are the outermost coating materials of the optical fibre, repeated three times, are shown in Table
III.
Table III. Measurement of the angle of contact 1 2 3 NEXBASETM 2008 480 490 490 MX 2108 450 460 460 PC756 24 As will be seen from the results in Table III, the oil used according to the present invention (PIO) has a positive effect on the behaviour of the filling material, by improving the "wettability" of the coatings of the optical fibres.
The compositions identified by the applicant, comprising a synthetic oil based on internal polyolefins, therefore show, with respect to similar compositions based on poly-x-olefins, an improvement in relation to the wetting capacity, resulting in a greater resistance to water permeation, since the ingress of water into the acrylate/filler interface is made more difficult.
eeeo* 15 EXAMPLE 3 .0 Measurements of resistance to the movement of the go fibres in the filler An important aspect to which the present filler .00:0, corresponds is the improved capacity which it has for making the optical fibres move within it.
The applicant has confirmed the improved capacity which the filler has for making the optical fibres move :i within it, by means of a test consisting in filling a V-shaped groove having a length of 1 m with a composition of the filler according to the present invention, embedding an optical fibre in the filler in the centre of the groove, connecting one end of the optical fibre to an Instrom dynamometer by means of a suitable return pulley, and monitoring the value of the PC756 25 energy required to extract a 100 mm portion of optical fibre under traction at a controlled velocity of mm/min.
Table IV shows the results of this test, and demonstrates the lower extraction force to be applied to an optical fibre embedded in a filling composition according to the present invention by comparison with the force to be applied if this fibre is embedded in a known comparative composition.
Table IV. Extraction test of optical fibres.
Composition
S
*e S
*SSS
*e S COMPONENT 1 2 3 (comparat ive) MX 2106 91 45.7 NEXBASETM 2006 91.3 NYFLEX 810 45.7 NYFLEX 800 KRATON G1702 8.6 8.2 9.6 8.3 IRGANOX 1010 0.4 0.4 0.4 0.4 VISCOSITY y 1.5 s- 84.4 83.5 88.4 81.7 (Pa-s) EXTRACTION ENERGY 12.7 15.9 14 18.2 (mJ) PERCENTAGE VARIATION -30.22 -12.64 -23.08 with respect to the comparative sample PC756 26 This final test has therefore confirmed the greater freedom of movement of the optical fibres within the filler, an important parameter in relation to the reduction of the phenomena of bending of the optical fibres, which are harmful to the transmission of the signals.
EXAMPLE 4 Measurements of flowing resistance The flowing test of the filling material according to the present invention is carried out to evaluate the tendency of said material to drip in the cable.
Table V shows the details of compositions evaluated by the applicant by means of flowing test.
15 The first composition is a filling material according to the present invention, based on internal polyolefin (MX2106), and the second is a comparative filling material, based on polyalphaolefin (NEXBASETM 2006) Table V. Composition for fillers according to the invention COMPONENT
(B)
.MX 2106 91 NEXBASETM 2006 91.3 IRGANOX 1010 0.4 0.4 KRATON G1702 8.6 8.3 Viscosity (mPas) 84.4 86.1 PC756 27 The dripping test of filling material consists in placing an annular shaped sample of each composition on the upper end of a aluminum plate 400x80x2 mm in dimensions.
Each annular sample has the following dimensions: 3±0.1 mm thickness; 36±0.1 mm internal diameter; 80±0.1 mm external diameter.
Each plate is then placed inside an oven whose temperature is regulated at about 200±3 0 C with their principal plane inclined with respect to oven horizontal plane so as to form an angle of The longest side of aluminum plate is provided with a scale for permitting the measurements of the distance that the head of each sample covers during the dripping test.
S* Once samples reach the temperature imposed inside the oven (at t=0, measurement of distances covered by the heads of samples begins and is registered at different subsequent times as reported in Table VI.
S Table VI. Distances covered by two test pieces evaluated Time(minutes) Distance(A)(mm) Distance(B) (mm) 11 1 1 16 10 19 23 26 27 100 P:\WPDOCS\MCC\730349 31/5/99 -28- The results of flowing test clearly demonstrate that filling material according to the present invention shows an appreciable reduction of flowing with respect to the comparative filling material comprising similar polyalphaolemin base oil.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
o o*S*
Claims (16)
- 2. Cable according to Claim 1, characterized in that the filling composition comprises from 30% to 98% by weight of internal polyolefin.
- 3. Cable according to Claim 1 or 2, characterized in that the filling composition comprises from approximately 45% to approximately 95% by weight of internal polyolefin.
- 4. Cable according to Claim 1, characterized in that the filler is in contact with the said at least one 15 optical fibre. Cable according to Claim 1, characterized in that the said internal polyolefin is produced by the polymerization of unsaturated hydrocarbon monomeric units, each containing from 10 to 20 carbon atoms.
- 6. Cable according to Claim 6, characterized in that preferably each of the said monomeric units contains from 12 to 18 carbon atoms.
- 7. Cable according to Claim 6, characterized in that even more preferably each of the said monomeric units contains from 15 to 16 carbon atoms.
- 8. Cable according to Claim 6, 7 or 8, characterized in that the said internal polyolefin is an oligomer comprising from 2 to 4 unsaturated hydrocarbon monomeric units. PC756 30
- 9. Optical cable according to one of Claims 1 to 8, characterized in that the said internal polyolefin is a mixture of polyolefins having different molecular weights.
- 10. Cable according to Claim 9, characterized in that the said mixture of internal polyolefins is a mixture of oligomers, each comprising from 2 to 4 unsaturated hydrocarbon monomeric units.
- 11. Cable according to Claim 1 or 2, characterized in that the said filler comprises a polymeric thickener.
- 12. Cable according to Claim 11, characterized in that the said thickener is a block copolymer of the type which comprises styrene, propylene and ethylene units.
- 13. Cable according to Claim 1 or 2, characterized in that the said filling mixture also comprises a mineral oil.
- 14. Cable according to Claim 13, characterized in that the said mineral oil is a refined naphthenic oil. Cable according to Claim 14, characterized in that the said naphthenic oil has a viscosity in the range from 4 to 60 mPa-s, a viscosity in the range from to 7 mPa-s at 100 0 C, and a pour point in the range from 0 C to -25 0 C.
- 16. Optical cable according to one of Claims 13 to characterized in that the said mineral oil in the filling mixture replaces the quantity of internal polyolefin for a percentage by weight which varies from 0% to 20/5/99 -31
- 17. Composition for filling material, particularly for optical cables, characterised in that it comprises an internal polyolefin.
- 18. An optical cable, substantially as herein described with reference to the accompanying drawings.
- 19. A composition for filling material, particularly for optical cables, substantially as herein described. DATED this 4th day of June, 1999 PIRELLI CAVI E SISTEMI SPA By Their Patent Attorneys DAVIES COLLISON CAVE 0 a
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98110353 | 1998-06-05 | ||
| EP98110353 | 1998-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3320199A true AU3320199A (en) | 1999-12-16 |
| AU753705B2 AU753705B2 (en) | 2002-10-24 |
Family
ID=8232072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU33201/99A Ceased AU753705B2 (en) | 1998-06-05 | 1999-06-04 | Optical cable with filling material comprising an internal olefin oligomer |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2000056194A (en) |
| AR (1) | AR020592A1 (en) |
| AU (1) | AU753705B2 (en) |
| BR (1) | BR9901781B1 (en) |
| CA (1) | CA2273287C (en) |
| DE (1) | DE69943366D1 (en) |
| NZ (1) | NZ335916A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102384619B1 (en) * | 2017-06-30 | 2022-04-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Filling composition for fiber optic cables |
| EP3821511B1 (en) * | 2018-07-11 | 2023-05-10 | Dow Global Technologies LLC | Flooding composition with polytetrafluoroethyene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5737469A (en) * | 1996-06-03 | 1998-04-07 | Witco Corporation | Filling compound for fiber optical cables |
| US5748823A (en) * | 1997-01-30 | 1998-05-05 | Siecor Corporation | Single-tube plenum ribbon cable |
| US5911023A (en) * | 1997-07-10 | 1999-06-08 | Alcatel Alsthom Compagnie Generale D'electricite | Polyolefin materials suitable for optical fiber cable components |
-
1999
- 1999-05-14 DE DE69943366T patent/DE69943366D1/en not_active Expired - Lifetime
- 1999-05-25 NZ NZ33591699A patent/NZ335916A/en not_active IP Right Cessation
- 1999-05-27 CA CA 2273287 patent/CA2273287C/en not_active Expired - Fee Related
- 1999-06-03 AR ARP990102625 patent/AR020592A1/en active IP Right Grant
- 1999-06-04 JP JP11158246A patent/JP2000056194A/en active Pending
- 1999-06-04 BR BR9901781A patent/BR9901781B1/en not_active IP Right Cessation
- 1999-06-04 AU AU33201/99A patent/AU753705B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CA2273287C (en) | 2008-04-08 |
| DE69943366D1 (en) | 2011-06-01 |
| CA2273287A1 (en) | 1999-12-05 |
| JP2000056194A (en) | 2000-02-25 |
| AR020592A1 (en) | 2002-05-22 |
| BR9901781B1 (en) | 2008-11-18 |
| BR9901781A (en) | 2000-05-02 |
| AU753705B2 (en) | 2002-10-24 |
| NZ335916A (en) | 2000-12-22 |
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