GB2168991A - Thermally reversible encapsulating gel compound for filling cables - Google Patents

Thermally reversible encapsulating gel compound for filling cables Download PDF

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Publication number
GB2168991A
GB2168991A GB08531389A GB8531389A GB2168991A GB 2168991 A GB2168991 A GB 2168991A GB 08531389 A GB08531389 A GB 08531389A GB 8531389 A GB8531389 A GB 8531389A GB 2168991 A GB2168991 A GB 2168991A
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United Kingdom
Prior art keywords
weight
percent
solvent
oil
gel
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
GB08531389A
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GB8531389D0 (en
Inventor
Jr Dale Lee Handlin
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to US68706684A priority Critical
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of GB8531389D0 publication Critical patent/GB8531389D0/en
Publication of GB2168991A publication Critical patent/GB2168991A/en
Application status is Withdrawn legal-status Critical

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Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Abstract

A fast forming, thermally reversible gel for filling cables at selective, specific gel temperatures comprises a styrene-ethylene-butene-styrene block copolymer and a naphthenic or paraffinic oil or solvent with an aromatic content up to 25% by weight.

Description

SPECIFICATION Thermally reversible encapsulating gel compound Cables for power, electronic (telephone) transmission, hydrophone cables for oil exploration at sea and other various uses have been filled with various substances in order to protect against water intrusion since 1970. Intrusion occurs when water penetrates into a localized opening in a cable sheath and is free to channel as far as physical processes for water spread and transport allow, often hundreds of feet. Not only does this upset capacitance balance of the transmission cable line but it introduces more potential corrosion sites in proportion to the length of wire that is wetted. The useful life of water-soaked wires is obviously shorter than that of dry wires.

The solution that has been widely adopted is to fill the voids in the cable with a water insoluble filling material that simply encapsulates the cable components to prevent water intrusion. The filling fluid serves four purposes: 1) it provides a sonic couple of the hydrophone with the jacket; 2) it protects the electrical wiring from corrosive salt water; 3) it protects the environment from oil spills, and 4) it protects a vessel crew from the dangers associated with handling harsh solvents and oils.

However, although this physical function of the cable filling material is straight-forward, the choice of the material is not. Among the many considerations that are important for materials used in this application are the hydrophobic nature of the material, low temperature properties, flow characteristics at elevated temperatures, the highest temperature at which the encapsulant may be used ("upper service temperature"), processing characteristics, handling characteristics, dielectric properties, toxicity and cost. In addition, it is desired that the material have the capacity to control the gellation or gel dissolution temperature by changing the character of the vel. This is so that a specific gel dissolution temperature may be selected.

Materials that satisfy most of these criteria and which have been widely used are described in US patent Nos. 3,607,487, 3,717,716 issued September 21, 1971 and February 20, 1973 respectively and US patent No. 3,775,548. These materials are essentially a petroleum jelly, mixed with a polymer, usually polyethylene, to impart consistency and prevent flowing at warm temperatures below the upper service temperature.

Similar hydrophobic encapsulants have been proposed for filling splice closures. For example, US patent No. 3,879,575 issued April 22, 1975 describes a mixture of a low viscosity oil gelled by a styrene-isoprene-styrene copolymer, again with polyethylene added. The polyethylene is used to obtain a high use temperature needed for use with power transmission cables which reach high temperatures. US patent No. 4,259,540 discloses the use of a styrene-ethylene butylene-styrene block copolymer, polyethylene, and a paraffinic or naphthenic oil, where the oil has a maximum of 5% aromatic oils, in order to enable the cable encapsulant to meet the functional requirements of the cable, i.e., high temperature resistance and to provide good handling characteristics that petroleum jelly material does not possess.

However, all of these above-described encapsulants have a predetermined gel dissolution temperature which cannot be selectively controlled.

Control of the gellation (i.e., dissolution) temperature, as well as maintenance of the other necessary and desirable factors discussed, is thus highly desirable; however; heretofore there has not been found an encapsulating material with the necessary advantages, which is also highly selective with regard to the gellation temperature desired.

For example, one might wish a gel dissolution temperature to be fairly high so that the gel would form fast upon filling and allow the cable to be used quickly. Or, one might desire a gel which forms at a low temperature so that it would be slower forming. In addition, in none of these previously used materials in the above-described patents may the density be selectively controlled for the amount of buoyancy desired, while still retaining gellation temperature control, etc.

In addition, an encapsulant which is thermally reversible has long been sought. This means that the encapsulant may be removed and replaced during maintenance time and time again at a temperature below the temperature that would damage the cables. An encapsulant which is thermally reversible can be heated to a liquid and then cooled to a gel over and over again without damage to the nature of the filling material, or cable components. This is especially true in hydrophone cables that are generally not permanently instailed but towed at sea where the utility of such invention is paramount.

This invention includes a fast forming, thermally reversible gel so that it may be heated to a liquid and cooled to a gel over and over again at a temperature above the use temperature where the gel may be removed and replaced during maintenance. The gellation or gel dissolution temperature may be specifically controlled in order to change the character of the gel. This may be done by the concentration of polymer in either solvent and/or oil, the aromatic content of oil or solvent, and the molecular weight of KRATON G thermoplastic elastomer.

In addition, this gel may be formulated so as to be selective for desired degree of buoyancy of the cable.

The gel is based on light hydrocarbon process oils or solvents and styrene-ethylene-butylene-styrene block copolymers. The filling material (KRA TON G thermoplastic elastomer, available from Shell Oil, Houston, Texas) or gel encapsulating compound, comprises from about 2 percent by weight to about 15 percent by weight styrene-ethylene-butylene-styrene block copolymers and from about 85 percent by weight to about 98 percent by weight of a naphthenic or paraffinic oil or solvent with an aromatic content of up to 25 percent by weight. The encapsulating compound is preferably about 5% by weight of the S-EB-S block copolymer, and preferably about 95 percent by weight of a naphthenic or paraffinic oil or solvent with an aromatic content of preferably about 15 percent by weight.

This invention also includes a cable or other conduit requiring water protection which contains the encapsulating compound described above.

The encapsulating compound or gel of the present invention has the following properties: 1) Above the gel temperature the material is a clear, low viscosity fluid.

2) Below the gel temperature, the material is a non-conductive, clear rubber gel with measurable tensile strength.

3) The gel is thermally reversible at a temperature below the temperature that will damage the cables so that the gel may be removed and replaced during maintenance.

4) The gel dissolution temperature may be controlled precisely by the polymer concentration or by the aromatic content of the solvent or oil to temperatures from 10 "C to above 100 "C.

5) The gel is hydrophobic and protects the cable from water leakage.

6) The gel's hardness and strength increases gradually at temperatures increasingly below the gel temperature.

7) The specific gravity of the gel can be between 0.76 and 0.90 depending on the solvent, to provide desired buoyancy.

8) The gel provides as good a sonic couple as the cable fluids in general use.

The gel is based on light hydrocarbon process oils and/or solvents and styrene-ethylene-butylenestyrene block copolymers. Because of the temperature dependence of their compatibility with the paraffinic oils, and solvents, the S-EB-S block polymers' styrene domains dissolve in the oils or solvents above the gel dissolution temperature. Once dissolved, these styrene blocks exhibit fast phase separation and gel network formation from solution as the temperature is lowered.

The gel dissolution temperature is a function of (1) the concentration of polymer in either solvent and/or oil, (2) the aromatic content of oil or solvent being less than 25% by weight, and (3) the moiecular weight of KRATON thermoplastic elastomer. It should be noted that with oils containing > 20% aromatics concentration one may need to cool the solution to below room temperature to reach the gel dissolution temperature.

It is thought that many hydrocarbon fluids above the molecular weight of 150 will be gelled by S-EB S block copolymers. For example, Isopar M, available from Exxon, Houston, Texas, which has an average molecular weight of 191, has been used.

Shellflex 371, which has an average molecular weight of 400, is also suitable for gel formation.

For example, Shellflex 210 oil has been used which has a 16 percent aromatic content. Shellflex 131, may also be used as a suitable oil which contains about 24 percent aromatic content as well as Sunpar 120 LW, which contains less than 5 percent aromatic content.

The S-EB-S block copolymer dissolves in the oils easily especially at elevated temperature. The S EB-S block copolymer dissolves in lower molecular weight solvents to form a gel at room temperature in a period of several hours. The gel may be homogenized by heating above the gel dissolution temperature prior to filling. Because the polymer is low molecular weight, it increases the viscosity of the solvent only slightly above the gel temperature. Concentrations of S-EB-S block copolymer may be from about 2% by weight to about 15% by weight, but preferably about 6% by weight. Gels have been made with KRATON G 1650, 1651, and 1652 thermoplastic elastomer, which range from about 50,000 to about 200,000 molecular weight of the entire KRATON G molecule with 30% by weight styrene.

Paraffinic solvents include Shell Sol 71, available from Shell Oil, Houston, Texas and Isopar M and Nopar-13. Paraffinic oils may also be used including Shellflexo 210 (HVI 100N), Shellflex 371 (HVI 400N) (both available from Shell Oil Co., Houston, Texas), and Sunpar 120 LW/Shellflex 131 blends. In order to form a gel at polymer concentrations of less than 10%, the oil or solvent must contain less than 25% aromatics.

The KRATON G 1652 rubber may be dissolved in the oil at the cable filling site at a temperature above the gel dissolution temperature, or dissolved earlier and the gel handled in drums, or made in two parts, one consisting of a solution of S-EB-S rubber dissolved in a more aromatic oil so that it has a gel dissolution temperature below room temperature and the other part being a lower aromatic content oil so that when the two parts are mixed a gel is formed.

Applicant's invention encompasses a fast forming gel material which is thermally reversible so that if the cable is later punctured and the gel material must be released and/or refilled into the cable, it may be heated to solution and cooled to the filling temperature over and over again without any loss of the gel materials' desirable filling characteristics.

Figure 1 shows the triblock network structure of the styrene-ethylene-butene-styrene block copolymer. The styrene domains are spherical. The solvent is the ethylene-butene molecules (rubber block). Upon reaching the gel dissolution temperature, the spherical styrene domains are dissolved and the gel becomes a liquid. Prior to dissolution of the styrene domains, the material is a gel.

Figure 2 is a graph of the conceptual behaviour of the S-EB-S block copolymers in solvent. As the temperature increases, the S-EB-S block copolymers approach a more true solution. As the temperature decreases, the S-EB-S block copolymers approach a gel.

Various additional modifications and extensions of this invention such as to various types of cable or not even to cable at all, will become apparent to those skilled in the art. All such variations and de viations -which basically rely on the teachings through which this invention has advanced the art are properly considered to be within the spirit and scope of this invention.

Example 1 KRATON G 1652 rubber was dissolved in Sun parX 120 LW, available from Sun Oil Co., at 80 C so that the solution contained 4 percent S-EB-S block copolymer. As the solution temperature was lowered the viscosity began to rise sharply at about 62 "C and the solution gelled immediately upon reaching 60 "C. The gel had a dissolution temperature of 60 C.

Example 2 KRATON G 1652 rubber was dissolved in Shellflexs 131 oil, which may be obtained from Shell Oil Co., Houston, Texas, at 30 "C so that the solution contained 4 percent S-EB-S block copolymer. The solution gelled upon cooling at 15 "C.

Example 3 A clear gel was formed in Norpar 13 solvent, available from Exxon, Houston, Texas, by adding 4% KRATON G 1652 rubber and allowing the mixture to stand at 20 "C for two hours. Upon heating to 29 "C the gel dissolved to a low viscosity fluid.

Upon cooling, the solution gelled at 29 "C. Also, 4% KRATON G 1650 was added to Norpar-13, with a resulting gel temperature of 38 "C. Likewise, 4% KRATON G 1651 was added to Norpar-13, with a resulting temperature of greater than 100 "C. The same gel could be formed by dissolving above the gel temperature as in Example 1.

Example 4 A gel was made by mixing 33% Sunpar 120 LW oil at 40 "C with 66% by weight of a solution of 6% by weight KRATON G 1652 dissolved in Shellflex 131 oil which has a gel dissolution temperature below room temperature (18 "C) so that it could be prepared by stirring at room temperature. The resultant solution gelled at 30 "C upon cooling.

Example 5 The ethylenic comonomer containing the S-EB-S gel of Example 2 is filled into a suitable cable before cooling from the solution. The cable is ready for use immediately after filling.

Example 6 The gel may also be selectively made to achieve the amount of buoyancy desired in the cable when used in aqueous environments. For example, maximum cable buoyancy was achieved by dissolving 6% by weight KRATON G 1650 rubber in Norpar 13. The gel resulted in a specific gravity of 0.78 and a gel temperature of 42 "C.

Example 7 Minimum buoyancy was achieved by dissolving 4% KRATON G 1652 rubber in a 50/50 by weight blend of SUNPAR 120 LW oil and SHELLFLEX 131 oil. The gel resulted in a specific gravity of 0.88 and a gel temperature of 37 "C.

Claims (9)

1. A fast forming, thermally reversible encapsulating gel compound for filling cables which comprises: from about 2 percent by weight to about 15 percent by weight styrene-ethylene-butene-styrene block copolymers and from about 85 percent by weight to about 98 percent by weight of a naphthenic or paraffinic oil, or solvent where said oil or solvent has an aromatic content of from about 0 percent by weight to about 25 percent by weight.
2. The encapsulating compound of claim 1, wherein said encapsulating compound comprises from about 4 percent by weight to about 8 percent by weight S-EB-S copolymer and from about 92 percent by weight to about 96 percent by weight of said naphthenic or paraffinic oil or solvent, wherein said oil or solvent has an aromatic content of from about 5 percent by weight to about 25 percent by weight.
3. The encapsulating compound of claim 1, wherein said encapsulating compound comprises preferably about 6 percent by weight S-EB-S copolymer, and preferably about 94 percent by weight of said naphthenic or paraffinic oil or solvent, wherein said oil or solvent has an aromatic content of about 15 percent by weight.
4. A fast forming, thermally reversible encapsulating gel compound for filling cables which comprises: from about 2 percent by weight to about 15 percent by weight styrene-ethylene-butene-styrene block copolymer and from about 85 percent by weight to about 98 percent by weight of a naphthenic or paraffinic oil, or solvent, where said oil or solvent has an aromatic content of from about 0 percent by weight to about 25 percent by weight, and where the specific gravity of the gel ranges from about 0.78 for maximum buoyancy, to about 0.88 for minimum buoyancy.
5. A cable which may be filled below a temperature which would damage the contents and which may be easily repaired, which comprises: a cable body, which contains a fast forming, thermally reversible encapsulating compound, wherein said encapsulating compound contains from about 2 percent by weight to about 15 percent by weight S-EB-S copolymer, and from about 85 percent by weight to about 98 percent by weight of a naphthenic or paraffinic oil, or solvent, wherein said oil or solvent has an aromatic content of from about 0 percent by weight to about 25 percent by weight.
6. The cable of claim 5, wherein said encapsulating compound comprises from about 4 percent by weight to about 8 percent by weight S-EB-S copolymer, and from about 92 percent by weight to about 96 percent by weight of said naphthenic or paraffinic oil, or solvent, wherein said oil or solvent has an aromatic content of from about 5 percent by weight to about 25 percent by weight.
7. The cable in claim 6, wherein said encapsulating compound comprises preferably about 6 percent by weight S-EB-S copolymer, and prefera bly about 94 percent by weight of said naphthenic or paraffinic oil or solvent, where said oil or solvent has an aromatic content of about 15 percent by weight.
8. An encapsulating gel compound according to claim 1 substantially as hereinbefore described with reference to the Examples and/or to the accompanying drawings.
9. A cable according to claim 5 substantially as hereinbefore described with reference to the Exam ples and/or to the accompanying drawings.
GB08531389A 1984-12-28 1985-12-20 Thermally reversible encapsulating gel compound for filling cables Withdrawn GB2168991A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4709982A (en) * 1984-11-27 1987-12-01 Bicc Public Limited Company Gelled oil filling compounds
EP0299718A2 (en) * 1987-07-13 1989-01-18 Raychem Corporation Heat-resistant gel compositions
US5256705A (en) * 1986-03-26 1993-10-26 Waterguard Industries, Inc. Composition with tackifier for protecting communication wires
EP0566686A1 (en) * 1991-01-10 1993-10-27 The West Company, Incorporated Modified plastic elastomers block copolymers
WO1993025614A1 (en) * 1992-06-05 1993-12-23 Shell Internationale Research Maatschappij B.V. Elastosols, preparation, use and products thereof
EP0586158A1 (en) * 1992-08-31 1994-03-09 AT&T Corp. Cables which include waterblocking provisions
US5313019A (en) * 1988-11-09 1994-05-17 N.V. Raychem S.A. Closure assembly
US5618882A (en) * 1992-05-13 1997-04-08 Raychem Limited Gels containing SEPS block polymers
US6245426B1 (en) * 1996-07-04 2001-06-12 Abb Research Ltd. Electric device with a porous conductor insulation impregnated with a dielectric fluid exhibiting a rheologic transition point
GB2421078A (en) * 2004-12-10 2006-06-14 Pgs Geophysical As Controlling the internal geometry of a seismic streamer during introduction of filler material
WO2006098980A2 (en) * 2005-03-11 2006-09-21 Kraton Polymers Research B.V. Oil gels of controlled distribution block copolymers and ester oils
US7625967B2 (en) 2005-03-11 2009-12-01 Kraton Polymers U.S. Llc Oil gels of controlled distribution block copolymers and ester oils

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1268431A (en) * 1968-01-29 1972-03-29 Minnesota Mining & Mfg Stable elastomeric block polymer gels
US4369284A (en) * 1977-03-17 1983-01-18 Applied Elastomerics, Incorporated Thermoplastic elastomer gelatinous compositions
GB2106266A (en) * 1981-09-21 1983-04-07 Western Electric Co Sheathed optical fiber cable
GB2144237A (en) * 1983-07-28 1985-02-27 American Telephone & Telegraph Optical fiber cable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1268431A (en) * 1968-01-29 1972-03-29 Minnesota Mining & Mfg Stable elastomeric block polymer gels
US4369284A (en) * 1977-03-17 1983-01-18 Applied Elastomerics, Incorporated Thermoplastic elastomer gelatinous compositions
GB2106266A (en) * 1981-09-21 1983-04-07 Western Electric Co Sheathed optical fiber cable
GB2144237A (en) * 1983-07-28 1985-02-27 American Telephone & Telegraph Optical fiber cable

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4709982A (en) * 1984-11-27 1987-12-01 Bicc Public Limited Company Gelled oil filling compounds
US5256705A (en) * 1986-03-26 1993-10-26 Waterguard Industries, Inc. Composition with tackifier for protecting communication wires
EP0299718A2 (en) * 1987-07-13 1989-01-18 Raychem Corporation Heat-resistant gel compositions
EP0299718A3 (en) * 1987-07-13 1991-03-27 Raychem Corporation Heat-resistant gel compositions
US5313019A (en) * 1988-11-09 1994-05-17 N.V. Raychem S.A. Closure assembly
EP0566686A1 (en) * 1991-01-10 1993-10-27 The West Company, Incorporated Modified plastic elastomers block copolymers
EP0566686A4 (en) * 1991-01-10 1994-11-17 West Co Modified plastic elastomers block copolymers.
US5618882A (en) * 1992-05-13 1997-04-08 Raychem Limited Gels containing SEPS block polymers
WO1993025614A1 (en) * 1992-06-05 1993-12-23 Shell Internationale Research Maatschappij B.V. Elastosols, preparation, use and products thereof
US5900455A (en) * 1992-06-05 1999-05-04 Shell Oil Company Elastosols, process for the preparation thereof, process for the use of such elastosols and products derived from them
AU670294B2 (en) * 1992-06-05 1996-07-11 Shell Internationale Research Maatschappij B.V. Elastosols, preparation, use and products thereof
EP0586158A1 (en) * 1992-08-31 1994-03-09 AT&T Corp. Cables which include waterblocking provisions
US6245426B1 (en) * 1996-07-04 2001-06-12 Abb Research Ltd. Electric device with a porous conductor insulation impregnated with a dielectric fluid exhibiting a rheologic transition point
GB2421078A (en) * 2004-12-10 2006-06-14 Pgs Geophysical As Controlling the internal geometry of a seismic streamer during introduction of filler material
GB2421078B (en) * 2004-12-10 2008-04-09 Pgs Geophysical As Method for manufacturing a marine seismic streamer
WO2006098980A2 (en) * 2005-03-11 2006-09-21 Kraton Polymers Research B.V. Oil gels of controlled distribution block copolymers and ester oils
WO2006098980A3 (en) * 2005-03-11 2006-12-07 Kraton Polymers Res Bv Oil gels of controlled distribution block copolymers and ester oils
US7625967B2 (en) 2005-03-11 2009-12-01 Kraton Polymers U.S. Llc Oil gels of controlled distribution block copolymers and ester oils

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Publication number Publication date
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