FR2669036A1 - Process for making ethylene and propylene resins adhere to a lead surface - Google Patents

Process for making ethylene and propylene resins adhere to a lead surface Download PDF

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FR2669036A1
FR2669036A1 FR9013855A FR9013855A FR2669036A1 FR 2669036 A1 FR2669036 A1 FR 2669036A1 FR 9013855 A FR9013855 A FR 9013855A FR 9013855 A FR9013855 A FR 9013855A FR 2669036 A1 FR2669036 A1 FR 2669036A1
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Prior art keywords
sulfur
lead
tube
polyethylene
polyethylene sheath
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FR2669036B1 (en
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Vasseur Edouard
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Nexans France SAS
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Alcatel Cable SA
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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/128—Adhesives without diluent
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/40—Thiurams, i.e. compounds containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators 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
    • H01B3/44—Insulators 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
    • H01B3/441—Insulators 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 from alkenes
    • 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
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

The process for making ethylene and propylene resins adhere to a lead surface is obtained by introducing sulphur with the resin placed in contact when hot with the lead surface. It is characterised in that this introduction results at least partially from an organic sulphur compound, in particular a thiuram, added to the said resin beforehand. Application: manufacture of power, particularly submarine cables with a lead tube and polyethylene sheeting.

Description

Procédé pour faire adhérer des résines d'éthylène et de propylène sur une surface de plomb.A method of adhering ethylene and propylene resins to a lead surface.

La présente invention concerne un procédé pour faire adhérer des résines d'éthylène et de propylène sur une surface de plomb. The present invention relates to a method for adhering ethylene and propylene resins to a lead surface.

Le problème de faire adhérer de façon sûre et durable de tels copolymères qui ne comprennent pas de soufre et qui ne sont pas réticulables au soufre sur une surface de plomb se pose notamment dans la fabrication des câbles d'énergie, notamment sous-marins, à gaine de plomb et gaine de protection couramment en polyéthylène. En effet, il souhaitable de faire adhérer de façon étroite et durable la gaine de protection sur la gaine de plomb, pour obtenir une excellente tenue mécanique en fatigue de la gaine de plomb et limiter la pénétration d'eau en cas d'avarie. The problem of making such copolymers which do not contain sulfur and which cannot crosslink with sulfur securely and durably adhere to a lead surface arises in particular in the manufacture of power cables, in particular submarines, to lead sheath and protective sheath commonly made of polyethylene. In fact, it is desirable to adhere the protective sheath closely and durably to the lead sheath, in order to obtain excellent mechanical fatigue resistance of the lead sheath and to limit the penetration of water in the event of damage.

On a déjà proposé pour résoudre ce problème d'utiliser une feuille de plomb laminé contrecouchée au polyéthylène, mais l'adhésion du polyéthylène sur la feuille de plomb se révèle faible. It has already been proposed to solve this problem of using a laminated lead sheet laminated with polyethylene, but the adhesion of polyethylene to the lead sheet proves to be weak.

On sait par ailleurs que le caoutchouc et le plomb se collent de façon étroite et durable en présence de soufre. Leur adhésion est obtenue en effectuant une vulcanisation par chauffage de caoutchouc mis en contact avec le plomb, au cours de laquelle le soufre réagit sur le plomb en donnant du sulfure de plomb dont la liaison chimique est très stable. We also know that rubber and lead stick closely and durably in the presence of sulfur. Their adhesion is obtained by carrying out vulcanization by heating of rubber brought into contact with lead, during which the sulfur reacts on the lead giving lead sulfide whose chemical bond is very stable.

On a également proposé dans le document DE-A-2328801 de faire adhérer du polyéthylène sur une surface de plomb en additionnant une dispersion de polyéthylène dans un solvant de soufre ou de sulfure de cadmium avant sa mise en contact à chaud avec la surface de plomb. It has also been proposed in document DE-A-2328801 to adhere polyethylene to a lead surface by adding a dispersion of polyethylene in a sulfur or cadmium sulfide solvent before it is brought into hot contact with the lead surface. .

L'adhésion du polyéthylène obtenue sur la surface de plomb s'est révélée faible.The adhesion of the polyethylene obtained on the lead surface was found to be weak.

La présente invention a pour but de permettre d'obtenir une adhésion ferme et durable de résines d'éthylène et de propylène sur une surface de plomb, notamment pour des câbles à tube de plomb entouré d'une gaine de polyéthylène, réalisée par apport de soufre mais présentant par rapport aux techniques connues une liaison soufre-résine comparable à la liaison soufre-plomb. The present invention aims to obtain a firm and durable adhesion of ethylene and propylene resins on a lead surface, in particular for cables with lead tube surrounded by a polyethylene sheath, produced by adding sulfur but having compared to known techniques a sulfur-resin bond comparable to the sulfur-lead bond.

Le procédé selon l'invention est caractérisé en ce que 1' apport de soufre pour cette adhésion résulte au moins en partie d'un composé organique soufré, contenant au moins un atome de soufre relié à un atome de carbone par une double liaison, additionné à la résine avant sa mise au contact à chaud avec le plomb. The process according to the invention is characterized in that the addition of sulfur for this adhesion results at least in part from a sulfur-containing organic compound, containing at least one sulfur atom linked to a carbon atom by a double bond, added with resin before it is brought into hot contact with lead.

De préférence, le composé organique soufré est un thiurame, et plus particulièrement le disulfure de tétraméthylthiurame, de formule

Figure img00020001

ou le tétrasulfure de dipentaméthylène thiurame de formule
Figure img00020002
Preferably, the organic sulfur compound is a thiuram, and more particularly the tetramethylthiuram disulfide, of formula
Figure img00020001

or dipentamethylene thiuram tetrasulfide of formula
Figure img00020002

Selon une autre caractéristique, seule la partie d'interface de la résine sur le plomb assure l'adhésion souhaitée et est réalisée à partir d'un mélange maître de résine, de soufre pulvérulent, de composé organique soufré, en forte concentration dans le mélange, et éventuellement, en outre, de terpolymère éthylène-propylène-diène vulcanisable par le soufre. According to another characteristic, only the interface part of the resin on the lead ensures the desired adhesion and is produced from a masterbatch of resin, of powdery sulfur, of sulfur-containing organic compound, in high concentration in the mixture. , and optionally, in addition, of ethylene-propylene-diene terpolymer vulcanizable by sulfur.

La proportion de ce composé soufré par rapport au soufre dans le mélange maître est d'environ 5.000 à 50.000 % en poids. The proportion of this sulfur compound relative to the sulfur in the masterbatch is approximately 5,000 to 50,000% by weight.

La mise en oeuvre du procédé selon l'invention est précisée ci-après dans le cadre de son application à la fabrication d'un câble à tube de plomb et gaine de polyéthylène. The implementation of the method according to the invention is specified below in the context of its application to the manufacture of a lead tube cable and polyethylene sheath.

Dans une première variante d'application du procédé de l'invention, on introduit dans une extrudeuse un mélange maître contenant du soufre pulvérulent, le composé organique soufré et le polyéthylène, avant d'extruder à chaud la gaine de polyéthylène sur le tube de plomb. In a first variant application of the process of the invention, a masterbatch containing powdered sulfur, the sulfur-containing organic compound and the polyethylene is introduced into an extruder, before hot extruding the polyethylene sheath on the lead tube .

Dans une seconde variante préférentielle d'application du procédé de l'invention, on introduit dans une première extrudeuse du polyéthylène mélangé de soufre et du composé organique soufré de préférence en plus forte proportion que dans la première variante, et on extrude à chaud une première gaine de polyéthylène formant couche d'interface de collage sur le tube de plomb, puis, avec une deuxième extrudeuse n'ayant reçu que du polyéthylène, on extrude une deuxième gaine formant la gaine de revêtement proprement dite, adhérant directement sur la couche d'interface de même nature qu'elle. In a second preferred variant of application of the process of the invention, polyethylene mixed with sulfur and the organic sulfur compound is preferably introduced into a first extruder, preferably in a higher proportion than in the first variant, and a first extrusion is hot. polyethylene sheath forming a bonding interface layer on the lead tube, then, with a second extruder having received only polyethylene, a second sheath forming the coating sheath proper, is adhered directly to the layer of same type of interface.

Dans ces deux variantes, le mélange maître et éventuellement le polyéthylène peuvent, en outre, être additionnés de terpolymère éthylène-propylène-diène vulcanisable par le soufre, favorisant l'adhérence de la ou des gaines de polyéthylène au tube de plomb. In these two variants, the masterbatch and optionally the polyethylene may, in addition, be added with ethylene-propylene-diene terpolymer vulcanizable by sulfur, promoting the adhesion of the polyethylene sheath (s) to the lead tube.

La liaison soufre-polyéthylène et la liaison spontanée soufre-plomb sont obtenues à partir de la ou des doubles liaisons
C = S du composé organique soufré, qui s'ouvrent et se partagent en formant des liaisons covalentes avec une chaîne du polyéthylène et avec le plomb. Ces liaisons covalentes sont très solides et assurent un collage efficace et fiable.The sulfur-polyethylene bond and the spontaneous sulfur-lead bond are obtained from the double bond (s)
C = S of the organic sulfur compound, which open and share, forming covalent bonds with a polyethylene chain and with lead. These covalent bonds are very strong and ensure efficient and reliable bonding.

La présence de soufre dispersé dans le polyéthylène et éventuellement de terpolymère renforce le collage. The presence of sulfur dispersed in the polyethylene and possibly of terpolymer reinforces the bonding.

La mise en oeuvre du procédé selon l'invention permet de manière analogue d'obtenir l'adhésion de polypropylène sur une surface de plomb.  The implementation of the method according to the invention similarly makes it possible to obtain the adhesion of polypropylene to a lead surface.

Claims (8)

Revendications:Claims: 1/ Procédé pour faire adhérer des résines d'éthylène et de propylène sur une surface de plomb, par apport de soufre avec la résine mise en contact avec la surface de plomb, caractérisé en ce que ledit apport de soufre résulte au moins en partie d'un composé organique soufré, contenant au moins un atome de soufre lié à un atome de carbone par une double liaison, additionné initialement à ladite résine et constituant avec elle un mélange maître.1 / A method for adhering ethylene and propylene resins to a lead surface, by adding sulfur with the resin brought into contact with the lead surface, characterized in that said supply of sulfur results at least in part from 'an organic sulfur compound, containing at least one sulfur atom linked to a carbon atom by a double bond, initially added to said resin and constituting with it a masterbatch. 2/ Procédé selon la revendication 1, caractérisé en ce que le composé organique soufré est un thiurame.2 / A method according to claim 1, characterized in that the organic sulfur compound is a thiuram. 3/ Procédé selon la revendication 2, caractérisé en ce que le thiurame est le sulfure de tétraméthylthiurame ou le tétrasulfure de dipentaméthylènethiurame.3 / A method according to claim 2, characterized in that the thiuram is tetramethylthiuram sulfide or dipentamethylenethiuram tetrasulfide. 4/ Procédé selon les revendications 2 ou 3, caractérisé en ce que ledit mélange maître contient en outre du soufre pulvérulent, le composé organique soufré étant en proportion de 5.000 % à 50.000 % en poids par rapport au soufre.4 / A method according to claims 2 or 3, characterized in that said masterbatch also contains powdered sulfur, the organic sulfur compound being in proportion from 5,000% to 50,000% by weight relative to the sulfur. 5/ Procédé selon la revendication 4, caractérisé en ce que le mélange maître contient en outre un terpolymère éthylène-propylène-diène vucanisable par le soufre.5 / A method according to claim 4, characterized in that the masterbatch also contains an ethylene-propylene-diene terpolymer which can be sulfurized. 6/ Procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'il consiste à réaliser une première couche dite d'interface de collage sur la surface de plomb, à partir dudit mélange maltre, puis une deuxième couche dite de revêtement proprement dit sur ladite première couche d'interface, à partir de résine exempte dudit composé organique soufré.6 / A method according to one of claims 1 to 5, characterized in that it consists in producing a first layer called bonding interface on the lead surface, from said malter mixture, then a second layer called coating proper on said first interface layer, from resin free from said sulfur-containing organic compound. 7/ Procédé selon l'une des revendications 1 à 5 et appliqué à la fabrication d'un câble à tube de plomb et gaine de polyéthylène collée sur ce tube, caractérisé en ce que l'on introduit dans une extrudeuse ledit mélange maître, avant d'extruder directement à chaud la gaine de polyéthylène sur le tube de plomb.7 / A method according to one of claims 1 to 5 and applied to the manufacture of a lead tube cable and polyethylene sheath glued to this tube, characterized in that said master mixture is introduced into an extruder, before hot extrude the polyethylene sheath on the lead tube. 8/ Procédé selon la revendication 6 et appliqué à la fabrication d'un câble à tube de plomb et gaine de polyéthylène collée sur ce tube, caractérisé en ce que l'on introduit ledit mélange maître dans une première extrudeuse, avant d'extruder une première gaine de polyéthylène correspondant à ladite première couche d'interface de collage sur le tube de plomb, et dans une deuxième extrudeuse du polyéthylène éventuellement additionné de terpolymère éthylène-propylène-diène vulcanisable par le soufre, avant d'extruder une deuxième gaine de polyéthylène correspondant à ladite deuxième couche sur le tube de plomb déjà revêtu de ladite couche d'interface8 / A method according to claim 6 and applied to the manufacture of a cable with lead tube and polyethylene sheath glued to this tube, characterized in that said master mixture is introduced into a first extruder, before extruding a first polyethylene sheath corresponding to said first bonding interface layer on the lead tube, and in a second polyethylene extruder optionally supplemented with ethylene-propylene-diene terpolymer vulcanizable by sulfur, before extruding a second polyethylene sheath corresponding to said second layer on the lead tube already coated with said interface layer Cde collage. Cde collage.
FR9013855A 1990-11-08 1990-11-08 PROCESS FOR ADHESIVING ETHYLENE AND PROPYLENE RESINS ON A LEAD SURFACE. Expired - Fee Related FR2669036B1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH384757A (en) * 1956-12-31 1965-02-26 Western Electric Co Method for joining a body made of a saturated aliphatic hydrocarbon polymer, in particular polyethylene, to a body made of another material, in particular rubber or metal
FR2344613A1 (en) * 1976-03-15 1977-10-14 Alcan Res & Dev COATING BASED ON POLYETHYLENE AND ELECTRIC CONDUCTIVE CABLE WITH SUCH COATING
JPS54116047A (en) * 1978-03-02 1979-09-10 Kawaguchi Chemical Ind Rubber blend composition
JPS61238837A (en) * 1985-04-16 1986-10-24 Tokai Rubber Ind Ltd Pigmented rubber blend composition for lead sheath curing
JPS62209170A (en) * 1986-03-10 1987-09-14 Toshiba Chem Corp Resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH384757A (en) * 1956-12-31 1965-02-26 Western Electric Co Method for joining a body made of a saturated aliphatic hydrocarbon polymer, in particular polyethylene, to a body made of another material, in particular rubber or metal
FR2344613A1 (en) * 1976-03-15 1977-10-14 Alcan Res & Dev COATING BASED ON POLYETHYLENE AND ELECTRIC CONDUCTIVE CABLE WITH SUCH COATING
JPS54116047A (en) * 1978-03-02 1979-09-10 Kawaguchi Chemical Ind Rubber blend composition
JPS61238837A (en) * 1985-04-16 1986-10-24 Tokai Rubber Ind Ltd Pigmented rubber blend composition for lead sheath curing
JPS62209170A (en) * 1986-03-10 1987-09-14 Toshiba Chem Corp Resin composition

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BASE DE DONNEES CHEMICALS ABSTRACTS, (HOST: STN), vol. 92, no. 8, 1991, résumé no. 60152K, Columbus, Ohio, US; & JP-A-54 116 047 (KAWAGUCHI CHEM. IND. CO.) 10-09-1979 *
BASE DE DONNEES WPIL, AN=86-322280 [49], Derwent Publications Ltd, Londres, GB; & JP-A-61 238 837 (TOKAI RUBBER IND. K.K.) *
BASE DE DONNEES WPIL, AN=87-296527 [42], Derwent Publications Ltd, Londres, GB; & JP-A-62 209 170 (TOSHIBA CHEM. K.K.) *

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