EP1808867B1 - Thermally stable fluoride composition - Google Patents
Thermally stable fluoride composition Download PDFInfo
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- EP1808867B1 EP1808867B1 EP06301243A EP06301243A EP1808867B1 EP 1808867 B1 EP1808867 B1 EP 1808867B1 EP 06301243 A EP06301243 A EP 06301243A EP 06301243 A EP06301243 A EP 06301243A EP 1808867 B1 EP1808867 B1 EP 1808867B1
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- Prior art keywords
- composition
- copolymer
- fluorinated
- electric conductor
- titanium dioxide
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- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—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 vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
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- 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
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
Definitions
- the present invention relates to an electrical conductor coated with such an extruded, thermally stable composition.
- this composition is used to isolate part of the cables of category 5, 5e, 6 and 6e, in particular the white part of these cables.
- these cables are formed by the assembly of four twisted pairs, where each twisted pair comprises a copper wire insulated with a white-colored insulator associated with a copper wire insulated with a colored insulator.
- the document WO01 / 80253 proposes a high-speed extruded electrical cable insulation mixture composed of a pigmented fluoropolymer.
- the pigment used is titanium oxide coated with at least one layer of silicone and aluminum oxides.
- this composition does not provide acceptable thermal stability during the extrusion step.
- the thermal degradation generated by this step results in an imperfect surface appearance and a non-homogeneous internal structure of the insulation.
- the sheath thus formed has insulation defects with risks of electrical malfunctions and areas of blackening or discoloration.
- the invention aims to solve the problems of the prior art by proposing a fluorinated composition, having improved thermal stability, in particular, during the thermal transformation steps of the composition, making it possible to obtain an insulating material free from any defect in the composition. insulation.
- the thermal degradation of the polymer during the extrusion process is significantly limited.
- the preferred filler is zinc oxide.
- Zinc oxide is the most suitable scavenger for neutralizing hydrofluoric acid, especially during reactions taking place at high temperature such as the extrusion steps of fluoropolymers.
- the concentration of the filler is less than 5% by weight of the composition, and preferably less than 2%.
- the concentration of the titanium dioxide is less than 30% by weight of the composition, and preferably between 5% and 15%. Said concentrations of the filler and titanium dioxide thus limit the changes in the rheological properties of the fluorinated composition.
- the fluoropolymer is a fluorinated ethylene propylene (FEP) copolymer.
- the FEP is chosen from the tetrafluoroethylene / hexafluoroisopropene copolymer or the tetrafluoroethylene / hexafluoroisopropene / perfluoroalkylvinylether copolymer. This type of copolymer is most commonly used in the isolation of twisted pairs of LAN cables.
- the invention relates to an electrical conductor coated with at least one insulating layer, said layer being obtained from the composition according to the invention.
- the advantage of such an insulator is to obtain a homogeneous protection of the entire electrical conductor to avoid, for example, electrical breakdowns and to have a uniform appearance uncolored.
- the figure 1 represents a comparison of the thermal stability of extruded fluorinated compositions according to the invention and according to the prior art.
- the fluoropolymers undergo different stresses, in particular shear stresses and thermal stresses, with a temperature profile varying between 250 ° C. and 400 ° C.
- Titanium dioxide is used to whiten some of the cable sheaths for data transmission, including LAN cables.
- Titanium dioxide is the most used white pigment in the coloring of plastics because of its coloring power higher than other white pigments such as zinc sulphide or lithopone white.
- titanium dioxide There are two types of titanium dioxide: rutile mesh and anatase mesh. In the case of coloring plastics, the commonly used grades are rutile type, because of their better durability.
- titanium dioxide in the fluorinated compositions, reacts with the hydrofluoric acid released during the extrusion phase to form titanium tetrafluoride.
- titanium dioxide when the titanium dioxide is covered with alumina in order to improve its dispersion in the plastic material, another metal halide is formed in the presence of hydrofluoric acid such as aluminum trifluoride.
- these metal halides will accelerate the chain splitting reactions and thus accelerate the thermal degradation process of the extruded fluorinated composition.
- the sheath obtained undergoes an irreversible degradation of its chemical structure, translated by the appearance of microbubbles, by the formation of aggregates and, ultimately, by the blackening of the initially white sheath.
- the invention therefore aims to limit the thermal degradation process of the extrudable compositions based on fluorinated polymer and comprising titanium dioxide.
- the invention proposes the addition in said composition of an inorganic filler, capable of neutralizing the acid formed during the extrusion step of the composition, having an average particle size of less than 100 nm, and of preferably less than 60 nm.
- This average size of particles makes it possible to obtain an effective action on the stabilization process of pigmented fluorinated compositions. Indeed, the smaller the average particle size, the greater the specific surface area of the filler, since the specific surface area is inversely proportional to the average particle size. It is necessary so that a maximum surface of the load is in contact with said composition.
- Said filler is a solid material which does not interact chemically with the polymer matrix and is intended to neutralize the hydrofluoric acid as it is formed.
- the insulating material thus formed is homogeneous in its chemical structure and presents no insulation defects or aggregates.
- the white color of the insulation is persistent and no trace of blackening is visible on its surface.
- the inorganic, acid scavenger is zinc oxide.
- zinc oxide is the most thermally stable filler.
- Zinc oxide is thus particularly suitable for the stabilization of systems whose processing temperatures are high, particularly in the case of the extrusion step of fluoropolymers.
- the composition comprises nanometric zinc oxide, the average particle size of which is between 35 and 55 nm.
- the filler is selected from dehydrated alkaline fillers such as magnesium oxide or calcium oxide.
- the composition comprises nanoscale magnesium oxide or nanoscale calcium oxide, the average particle size of which is approximately 30 or 40 nm, respectively.
- the concentration of the filler is less than 5% by weight of the composition, and preferably less than 2%.
- the concentration of the titanium dioxide is less than 30% by weight of the composition, and preferably between 5% and 15%.
- the concentration of the pigment in the extruded fluorinated composition and the dilution of this composition in a virgin fluorine resin during the insulation phase of an electrical conductor, in particular a copper wire, are the two parameters that govern the coloring. final insulation.
- the concentration of the pigment is greater than 30%, problems of rheology appear: the quality of the dispersion of the pigment in the fluorinated composition is impaired by the formation of aggregates and agglomerates of pigments. This results in a final non-homogeneous coloration of the insulation.
- concentration of the pigment is less than 5%, a much larger proportion of extruded fluorinated composition should be used in addition to the virgin fluorine resin.
- the fluorinated polymer may be chosen in particular from tetrafluoroethylene copolymers such as fluorinated ethylene propylene copolymer (FEP), ethylene tetrafluoroethylene (ETFE) copolymer, ethylene and fluorinated ethylene-propylene terpolymer ( DAIKIN EFEP or DYNEON HTE), copolymer of tetrafluoroethylene and perfluoromethylvinylether (MFA) and copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), as well as homopolymers, copolymers and terpolymers containing vinylidene fluoride (PVDF, THV).
- FEP fluorinated ethylene propylene copolymer
- ETFE ethylene tetrafluoroethylene
- DAIKIN EFEP or DYNEON HTE fluorinated ethylene-propylene terpolymer
- the composition comprises a fluorinated ethylene propylene (FEP) copolymer, especially tetrafluoroethylene (TFE) / hexafluoroisopropene (HFP) copolymer.
- FEP fluorinated ethylene propylene
- TFE tetrafluoroethylene
- HFP hexafluoroisopropene
- Modified FEP copolymers can also be used.
- the modification is made by the addition, in a minor amount, of a third monomer during the synthesis of the modified FEPs, which may be a perfluoroalkylvinyl ether (PAVE) monomer of the perfluoropropylvinyl ether (PPVE) or perfluoroethylvinyl ether (PEVE) type. .
- PAVE perfluoroalkylvinyl ether
- PPVE perfluoropropylvinyl ether
- PEVE perfluoroethylvinyl ether
- the main but non-limiting application of the invention lies in the field of data transmission cables. It concerns, in fact, electrical conductors coated with at least one insulating layer obtained from the composition according to the invention.
- the stability of the material can be evaluated in two ways. The first is to follow the evolution of the Newtonian viscosity of the fluorinated composition at different stages of thermal degradation: the composition having the lowest viscosity drop as a function of the treatment time is the most thermally stable. The second analysis consists in progressively comparing the evolution of the white color of the composition towards a gray discoloration, consequence of its thermal degradation.
- Samples were prepared by mixing the FEP resin, pigments and fillers with a Berstorff Corotative Bi-Vis extruder.
- the inorganic filler used is nanometric zinc oxide, the average particle size of which is between 35 and 55 nm and whose specific surface area is of the order of 20-30 m 2 / g.
- Table 1 gives the compositions of the samples of the various mixtures studied in the context of the invention.
- the extruded fluorinated composition is then cooled in a tray of water, then dried and granulated.
- Sample A was aged according to the procedure described above and has the highest thermal stability among the samples tested in the study.
- Sample B was aged according to the procedure described above. Its thermal stability decreases by 4.1% compared to that of the standard sample A.
- Sample C was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 15% by weight of TiO 2 .
- the capillary rheometry analysis of the sample shows that the thermal stability drops by 22.6% compared to the standard sample A.
- Sample D was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 14.8% by weight of TiO 2 and 0.2% by weight of nanometric ZnO, the average particle size of which is between 0.035 and 0.055 ⁇ m.
- the capillary rheometry analysis of the sample shows that the thermal stability drops by 19.1% compared to the standard sample A.
- Sample E was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 14% by weight of TiO 2 and 1% by weight of nanometric ZnO, the average particle size of which is between 0.035 and 0.055 ⁇ m.
- the capillary rheometry analysis of the sample shows that the thermal stability drops by 13.7% compared to the standard sample A.
- sample D The presence of 0.2% of nanometric ZnO (sample D) and 1% of nanometric ZnO (sample E) makes it possible to improve the thermal stability of the mixture by 4.2% and 10.3%, respectively, compared to sample C.
- a second simple and effective means, not shown, for evaluating the thermal stability of extruded fluorinated compositions is to observe the evolution of the discoloration of the material, in particular its blackening, as a function of the thermal aging time at 400 ° C.
- sample C begins to darken after 5 minutes in the sleeve of the capillary rheometer.
- samples D and E having undergone the same type of thermal aging, begin to be discolored only after 10 minutes in the sleeve of the capillary rheometer.
- fillers such as synthetic hydrocalcites or hydrocalumites can also be used.
Abstract
Description
La présente invention concerne un conducteur électrique revêtu d'une telle composition extrudée, thermiquement stable.The present invention relates to an electrical conductor coated with such an extruded, thermally stable composition.
Elle s'applique typiquement à l'isolation, à base de polymère fluoré, des fils de cuivre dans le domaine des câbles LAN ou Local Area Network (réseau local) et, plus généralement, à des câbles de transmission de données.It typically applies to the fluoropolymer-based insulation of copper wires in the field of LAN or Local Area Network (LAN) cables and, more generally, to data transmission cables.
Dans un exemple de réalisation, cette composition est utilisée pour isoler une partie des câbles de catégorie 5, 5e, 6 et 6e, notamment la partie blanche de ces câbles. En effet, ces câbles sont formés par l'assemblage de quatre paires torsadées, où chaque paire torsadée comporte un fil de cuivre isolé par un isolant de couleur blanche associé à un fil de cuivre isolé par un isolant coloré.In an exemplary embodiment, this composition is used to isolate part of the cables of category 5, 5e, 6 and 6e, in particular the white part of these cables. Indeed, these cables are formed by the assembly of four twisted pairs, where each twisted pair comprises a copper wire insulated with a white-colored insulator associated with a copper wire insulated with a colored insulator.
Le document
L'invention vise à résoudre les problèmes de l'art antérieur en proposant une composition fluorée, ayant une stabilité thermique améliorée, notamment, lors des étapes de transformation thermique de la composition, permettant d'obtenir un matériau isolant exempt de tout défaut d'isolation.The invention aims to solve the problems of the prior art by proposing a fluorinated composition, having improved thermal stability, in particular, during the thermal transformation steps of the composition, making it possible to obtain an insulating material free from any defect in the composition. insulation.
A cet effet, l'invention a pour objet un conducteur électrique revêtu d'au moins une couche isolante, caractérisé en ce que ladite couche est obtenue a partir dune composition extrudable, thermiquement stable, comprenant:
- un polymère fluoré,
- du dioxyde de titane, et
- une charge inorganique dite piégeuse d'acide, apte a neutraliser l'acide fluorhydrique formé lors de l'étape d'extrusion de la composition, la charge inorganique étant choisie parmi l'oxyde de zinc nanométrique, l'oxyde de magnésium nanométrique ou l'oxyde de calcium nanométrique.
- a fluorinated polymer,
- titanium dioxide, and
- an inorganic so-called acid scavenger, capable of neutralizing the hydrofluoric acid formed during the extrusion step of the composition, the inorganic filler being chosen from nanometric zinc oxide, nanometric magnesium oxide or nanoscale calcium oxide.
Grâce à l'invention, la dégradation thermique du polymère, lors du processus d'extrusion, est limitée de façon significative.Thanks to the invention, the thermal degradation of the polymer during the extrusion process is significantly limited.
En particulier, la charge préférée est l'oxyde de zinc. L'oxyde de zinc est le piégeur le plus adéquat pour neutraliser l'acide fluorhydrique, en particulier lors des réactions se déroulant à température élevée telle que les étapes d'extrusions des polymères fluorés.In particular, the preferred filler is zinc oxide. Zinc oxide is the most suitable scavenger for neutralizing hydrofluoric acid, especially during reactions taking place at high temperature such as the extrusion steps of fluoropolymers.
Dans un exemple de réalisation, la concentration de la charge est inférieure à 5% en poids de la composition, et de préférence inférieure à 2%.In an exemplary embodiment, the concentration of the filler is less than 5% by weight of the composition, and preferably less than 2%.
Selon une autre caractéristique, la concentration du dioxyde de titane est inférieure à 30% en poids de la composition, et de préférence comprise entre 5% et 15%. Lesdites concentrations de la charge et du dioxyde de titane limitent ainsi les modifications des propriétés rhéologiques de la composition fluorée.According to another characteristic, the concentration of the titanium dioxide is less than 30% by weight of the composition, and preferably between 5% and 15%. Said concentrations of the filler and titanium dioxide thus limit the changes in the rheological properties of the fluorinated composition.
Par ailleurs, le polymère fluoré est un copolymère d'éthylène propylène fluoré (FEP).In addition, the fluoropolymer is a fluorinated ethylene propylene (FEP) copolymer.
De préférence, le FEP est choisi parmi le copolymère tétrafluoroéthylène / hexafluoroisopropène ou le copolymère tétrafluoroéthylène / hexafluoroisopropène / perfluoroalkylvinyléther. Ce type de copolymère est le plus couramment utilisé dans l'isolation des paires torsadées des câbles LAN.Preferably, the FEP is chosen from the tetrafluoroethylene / hexafluoroisopropene copolymer or the tetrafluoroethylene / hexafluoroisopropene / perfluoroalkylvinylether copolymer. This type of copolymer is most commonly used in the isolation of twisted pairs of LAN cables.
Selon un deuxième aspect, l'invention concerne un conducteur électrique revêtu d'au moins une couche isolante, ladite couche étant obtenue à partir de la composition selon l'invention.According to a second aspect, the invention relates to an electrical conductor coated with at least one insulating layer, said layer being obtained from the composition according to the invention.
L'avantage d'un tel isolant est d'obtenir une protection homogène de tout le conducteur électrique afin d'éviter, par exemple, les claquages électriques et de présenter un aspect uniforme non décoloré.The advantage of such an insulator is to obtain a homogeneous protection of the entire electrical conductor to avoid, for example, electrical breakdowns and to have a uniform appearance uncolored.
L'invention sera mieux comprise grâce à la description qui suit en référence aux dessins annotés et illustrant divers modes de réalisation.The invention will be better understood from the description which follows with reference to the annotated drawings and illustrating various embodiments.
La
Lors des étapes d'extrusion, les polymères fluorés subissent différentes contraintes, en particulier des contraintes de cisaillements et des contraintes thermiques, avec un profil de température variant entre 250°C et 400°C.During the extrusion stages, the fluoropolymers undergo different stresses, in particular shear stresses and thermal stresses, with a temperature profile varying between 250 ° C. and 400 ° C.
La conséquence inévitable de ces deux types de contraintes est la dégradation des extrémités des chaînes carbonyles telles que les groupements -COF ou -COOH et des défauts d'enchaînement intramacromoléculaires, par exemple provenant des diades d'hexaflurorisopropylène (HFP), thermiquement instables.The inevitable consequence of these two types of constraints is the degradation of the ends of the carbonyl chains such as -COF or -COOH groups and intramacromolecular chain defects, for example from thermally unstable hexaflurorisopropylene (HFP) diads.
Ces sites sont donc précurseurs du processus de dégradation thermique des polymères fluorés.These sites are therefore precursors of the thermal degradation process of fluoropolymers.
Cette dégradation thermique va engendrer la formation de l'acide fluorhydrique qui va ainsi alimenter le processus de dégradation de la composition fluorée extrudée.This thermal degradation will cause the formation of hydrofluoric acid which will thus feed the degradation process of the extruded fluorinated composition.
Le dioxyde de titane est utilisé pour blanchir une partie des gaines de câbles pour la transmission de données, notamment des câbles LAN.Titanium dioxide is used to whiten some of the cable sheaths for data transmission, including LAN cables.
Le dioxyde de titane est le pigment blanc le plus employé dans la coloration des matières plastiques en raison de son pouvoir de coloration supérieur à celui des autres pigments blancs tels que le sulfure de zinc ou le blanc de lithopone.Titanium dioxide is the most used white pigment in the coloring of plastics because of its coloring power higher than other white pigments such as zinc sulphide or lithopone white.
Il existe deux types de dioxyde de titane : la maille rutile et la maille anatase. Dans le cas de la coloration des matières plastiques, les grades couramment utilisés sont de type rutile, en raison de leur meilleure durabilité.There are two types of titanium dioxide: rutile mesh and anatase mesh. In the case of coloring plastics, the commonly used grades are rutile type, because of their better durability.
Il est connu que le dioxyde de titane, dans les compositions fluorées, réagit avec l'acide fluorhydrique libéré lors de la phase d'extrusion pour former du tétrafluorure de titane.It is known that titanium dioxide, in the fluorinated compositions, reacts with the hydrofluoric acid released during the extrusion phase to form titanium tetrafluoride.
Dans un exemple particulier, lorsque le dioxyde de titane est recouvert d'alumine afin d'améliorer sa dispersion dans la matière plastique, un autre halogénure métallique se forme en présence d'acide fluorhydrique tel que du trifluorure d'aluminium.In a particular example, when the titanium dioxide is covered with alumina in order to improve its dispersion in the plastic material, another metal halide is formed in the presence of hydrofluoric acid such as aluminum trifluoride.
Dès lors, ces halogénures métalliques vont accélérer les réactions de scissions de chaînes et ainsi accélérer le processus de dégradation thermique de la composition fluorée extrudée.Therefore, these metal halides will accelerate the chain splitting reactions and thus accelerate the thermal degradation process of the extruded fluorinated composition.
La gaine obtenue subit une dégradation irréversible de sa structure chimique, traduite par l'apparition de microbulles, par la formation d'agrégats et, au final, par le noircissement de la gaine initialement de couleur blanche.The sheath obtained undergoes an irreversible degradation of its chemical structure, translated by the appearance of microbubbles, by the formation of aggregates and, ultimately, by the blackening of the initially white sheath.
L'invention vise donc à limiter le processus de dégradation thermique des compositions extrudables à base de polymère fluoré et comprenant du dioxyde de titane.The invention therefore aims to limit the thermal degradation process of the extrudable compositions based on fluorinated polymer and comprising titanium dioxide.
Pour cela, l'invention propose l'ajout dans ladite composition d'une charge inorganique, apte à neutraliser l'acide formé lors de l'étape d'extrusion de la composition, ayant une taille moyenne de particules inférieure à 100nm, et de préférence inférieure à 60nm.For this, the invention proposes the addition in said composition of an inorganic filler, capable of neutralizing the acid formed during the extrusion step of the composition, having an average particle size of less than 100 nm, and of preferably less than 60 nm.
Cette taille moyenne de particules permet d'obtenir une action efficace sur le processus de stabilisation de compositions fluorées pigmentées. En effet, plus la taille moyenne de particules est faible, plus la surface spécifique de la charge est importante puisque la surface spécifique est inversement proportionnelle à la taille moyenne des particules. Il faut donc qu'une surface maximale de la charge soit en contact avec ladite composition.This average size of particles makes it possible to obtain an effective action on the stabilization process of pigmented fluorinated compositions. Indeed, the smaller the average particle size, the greater the specific surface area of the filler, since the specific surface area is inversely proportional to the average particle size. It is necessary so that a maximum surface of the load is in contact with said composition.
Ladite charge est un matériau solide qui n'interagit pas chimiquement avec la matrice polymère et a pour objet de neutraliser l'acide fluorhydrique au fur et à mesure de sa formation.Said filler is a solid material which does not interact chemically with the polymer matrix and is intended to neutralize the hydrofluoric acid as it is formed.
La formation des halogénures métalliques est ainsi sensiblement évitée, ce qui a pour conséquence de ralentir considérablement la cinétique de dégradation de la résine polymère extrudée.The formation of metal halides is thus substantially avoided, which has the effect of considerably slowing down the kinetics of degradation of the extruded polymer resin.
Le matériau isolant ainsi formé est homogène dans sa structure chimique et ne présente ni défauts d'isolation, ni agrégats.The insulating material thus formed is homogeneous in its chemical structure and presents no insulation defects or aggregates.
De ce fait, la couleur blanche de l'isolant est persistante et aucune trace de noircissement n'est visible à sa surface.As a result, the white color of the insulation is persistent and no trace of blackening is visible on its surface.
Dans un mode de réalisation particulier, la charge inorganique, piégeuse d'acide, est l'oxyde de zinc.In a particular embodiment, the inorganic, acid scavenger is zinc oxide.
Parmi les diverses charges « piégeuses d'acide » tels que les stéarates métalliques et les grades d'hydrotalcite et d'hydrocalumite, l'oxyde de zinc est la charge la plus stable thermiquement.Among the various "acid scavenger" fillers such as metal stearates and hydrotalcite and hydrocalumite grades, zinc oxide is the most thermally stable filler.
L'oxyde de zinc est ainsi particulièrement adapté pour la stabilisation de systèmes dont les températures de transformation sont élevées, notamment dans le cas de l'étape d'extrusion des polymères fluorés.Zinc oxide is thus particularly suitable for the stabilization of systems whose processing temperatures are high, particularly in the case of the extrusion step of fluoropolymers.
Dans un exemple particulier, la composition comprend de l'oxyde de zinc nanométrique, dont la taille moyenne de particules est comprise entre 35 et 55nm.In a particular example, the composition comprises nanometric zinc oxide, the average particle size of which is between 35 and 55 nm.
Dans un autre mode de réalisation de l'invention, la charge est choisie parmi les charges alcalines déshydratées telles que l'oxyde de magnésium ou l'oxyde de calcium.In another embodiment of the invention, the filler is selected from dehydrated alkaline fillers such as magnesium oxide or calcium oxide.
Dans un exemple particulier, la composition comprend de l'oxyde de magnésium nanométrique ou de l'oxyde de calcium nanométrique dont la taille moyenne de particules est respectivement d'environ 30 ou 40nm.In a particular example, the composition comprises nanoscale magnesium oxide or nanoscale calcium oxide, the average particle size of which is approximately 30 or 40 nm, respectively.
La concentration de la charge est inférieure à 5% en poids de la composition, et de préférence inférieure à 2%.The concentration of the filler is less than 5% by weight of the composition, and preferably less than 2%.
L'intérêt d'utiliser une charge présentant une surface spécifique importante permet de stabiliser la composition avec une faible concentration de ladite charge par rapport à la concentration de dioxyde de titane et ainsi de ne pas modifier les propriétés rhéologiques de la composition fluorée pigmentée.The advantage of using a filler having a large specific surface makes it possible to stabilize the composition with a low concentration of said filler relative to the concentration of titanium dioxide and thus not to modify the rheological properties of the pigmented fluorinated composition.
Selon une autre caractéristique de l'invention, la concentration du dioxyde de titane est inférieure à 30% en poids de la composition, et de préférence entre 5% et 15%.According to another characteristic of the invention, the concentration of the titanium dioxide is less than 30% by weight of the composition, and preferably between 5% and 15%.
La concentration du pigment dans la composition fluorée extrudée et la dilution de cette composition dans une résine fluorée vierge au cours de la phase d'isolation d'un conducteur électrique, notamment d'un fil de cuivre, sont les deux paramètres qui gouvernent la coloration finale de l'isolant.The concentration of the pigment in the extruded fluorinated composition and the dilution of this composition in a virgin fluorine resin during the insulation phase of an electrical conductor, in particular a copper wire, are the two parameters that govern the coloring. final insulation.
Si la concentration du pigment est supérieure à 30%, des problèmes de rhéologie apparaissent : la qualité de la dispersion du pigment dans la composition fluorée est altérée par la formation d'agrégats et d'agglomérats de pigments. Il en résulte une coloration finale non homogène de l'isolant.If the concentration of the pigment is greater than 30%, problems of rheology appear: the quality of the dispersion of the pigment in the fluorinated composition is impaired by the formation of aggregates and agglomerates of pigments. This results in a final non-homogeneous coloration of the insulation.
Si la concentration du pigment est inférieure à 5%, une proportion beaucoup plus importante de composition fluorée extrudée doit être utilisée en complément de la résine fluorée vierge.If the concentration of the pigment is less than 5%, a much larger proportion of extruded fluorinated composition should be used in addition to the virgin fluorine resin.
Le polymère fluoré peut être choisi notamment parmi les copolymères du tetrafluoréthylène tels que le copolymère d'éthylène propylène fluoré (FEP), le copolymère d'éthylène et de tétrafluoroéthylène (ETFE), le terpolymère d'éthylène et d'éthylène-propylène fluoré (EFEP de DAIKIN ou HTE de DYNEON), le copolymère de tétrafluoroéthylène et de perfluorométhylvinyléther (MFA) et le copolymère de tétrafluoroéthylène et de perfluoropropylvinyléther (PFA), ainsi que les homopolymères, copolymères et terpolymères contenant le fluorure de vinylidène (PVDF, THV).The fluorinated polymer may be chosen in particular from tetrafluoroethylene copolymers such as fluorinated ethylene propylene copolymer (FEP), ethylene tetrafluoroethylene (ETFE) copolymer, ethylene and fluorinated ethylene-propylene terpolymer ( DAIKIN EFEP or DYNEON HTE), copolymer of tetrafluoroethylene and perfluoromethylvinylether (MFA) and copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), as well as homopolymers, copolymers and terpolymers containing vinylidene fluoride (PVDF, THV).
Dans une réalisation particulière de l'invention, la composition comprend un copolymère d'éthylène propylène fluoré (FEP), notamment le copolymère tétrafluoroéthylène (TFE) / hexafluoroisopropène (HFP).In a particular embodiment of the invention, the composition comprises a fluorinated ethylene propylene (FEP) copolymer, especially tetrafluoroethylene (TFE) / hexafluoroisopropene (HFP) copolymer.
Des copolymères FEP modifiés peuvent également être utilisés. La modification est apportée par l'ajout, en quantité minoritaire, d'un troisième monomère lors de la synthèse des FEP modifiés, qui peut être un monomère de perfluoroalkylvinyl éther (PAVE) de type perfluoropropylvinyl éther (PPVE) ou perfluoroéthylvinyl éther (PEVE).Modified FEP copolymers can also be used. The modification is made by the addition, in a minor amount, of a third monomer during the synthesis of the modified FEPs, which may be a perfluoroalkylvinyl ether (PAVE) monomer of the perfluoropropylvinyl ether (PPVE) or perfluoroethylvinyl ether (PEVE) type. .
Ces monomères sont utilisés dans la synthèse des FEP non seulement pour apporter un meilleur contrôle de la distribution molaire du fluoropolymère, mais leur présence permet d'améliorer significativement les propriétés mécaniques de ce type de composition et notamment la résistance à la fatigue sous contrainte. Toutefois, les motifs perfluoroalkylvinyl éthers sont beaucoup plus sensibles aux halogénures métalliques que les motifs TFE ou HFP, ce qui rend la chaîne macromoléculaire plus vulnérable.These monomers are used in the synthesis of FEP not only to provide better control of the molar distribution of the fluoropolymer, but their presence significantly improves the mechanical properties of this type of composition and in particular the resistance to fatigue under stress. However, the perfluoroalkylvinyl ether units are much more sensitive to metal halides than the TFE or HFP units, which makes the macromolecular chain more vulnerable.
L'application principale mais non limitative de l'invention se trouve dans le domaine des câbles de transmission de données. Elle concerne, en effet, les conducteurs électriques revêtus d'au moins une couche isolante obtenue à partir de la composition selon l'invention.The main but non-limiting application of the invention lies in the field of data transmission cables. It concerns, in fact, electrical conductors coated with at least one insulating layer obtained from the composition according to the invention.
Afin de montrer les avantages obtenus avec les compositions selon l'invention, un protocole expérimental a été mis au point afin de placer la composition fluorée dans des conditions de température et de cisaillement proches de celles rencontrées dans le corps d'une extrudeuse monovis.In order to show the advantages obtained with the compositions according to the invention, an experimental protocol was developed in order to place the fluorinated composition under temperature and shear conditions close to those encountered in the body of a single-screw extruder.
La stabilité de la matière peut être évaluée de deux façons. La première consiste à suivre l'évolution de la viscosité newtonienne de la composition fluorée à différents stades de dégradation thermique : la composition présentant la chute de viscosité la plus faible en fonction de la durée de traitement est la plus stable thermiquement. La seconde analyse consiste à comparer progressivement l'évolution de la coloration blanche de la composition vers une décoloration grise, conséquence de sa dégradation thermique.The stability of the material can be evaluated in two ways. The first is to follow the evolution of the Newtonian viscosity of the fluorinated composition at different stages of thermal degradation: the composition having the lowest viscosity drop as a function of the treatment time is the most thermally stable. The second analysis consists in progressively comparing the evolution of the white color of the composition towards a gray discoloration, consequence of its thermal degradation.
Les échantillons ont été préparés en mélangeant la résine FEP, les pigments et les charges à l'aide d'une extrudeuse Bi-Vis corotative Berstorff.Samples were prepared by mixing the FEP resin, pigments and fillers with a Berstorff Corotative Bi-Vis extruder.
La charge inorganique utilisée est de l'oxyde de zinc nanométrique, dont la taille moyenne de particules est comprise entre 35 et 55nm et dont la surface spécifique est de l'ordre de 20-30 m2/g.The inorganic filler used is nanometric zinc oxide, the average particle size of which is between 35 and 55 nm and whose specific surface area is of the order of 20-30 m 2 / g.
Le Tableau 1 donne les compositions des échantillons des différents mélanges étudiés dans le cadre de l'invention.
La composition fluorée extrudée est ensuite refroidie dans un bac d'eau, puis séchée et granulée.The extruded fluorinated composition is then cooled in a tray of water, then dried and granulated.
Les granulés obtenus sont placés dans le fourreau d'un rhéomètre capillaire à 400°C. Ils sont extrudés à travers une filière (L/D=30) sous un cisaillement de 1500 s-1 après 60s, réduit ensuite à 50 s-1 après une période de 150s. Une mesure de viscosité est enregistrée toutes les 30 secondes entre 180 secondes et 900 secondes.The granules obtained are placed in the sheath of a capillary rheometer at 400 ° C. They are extruded through a die (L / D = 30) under a shear of 1500 s -1 after 60s, then reduced to 50 s -1 after a period of 150s. A viscosity measurement is recorded every 30 seconds between 180 seconds and 900 seconds.
Pour chaque échantillon analysé, l'évolution du log de la viscosité des échantillons A, B, C, D et E en fonction de la durée du vieillissement desdits échantillons permet d'évaluer leur stabilité thermique.For each sample analyzed, the evolution of the log of the viscosity of the samples A, B, C, D and E as a function of the aging time of said samples makes it possible to evaluate their thermal stability.
Cette stabilité thermique est déterminée par le calcul des pentes des courbes ainsi obtenues.This thermal stability is determined by the calculation of the slopes of the curves thus obtained.
En affectant un coefficient égal à 100 pour l'échantillon dont la vitesse de dégradation à 400°C est la plus lente (échantillon A) ou, en d'autres termes, correspondant à la stabilité thermique la plus élevée, on peut ainsi représenter les stabilités thermiques relatives à chaque échantillon par rapport à l'échantillon A de référence, comme illustré sur la
L'échantillon A a été vieilli selon la procédure décrite ci-dessus et présente la stabilité thermique la plus élevée parmi les échantillons testés dans le cadre de l'étude.Sample A was aged according to the procedure described above and has the highest thermal stability among the samples tested in the study.
L'échantillon B a été vieilli selon la procédure décrite ci-dessus. Sa stabilité thermique diminue de 4,1% par rapport à celle de l'échantillon standard A.Sample B was aged according to the procedure described above. Its thermal stability decreases by 4.1% compared to that of the standard sample A.
L'échantillon C a été préparé selon la procédure décrite ci-dessus en mélangeant le copolymère TFE/HFP/PAVE avec 15% en poids de TiO2.Sample C was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 15% by weight of TiO 2 .
L'analyse par rhéométrie capillaire de l'échantillon montre que la stabilité thermique chute de 22,6% par rapport à l'échantillon standard A.The capillary rheometry analysis of the sample shows that the thermal stability drops by 22.6% compared to the standard sample A.
L'échantillon D a été préparé selon la procédure décrite ci-dessus en mélangeant le copolymère TFE/HFP/PAVE avec 14,8% en poids de TiO2 et 0,2% en poids de ZnO nanométrique, dont la taille moyenne de particules est comprise entre 0,035 et 0,055 µm.Sample D was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 14.8% by weight of TiO 2 and 0.2% by weight of nanometric ZnO, the average particle size of which is between 0.035 and 0.055 μm.
L'analyse par rhéométrie capillaire de l'échantillon montre que la stabilité thermique chute de 19,1% par rapport à l'échantillon standard A.The capillary rheometry analysis of the sample shows that the thermal stability drops by 19.1% compared to the standard sample A.
L'échantillon E a été préparé selon la procédure décrite ci-dessus en mélangeant le copolymère TFE/HFP/PAVE avec 14% en poids de TiO2 et 1% en poids de ZnO nanométrique, dont la taille moyenne de particules est comprise entre 0,035 et 0,055 µm.Sample E was prepared according to the procedure described above by mixing the TFE / HFP / PAVE copolymer with 14% by weight of TiO 2 and 1% by weight of nanometric ZnO, the average particle size of which is between 0.035 and 0.055 μm.
L'analyse par rhéométrie capillaire de l'échantillon montre que la stabilité thermique chute de 13,7% par rapport à l'échantillon standard A.The capillary rheometry analysis of the sample shows that the thermal stability drops by 13.7% compared to the standard sample A.
Ainsi, au vu des résultats obtenus, l'ajout d'oxyde de zinc dans une composition fluorée contenant du dioxyde de titane permet d'obtenir un mélange extrudé plus stable thermiquement.Thus, in view of the results obtained, the addition of zinc oxide in a fluorinated composition containing titanium dioxide makes it possible to obtain an extruded mixture which is more thermally stable.
En effet, comme représenté sur la
La présence de 0,2% de ZnO nanométrique (échantillon D) et de 1% de ZnO nanométrique (échantillon E) permettent d'améliorer la stabilité thermique du mélange respectivement de 4,2% et de 10,3% par rapport à l'échantillon C.The presence of 0.2% of nanometric ZnO (sample D) and 1% of nanometric ZnO (sample E) makes it possible to improve the thermal stability of the mixture by 4.2% and 10.3%, respectively, compared to sample C.
Un second moyen simple et efficace, non représenté, pour évaluer la stabilité thermique de compositions fluorées extrudées, est d'observer l'évolution de la décoloration du matériau, notamment son noircissement, en fonction du temps de vieillissement thermique à 400°C.A second simple and effective means, not shown, for evaluating the thermal stability of extruded fluorinated compositions is to observe the evolution of the discoloration of the material, in particular its blackening, as a function of the thermal aging time at 400 ° C.
On observe effectivement que l'échantillon C commence à se noircir après 5 minutes dans le fourreau du rhéomètre capillaire.It is actually observed that the sample C begins to darken after 5 minutes in the sleeve of the capillary rheometer.
En comparaison, les échantillons D et E, ayant subit le même type de vieillissement thermique, commence à être décoloré seulement après 10 minutes dans le fourreau du rhéomètre capillaire.In comparison, samples D and E, having undergone the same type of thermal aging, begin to be discolored only after 10 minutes in the sleeve of the capillary rheometer.
On peut également employer d'autres charges telles que des hydrocalcites synthétiques ou des hydrocalumites.Other fillers such as synthetic hydrocalcites or hydrocalumites can also be used.
Enfin, les valeurs limites des intervalles donnés ne sont pas à considérer au sens strict et peuvent varier dans des tolérances habituelles bien connues de l'homme du métier.Finally, the limit values of the given intervals are not to be considered in the strict sense and may vary within customary tolerances well known to those skilled in the art.
Claims (5)
- An electric conductor coated with at least one insulating layer, characterized in that said layer is obtained from an extrudable, thermally stable composition, comprising:- a fluorinated polymer,- titanium dioxide, and- an inorganic filler, a so-called acid scavenger, capable of neutralizing hydrofluoric acid formed during the extrusion step of the composition, the inorganic filler being selected from nanometric zinc oxide, nanometric magnesium oxide or nanometric calcium oxide.
- The electric conductor according to claim 1, characterized in that the titanium dioxide concentration is less than 30% by weight of the composition, and preferably comprised between 5% and 15%.
- The electric conductor according to claim 1 or 2, characterized in that the inorganic filler concentration is less than 5% by weight of the composition, and preferably less than 2%.
- The electric conductor according to any of claims 1 to 3, characterized in that the fluorinated polymer is a copolymer of fluorinated ethylene-propylene (FEP).
- The electric conductor according to claim 4, characterized in that the FEP is selected from tetrafluoroethylene / hexafluoroisopropene copolymer or tetrafluoroethylene / hexafluoroisopropene / perfluoroalkylvinylether copolymer.
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FR0650112A FR2895990B1 (en) | 2006-01-12 | 2006-01-12 | THERMALLY STABLE FLUORINATED COMPOSITION |
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US (1) | US20070203281A1 (en) |
EP (1) | EP1808867B1 (en) |
KR (1) | KR20070075285A (en) |
CN (1) | CN101003654A (en) |
AT (1) | ATE505796T1 (en) |
CA (1) | CA2573187C (en) |
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WO2009019209A1 (en) | 2007-08-03 | 2009-02-12 | Solvay Solexis, Inc. | Perfluoropolymer foamable composition |
KR100937226B1 (en) * | 2008-01-14 | 2010-01-15 | 한국생산기술연구원 | Thixoextrusion method of CaO added Magnesium Alloys |
CA2712084C (en) * | 2008-01-14 | 2013-07-30 | Korea Institute Of Industrial Technology | Forming device for thixoextrusion and method thereof |
US10031301B2 (en) * | 2014-11-07 | 2018-07-24 | Cable Components Group, Llc | Compositions for compounding, extrusion, and melt processing of foamable and cellular polymers |
EP3216030B1 (en) | 2014-11-07 | 2020-05-06 | Cable Components Group, LLC | Compositions for compounding, extrusion and melt processing of foamable and cellular halogen-free polymers |
US9728298B2 (en) | 2015-06-26 | 2017-08-08 | Daikin America, Inc. | Radiation crosslinked fluoropolymer compositions containing low level of extractable fluorides |
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US5916937A (en) * | 1997-09-30 | 1999-06-29 | General Electric Company | Heat cured fluorosilicone rubber compositions having improved compression set |
US6429237B2 (en) * | 2000-04-13 | 2002-08-06 | E. I. Du Pont De Nemours & Company | Wire coating compositions |
WO2005073984A1 (en) * | 2004-01-23 | 2005-08-11 | E.I. Dupont De Nemours And Company | Filled perfluoropolymers |
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- 2006-11-07 US US11/594,000 patent/US20070203281A1/en not_active Abandoned
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DE602006021272D1 (en) | 2011-05-26 |
CA2573187C (en) | 2014-06-03 |
CN101003654A (en) | 2007-07-25 |
FR2895990A1 (en) | 2007-07-13 |
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ATE505796T1 (en) | 2011-04-15 |
KR20070075285A (en) | 2007-07-18 |
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