EP2244267A1 - Bipolymer-based composition for a cable and/or a telecommunication cable - Google Patents

Bipolymer-based composition for a cable and/or a telecommunication cable Download PDF

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Publication number
EP2244267A1
EP2244267A1 EP10167309A EP10167309A EP2244267A1 EP 2244267 A1 EP2244267 A1 EP 2244267A1 EP 10167309 A EP10167309 A EP 10167309A EP 10167309 A EP10167309 A EP 10167309A EP 2244267 A1 EP2244267 A1 EP 2244267A1
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EP
European Patent Office
Prior art keywords
energy
polylactic acid
telecommunication cable
polyester
cable according
Prior art date
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Application number
EP10167309A
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German (de)
French (fr)
Inventor
Jérôme Fournier
Sophie Barbeau
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Nexans SA
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Nexans SA
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Publication of EP2244267A1 publication Critical patent/EP2244267A1/en
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Classifications

    • 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
    • H01B3/185—Substances or derivates of cellulose
    • 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
    • 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
    • H01B3/42—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 polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
    • H01B3/422—Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to energy and / or telecommunication cables comprising at least one constituent element made of an extruded material derived from an extrudable composition.
  • Energy and / or telecommunication cables generally comprise coatings or insulating sheaths of synthetic polymers such as polyethylene, polyethylene vinyl acetate or polyvinyl chloride.
  • the document JP2004-311063 presents an energy cable comprising an extruded layer of a biodegradable polymer, in particular a polylactic resin.
  • the technical problem to be solved, by the object of the present invention is to propose an energy and / or telecommunication cable comprising at least one constituent element made of an extruded material resulting from an extrudable composition making it possible to avoid the problems of the state of the art by offering in particular alternative compositions to those of the prior art.
  • the Applicant has carried out intensive tests to find compositions making it possible to limit the significant use of polymers. synthetic while maintaining mechanical properties, insulation and fire resistance identical to or even superior to the properties of the cable sheaths of the prior art.
  • said extrudable composition comprises a biopolymer chosen from cellulose ester polymers, starch polymers complexed with a biodegradable polyester, polyhydroxyalkanoate polymers, and / or or polylactic acid polymers comprising a mixture of polylactic acid and polyester.
  • biopolymer means that the carbons of said polymer come from renewable biological sources.
  • the biopolymer can come from a direct extraction from biomass, a regeneration of the biomass by fermentation or hydrolysis, or by microbial transformation of biomonomers.
  • biopolymers are biodegradable, that is, they break down by the enzymatic action of microorganisms into carbon dioxide, methane, water and inorganic compounds.
  • Cellulose or cellulose-based polymers are generally produced by the chemical modification of natural cellulose.
  • Cotton and wood are the materials behind the industrial production of cellulose.
  • Starch polymers are thermoplastic polymers derived from the chemical, thermal and / or mechanical treatment of starch.
  • Starch is found in many plants such as maize, wheat, legumes, roots, tubers and rhizomes such as potatoes or cassava.
  • Polyhydroxyalkanoate or polyhydroxyalkanoate polymers are naturally produced by bacterial fermentation of sugars or lipids and may have thermoplastic or elastomeric properties.
  • the polylactic acid or polylactic acid polymers are aliphatic polyesters produced from corn starch.
  • said extrudable composition further comprises a synthetic polymer, preferably selected from polyethylene, polypropylene, ethyl vinyl acetate copolymer, polyvinyl chloride and polyester, or their mixture.
  • a synthetic polymer preferably selected from polyethylene, polypropylene, ethyl vinyl acetate copolymer, polyvinyl chloride and polyester, or their mixture.
  • each constituent element of said cable is selected from an insulating coating, a protective sheath and a filler.
  • a cable is schematically constituted by at least one electrical or optical conducting element extending inside at least one insulating element. .
  • At least one of the insulating elements may also act as protection means and / or that the cable may also have at least one specific protective element forming a sheath, in particular for electrical cables.
  • the cable may comprise a filling material which is essentially intended to maintain said insulated conductors and which is commonly called stuffing.
  • the cellulose ester polymers are chosen from cellulose butyrate polymer, cellulose acetate polymer and cellulose propionate polymer.
  • the polyhydroxyalkanoate polymer is a homopolymer or a copolymer of poly (3-hydroxybutyrate).
  • the polylactic acid polymers comprise at least about 10% by weight of polylactic acid, preferably at least about 40% by weight of polylactic acid, and more preferably at most about 90% by weight of polylactic acid. polylactic acid.
  • the polylactic acid polymers may comprise at least 40% by weight of polyester.
  • polylactic acid polymers comprising about 40% by weight of polylactic acid and about 60% by weight of polyester, or comprising about 10% by weight of polylactic acid and about 90% by weight of polylactic acid. polyester weight.
  • the extrudable composition further comprises a flame retardant filler.
  • the flame-retardant filler is chosen from aluminum trihydroxide Al (OH) 3 , magnesium dihydroxide Mg (OH) 2 , a mixture of hydrated magnesium carbonate and calcium and magnesium carbonate, zinc borate, and / or cork powder.
  • Table 1 details various samples according to the invention and according to the prior art, whose mechanical properties and fire resistance are studied.
  • compositions referenced from 1 to 5 correspond to a composition according to the present invention comprising a biopolymer combined or not with a synthetic polymer.
  • compositions referenced 6 and 7 are those relating to the prior art.
  • Table 1 the amounts mentioned in Table 1 are expressed in parts by weight (phr) per 100 parts of polymer.
  • Table 1 ⁇ / u> Composition constituents 1 100 pcr Cellulose 2 100 pcr Starch N F03A 2 bis 100 pcr Starch NF08 3 25 pcr Starch NF03A, and 75 pc PE 4 100 pb PHB 5 100 pcr PLA-polyester 467F 5 bis 100 pcr PLA-polyester 219F 6 100 pcr EVA 7 100 pb PE
  • the plates After cooling and demolding, the plates are cut to make the samples on which mechanical tests are performed.
  • Table 2 summarizes the results of a number of measurements from samples 1 to 7 to evaluate their tensile strength and elongation at break. ⁇ u> Table 2 ⁇ / u> Sample Tensile strength (MPa) Elongation at break (%) 1 33 26 2 11 500 2 bis 15 240 3 14 640 4 17 9 5 26 410 5 bis 13 430 6 29 767 7 16 630
  • Cone-calorimeter analyzes are also performed to evaluate and compare the fire behavior of the different samples.
  • This type of analysis consisting of burning samples in the ambient air while subjecting them to an external energy radiation of less than 100 kW / m 2 power and imposed by a radiant heating controlled in temperature, makes it possible to obtain the released heat expressed in MJ / m 2 and the peak of heat output expressed in kW / m 2 .
  • each sample is shaped into square plates 10 cm square and 3 mm thick.
  • Table 3 collects the data collected by the cone-calorimeter analyzes with the samples from Table 2. ⁇ u> Table 3 ⁇ / u> Sample Heat release rate (MJ / kg) Peak of heat released (kW / m 2 ) 1 23 910 2 21 1030 2 bis 19 756 4 23 755 5 22 860 5 bis 23 228 6 37 1360 7 43 1310
  • biopolymer-based samples according to the present invention have identical or better mechanical properties as well as fire resistance properties than the polymers of the prior art. and EVA.
  • Sample 8 is a composition comprising a biopolymer (Cellulose), a synthetic polymer (EVA) and magnesium hydroxide.
  • Samples 9 to 11 respectively correspond to samples 2, 6 and 7 added with a flame retardant filler.
  • Samples 12 to 14 correspond to sample 2, supplemented with a flame retardant filler.
  • Samples 15 to 17 correspond to the sample 5 bis supplemented with a flame retardant filler.
  • Sample 18 corresponds to sample 2 bis added with a flame retardant filler.
  • the samples in accordance with the invention have better flame-retarding properties since the heat content released from samples 8, 9 and 12 to 18 according to the invention are much lower than those of samples 10 and 11. for lower or equivalent peak heat values.
  • the sample 12 thus obtained makes it possible to obtain a tensile strength of 19 MPa and an elongation at break of 70%.
  • the mixture of these two biopolymers advantageously has well-balanced mechanical properties, whose tensile strength is greater than that of the sample 2 and the elongation at break is greater than that of the sample 1.
  • compositions 1, 2, 5 and 5 bis of Table 1 are extruded on a metal conductor of 1.03 mm diameter in a layer of approximately 0.50 mm, in order to obtain the respective electrical wires 1, 2, 5 and 5 bis.
  • the extrusion profile for the composition 1 extends from 145 ° C. to 200 ° C. under a pressure of 150 bar, that of the composition 2 extends from 100 ° C. to 135 ° C. under a pressure of 135 bar. and that of compositions 5 and 5a extends from 120 to 150 ° C under a pressure of 190 bars, these extrusion profiles being well known to those skilled in the art.
  • the insulation test according to IEC 60502-1 consists in immersing the electric wires in water for at least one hour before said test.
  • a continuous voltage of between 80V and 500V is then applied for a sufficient duration (between 1 and 5 min) then the resistance of the crown is measured. This is used to determine the insulation constant.
  • Ki values are advantageously greater than those recommended for certain materials, especially for polyvinyl chloride.
  • the extrusion of said composition makes it possible to achieve significant layer thicknesses of the order of at least 0.3-0.5 mm, unlike film-forming coatings, and thus makes it possible to obtain optimized insulating properties.
  • compositions in question are used in the production of extruded insulating and / or sheathing and / or stuffing materials for energy and / or telecommunication cables.
  • composition may furthermore comprise other additives, especially antioxidants, UV stabilizing agents, plasticizing agents, pigmentation agents or coloring agents.
  • the plasticizing agents may be added to the composition according to the present invention in order to improve the elongation at break of said composition.
  • plasticizer of castor oil, crodamide or triethyl citrate.
  • the present invention is not limited to the examples of compositions which have just been described and generally relates to all the cables that can be envisaged from the general indications given in the description of the invention.

Abstract

A power and/or telecommunications cable comprises component element(s) having material extruded from an extrudable composition. The extrudable composition includes biopolymer of cellulose ester, starch complexed with a biodegradable polyester, polyhydroxyalkanoate, and/or polylactic acid with mixture of polylactic and polyester.

Description

La présente invention se rapporte à des câbles d'énergie et/ou de télécommunication comportant au moins un élément constitutif réalisé en un matériau extrudé issu d'une composition extrudable.The present invention relates to energy and / or telecommunication cables comprising at least one constituent element made of an extruded material derived from an extrudable composition.

Les ressources naturelles minérales telles que le pétrole ou le gaz sont à l'origine de la synthèse de nombreux polymères synthétiques tels que les polyoléfines, et se font de plus en plus rares.Mineral natural resources such as oil or gas are at the origin of the synthesis of many synthetic polymers such as polyolefins, and are becoming increasingly rare.

Il est crucial de limiter l'utilisation de ces ressources naturelles afin de préserver leur existence mais aussi de s'affranchir d'une hausse des prix trop importante.It is crucial to limit the use of these natural resources in order to preserve their existence but also to avoid excessive price increases.

Les câbles d'énergie et/ou de télécommunication comprennent généralement des revêtements ou des gaines isolantes en polymères synthétiques tels qu'en polyéthylène, en polyéthylène vinyle acétate ou en polychlorure de vinyle.Energy and / or telecommunication cables generally comprise coatings or insulating sheaths of synthetic polymers such as polyethylene, polyethylene vinyl acetate or polyvinyl chloride.

Le document JP2004-311063 présente un câble d'énergie comprenant une couche extrudée d'un polymère biodégradable, notamment d'une résine polylactique.The document JP2004-311063 presents an energy cable comprising an extruded layer of a biodegradable polymer, in particular a polylactic resin.

Toutefois, il est important de pouvoir diversifier le nombre de compositions polymères extrudables limitant l'utilisation de polymère synthétique, voire n'en comprenant pas du tout, et présentant des caractéristiques thermomécaniques au moins semblables aux compositions existantes sur le marché pour l'application câble.However, it is important to be able to diversify the number of extrudable polymer compositions limiting the use of synthetic polymer, or even not including it at all, and having thermomechanical characteristics at least similar to the existing compositions on the market for the cable application. .

Aussi le problème technique à résoudre, par l'objet de la présente invention, est de proposer un câble d'énergie et/ou de télécommunication comportant au moins un élément constitutif réalisé en un matériau extrudé issu d'une composition extrudable permettant d'éviter les problèmes de l'état de la technique en offrant notamment des compositions alternatives à celles de l'art antérieur.Therefore, the technical problem to be solved, by the object of the present invention, is to propose an energy and / or telecommunication cable comprising at least one constituent element made of an extruded material resulting from an extrudable composition making it possible to avoid the problems of the state of the art by offering in particular alternative compositions to those of the prior art.

Ainsi, la demanderesse a effectué des essais intensifs pour trouver des compositions permettant de limiter l'utilisation significative de polymères synthétiques tout en gardant des propriétés mécaniques, isolantes et de résistances au feu identiques, voire supérieures aux propriétés des gaines de câbles de l'art antérieur.Thus, the Applicant has carried out intensive tests to find compositions making it possible to limit the significant use of polymers. synthetic while maintaining mechanical properties, insulation and fire resistance identical to or even superior to the properties of the cable sheaths of the prior art.

La solution du problème technique posé réside, selon la présente invention, en ce que ladite composition extrudable comprend un biopolymère choisi parmi les polymères d'ester de cellulose, les polymères d'amidon complexé avec un polyester biodégradable, les polymères de polyhydroxyalkanoate, et/ou les polymères d'acide polylactique comprenant un mélange d'acide polylactique et de polyester.The solution of the technical problem lies, according to the present invention, in that said extrudable composition comprises a biopolymer chosen from cellulose ester polymers, starch polymers complexed with a biodegradable polyester, polyhydroxyalkanoate polymers, and / or or polylactic acid polymers comprising a mixture of polylactic acid and polyester.

Le terme « biopolymère » signifie que les carbones dudit polymère proviennent de sources biologiques renouvelables.The term "biopolymer" means that the carbons of said polymer come from renewable biological sources.

A titre d'exemples, le biopolymère peut provenir d'une extraction directe à partir de la biomasse, d'une régénération de la biomasse par fermentation ou hydrolyse, ou encore par transformation microbienne de biomonomères.By way of examples, the biopolymer can come from a direct extraction from biomass, a regeneration of the biomass by fermentation or hydrolysis, or by microbial transformation of biomonomers.

La plupart des biopolymères sont biodégradables, c'est-à-dire qu'ils se décomposent par l'action enzymatique de microorganismes en dioxyde de carbone, méthane, eau et en composés inorganiques.Most biopolymers are biodegradable, that is, they break down by the enzymatic action of microorganisms into carbon dioxide, methane, water and inorganic compounds.

Les polymères de cellulose, ou à base de cellulose, sont produits généralement par la modification chimique de la cellulose naturelle.Cellulose or cellulose-based polymers are generally produced by the chemical modification of natural cellulose.

Le coton et le bois sont des matériaux à l'origine de la production industrielle de cellulose.Cotton and wood are the materials behind the industrial production of cellulose.

Les polymères d'amidon, ou à base d'amidon, sont des polymères thermoplastiques provenant du traitement chimique, thermique et/ou mécanique de l'amidon.Starch polymers, or starch-based polymers, are thermoplastic polymers derived from the chemical, thermal and / or mechanical treatment of starch.

On trouve l'amidon dans de nombreux végétaux tels que le maïs, le froment, les légumineuses, les racines, tubercules et rhizomes comme la pomme de terre ou le manioc.Starch is found in many plants such as maize, wheat, legumes, roots, tubers and rhizomes such as potatoes or cassava.

Les polymères de polyhydroxyalkanoate, ou à base de polyhydroxyalkanoate, sont produits naturellement par fermentation bactérienne de sucres ou de lipides et peuvent avoir des propriétés thermoplastiques ou élastomériques.Polyhydroxyalkanoate or polyhydroxyalkanoate polymers are naturally produced by bacterial fermentation of sugars or lipids and may have thermoplastic or elastomeric properties.

La formule générale I des polyhydroxyalkanoates est la suivante :

Figure imgb0001
dans laquelle :

  • R peut être un hydrogène ou une chaîne hydrocarbonée en C1-C16, et
  • X est un entier supérieur ou égale à 1.
The general formula I of the polyhydroxyalkanoates is as follows:
Figure imgb0001
 in which :
  • R can be a hydrogen or a C 1 -C 16 hydrocarbon chain, and
  • X is an integer greater than or equal to 1.

Les polymères d'acide polylactique, ou à base d'acide polylactique, sont des polyesters aliphatiques produits à partir d'amidon de maïs.The polylactic acid or polylactic acid polymers are aliphatic polyesters produced from corn starch.

Dans une réalisation particulière, ladite composition extrudable comprend en outre un polymère synthétique, de préférence choisi parmi le polyéthylène, le polypropylène, le copolymère d'éthyle vinyle acétate, le polychlorure de vinyle et le polyester, ou leur mélange.In a particular embodiment, said extrudable composition further comprises a synthetic polymer, preferably selected from polyethylene, polypropylene, ethyl vinyl acetate copolymer, polyvinyl chloride and polyester, or their mixture.

Selon une caractéristique de la présente invention, chaque élément constitutif dudit câble est choisi parmi un revêtement isolant, une gaine de protection et une matière de remplissage.According to a feature of the present invention, each constituent element of said cable is selected from an insulating coating, a protective sheath and a filler.

Qu'il soit électrique ou optique, destiné au transport d'énergie ou à la transmission de données, un câble est schématiquement constitué d'au moins un élément conducteur électrique ou optique s'étendant à l'intérieur d'au moins un élément isolant.Whether electrical or optical, intended for energy transmission or data transmission, a cable is schematically constituted by at least one electrical or optical conducting element extending inside at least one insulating element. .

Il est à noter qu'au moins un des éléments isolants peut également jouer le rôle de moyen de protection et/ou que le câble peut disposer en outre d'au moins un élément de protection spécifique formant une gaine, notamment pour les câbles électriques.It should be noted that at least one of the insulating elements may also act as protection means and / or that the cable may also have at least one specific protective element forming a sheath, in particular for electrical cables.

Par ailleurs, dans le cas où il intègre plusieurs conducteurs électriques isolés, le câble peut comporter une matière de remplissage qui est essentiellement destinée à maintenir lesdits conducteurs isolés et qui est communément appelée bourrage.On the other hand, in the case where it incorporates several insulated electrical conductors, the cable may comprise a filling material which is essentially intended to maintain said insulated conductors and which is commonly called stuffing.

Selon une composition préférée, les polymères d'ester de cellulose sont choisis parmi le polymère de butyrate de cellulose, le polymère d'acétate de cellulose et le polymère de propionate de cellulose.According to a preferred composition, the cellulose ester polymers are chosen from cellulose butyrate polymer, cellulose acetate polymer and cellulose propionate polymer.

Selon une autre composition préférée, le polymère de polyhydroxyalkanoate est un homopolymère ou un copolymère de poly(3-hydroxybutyrate).According to another preferred composition, the polyhydroxyalkanoate polymer is a homopolymer or a copolymer of poly (3-hydroxybutyrate).

Selon une autre composition préférée, les polymères d'acide polylactique comprennent au moins environ 10 % en poids d'acide polylactique, de préférence au moins environ 40 % en poids d'acide polylactique, et plus préférentiellement au plus environ 90 % en poids d'acide polylactique.According to another preferred composition, the polylactic acid polymers comprise at least about 10% by weight of polylactic acid, preferably at least about 40% by weight of polylactic acid, and more preferably at most about 90% by weight of polylactic acid. polylactic acid.

Avantageusement, les polymères d'acide polylactique peuvent comprendre au moins 40 % en poids de polyester.Advantageously, the polylactic acid polymers may comprise at least 40% by weight of polyester.

A titre d'exemple, on peut citer les polymères d'acide polylactique comprenant environ 40 % en poids d'acide polylactique et environ 60 % en poids de polyester, ou comprenant environ 10 % en poids d'acide polylactique et environ 90 % en poids de polyester.By way of example, mention may be made of polylactic acid polymers comprising about 40% by weight of polylactic acid and about 60% by weight of polyester, or comprising about 10% by weight of polylactic acid and about 90% by weight of polylactic acid. polyester weight.

Dans un mode de réalisation particulier, la composition extrudable comprend en outre une charge ignifugeante.In a particular embodiment, the extrudable composition further comprises a flame retardant filler.

De préférence, la charge ignifugeante est choisie parmi le trihydroxyde d'aluminium Al(OH)3, le dihydroxyde de magnésium Mg(OH)2, un mélange de carbonate de magnésium hydraté et carbonate de calcium et de magnésium, le borate de zinc, et/ou de la poudre de liège.Preferably, the flame-retardant filler is chosen from aluminum trihydroxide Al (OH) 3 , magnesium dihydroxide Mg (OH) 2 , a mixture of hydrated magnesium carbonate and calcium and magnesium carbonate, zinc borate, and / or cork powder.

D'autres caractéristiques et avantages de la présente invention apparaîtront à la lumière des exemples qui vont suivre, lesdits exemples étant donnés à titre illustratif et nullement limitatif.Other features and advantages of the present invention will emerge in the light of the examples which follow, said examples being given by way of illustration and in no way limiting.

Afin de montrer les avantages obtenus avec les compositions extrudables selon la présente invention, le Tableau 1 détaille différents échantillons selon l'invention et selon l'art antérieur, dont les propriétés mécaniques et de résistances au feu sont étudiées.In order to show the advantages obtained with the extrudable compositions according to the present invention, Table 1 details various samples according to the invention and according to the prior art, whose mechanical properties and fire resistance are studied.

Les compositions référencées de 1 à 5 correspondent à une composition selon la présente invention comprenant un biopolymère combiné ou non avec un polymère synthétique.The compositions referenced from 1 to 5 correspond to a composition according to the present invention comprising a biopolymer combined or not with a synthetic polymer.

Les compositions référencées de 6 et 7 sont celles relatives à l'art antérieur.The compositions referenced 6 and 7 are those relating to the prior art.

Il est noté que les quantités mentionnées dans le Tableau 1 sont exprimées en parties en poids (pcr) pour 100 parties de polymère. Tableau 1 Composition Constituants 1 100 pcr Cellulose 2 100 pcr Amidon N F03A 2 bis 100 pcr Amidon NF08 3 25 pcr Amidon NF03A, et 75 pcr PE 4 100 pcr PHB 5 100 pcr PLA-polyester 467F 5 bis 100 pcr PLA-polyester 219F 6 100 pcr EVA 7 100 pcr PE It is noted that the amounts mentioned in Table 1 are expressed in parts by weight (phr) per 100 parts of polymer. <u> Table 1 </ u> Composition constituents 1 100 pcr Cellulose 2 100 pcr Starch N F03A 2 bis 100 pcr Starch NF08 3 25 pcr Starch NF03A, and 75 pc PE 4 100 pb PHB 5 100 pcr PLA-polyester 467F 5 bis 100 pcr PLA-polyester 219F 6 100 pcr EVA 7 100 pb PE

L'origine des différents constituants du Tableau 1 est la suivante :

  • « Cellulose » correspond au polymère d'acétate de butyrate de cellulose, référencé Tenite 485E2R30010 et commercialisé par la société Eastman.
  • « Amidon NF03A» correspond au polymère d'amidon complexé avec un polyester biodégradable, référencé Mater-bi NF03A et commercialisé par la société Novamont.
  • « Amidon NF08 » correspond au polymère d'amidon complexé avec un polyester biodégradable, référencé Mater-bi NF08 et commercialisé par la société Novamont.
  • « PHB » correspond au polymère de polyhydroxyde butyrate, référencé P209 et commercialisé par la société Biomer.
  • « PLA-polyester 467F» correspond au polymère d'acide polylactique, référencé 467F, comprenant environ 40 % en poids d'acide polylactique et environ 60 % en poids de polyester, et commercialisé par la société FKUR.
  • « PLA-polyester 219F » correspond au polymère d'acide polylactique, référencé 219F, comprenant environ 10 % d'acide polylactique et environ 90 % de polyester, et commercialisé par la société FKUR.
  • « EVA » correspond au copolymère d'éthylène vinyle acétate (polymère synthétique), référencé EVATANE 2803 et commercialisé par la société ARKEMA.
  • « PE » correspond au polyéthylène (polymère synthétique), référencé LL4004 et commercialisé par la société Exxon.
The origin of the different constituents of Table 1 is as follows:
  • "Cellulose" corresponds to the polymer of cellulose butyrate acetate, referenced Tenite 485E2R30010 and marketed by Eastman.
  • "Starch NF03A" corresponds to the starch polymer complexed with a biodegradable polyester, referenced Mater-bi NF03A and marketed by Novamont.
  • "Starch NF08" corresponds to the starch polymer complexed with a biodegradable polyester, referenced Mater-bi NF08 and marketed by Novamont.
  • "PHB" corresponds to the polyhydroxide butyrate polymer, referenced P209 and sold by the company Biomer.
  • "PLA-polyester 467F" corresponds to the polylactic acid polymer, referenced 467F, comprising approximately 40% by weight of polylactic acid and about 60% by weight of polyester, and marketed by FKUR.
  • "PLA-polyester 219F" corresponds to the polylactic acid polymer, referenced 219F, comprising about 10% of polylactic acid and about 90% of polyester, and marketed by FKUR.
  • "EVA" corresponds to the copolymer of ethylene vinyl acetate (synthetic polymer), referenced EVATANE 2803 and sold by the company Arkema.
  • "PE" corresponds to polyethylene (synthetic polymer), referenced LL4004 and marketed by Exxon.

Pour étudier les propriétés mécaniques, des échantillons 1 à 7 correspondant respectivement aux compositions 1 à 7, ont été préparés selon le protocole suivant :

  • mettre en oeuvre le ou les polymères dans un mélangeur interne, et
  • mouler la composition en formant des plaques dans une presse chauffante, sous une pression de 100 bars pendant 5 minutes.
To study the mechanical properties, samples 1 to 7 corresponding respectively to compositions 1 to 7, were prepared according to the following protocol:
  • to use the polymer (s) in an internal mixer, and
  • molding the composition by forming plates in a heating press at a pressure of 100 bar for 5 minutes.

Après refroidissement et démoulage, les plaques sont coupées pour réaliser les échantillons sur lesquels des tests mécaniques sont effectués.After cooling and demolding, the plates are cut to make the samples on which mechanical tests are performed.

Le Tableau 2 rassemble les résultats d'un certain nombre de mesures relevées sur les échantillons 1 à 7 afin d'évaluer leur résistance à la traction et leur allongement à la rupture. Tableau 2 Echantillon Résistance à la traction (MPa) Allongement à la rupture (%) 1 33 26 2 11 500 2 bis 15 240 3 14 640 4 17 9 5 26 410 5 bis 13 430 6 29 767 7 16 630 Table 2 summarizes the results of a number of measurements from samples 1 to 7 to evaluate their tensile strength and elongation at break. <u> Table 2 </ u> Sample Tensile strength (MPa) Elongation at break (%) 1 33 26 2 11 500 2 bis 15 240 3 14 640 4 17 9 5 26 410 5 bis 13 430 6 29 767 7 16 630

Des analyses par cône-calorimétre sont également réalisées afin d'évaluer et de comparer le comportement au feu des différents échantillons.Cone-calorimeter analyzes are also performed to evaluate and compare the fire behavior of the different samples.

Ce type d'analyse, consistant à brûler des échantillons à l'air ambiant tout en les soumettant à un rayonnement énergétique externe de puissance inférieure à 100 kW/m2 et imposé par un chauffage radiant contrôlé en température, permet d'obtenir le taux de chaleur dégagée exprimé en MJ/m2 et le pic de chaleur dégagée exprimé en kW/m2.This type of analysis, consisting of burning samples in the ambient air while subjecting them to an external energy radiation of less than 100 kW / m 2 power and imposed by a radiant heating controlled in temperature, makes it possible to obtain the released heat expressed in MJ / m 2 and the peak of heat output expressed in kW / m 2 .

Pour ce faire, chaque échantillon est façonné en plaques carrées de 10 cm de côté et de 3 mm d'épaisseur.To do this, each sample is shaped into square plates 10 cm square and 3 mm thick.

Les échantillons ainsi conformés sont testés au moyen d'un calorimètre à cône conformément à la norme ISO 5660-1 relative aux débits calorifiques des produits du bâtiment.The samples thus conformed are tested using a cone calorimeter in accordance with the ISO 5660-1 standard relating to the heat flows of building products.

Plus le pic de chaleur dégagée et le taux de chaleur dégagée sont faibles numériquement, meilleures sont les propriétés ignifugeantes de la composition.The higher the peak of heat released and the rate of heat released are numerically lower, the better the flame retardant properties of the composition.

Le Tableau 3 rassemble les données collectées par les analyses en cône-calorimètre avec les échantillons du Tableau 2. Tableau 3 Echantillon Taux de chaleur dégagée (MJ/kg) Pic de chaleur dégagée (kW/m2) 1 23 910 2 21 1030 2 bis 19 756 4 23 755 5 22 860 5 bis 23 228 6 37 1360 7 43 1310 Table 3 collects the data collected by the cone-calorimeter analyzes with the samples from Table 2. <u> Table 3 </ u> Sample Heat release rate (MJ / kg) Peak of heat released (kW / m 2 ) 1 23 910 2 21 1030 2 bis 19 756 4 23 755 5 22 860 5 bis 23 228 6 37 1360 7 43 1310

Au regard des résultats des Tableaux 2 et 3, il apparaît clairement que les échantillons à base de biopolymères selon la présente invention présentent des propriétés mécaniques ainsi que des propriétés de résistance au feu identiques, voire meilleures, que les polymères de l'art antérieur PE et EVA.With regard to the results of Tables 2 and 3, it is clear that the biopolymer-based samples according to the present invention have identical or better mechanical properties as well as fire resistance properties than the polymers of the prior art. and EVA.

Pour améliorer les propriétés de résistance au feu, de nouveaux échantillons comprenant une charge ignifugeante sont détaillés dans le Tableau 4.To improve the fire resistance properties, new samples comprising a flame retardant filler are detailed in Table 4.

L'échantillon 8 est une composition comprenant un biopolymère (Cellulose), un polymère synthétique (EVA) et de l'hydroxyde de magnésium.Sample 8 is a composition comprising a biopolymer (Cellulose), a synthetic polymer (EVA) and magnesium hydroxide.

Les échantillons 9 à 11 correspondent respectivement aux échantillons 2, 6 et 7 additionnés d'une charge ignifugeante.Samples 9 to 11 respectively correspond to samples 2, 6 and 7 added with a flame retardant filler.

Les échantillons 12 à 14 correspondent à l'échantillon 2 additionné d'une charge ignifugeante.Samples 12 to 14 correspond to sample 2, supplemented with a flame retardant filler.

Les échantillons 15 à 17 correspondent à l'échantillon 5 bis additionné d'une charge ignifugeante.Samples 15 to 17 correspond to the sample 5 bis supplemented with a flame retardant filler.

L'échantillon 18 correspond à l'échantillon 2 bis additionné d'une charge ignifugeante.Sample 18 corresponds to sample 2 bis added with a flame retardant filler.

A cet égard, il est noté que les quantités mentionnées dans le Tableau 4 sont exprimées en parties en poids (pcr) pour 100 parties de polymère. Tableau 4 Echantillon Constituants Taux de chaleur dégagée (MJ/kg) Pic de chaleur dégagée (kW/m2) 8 25 pcr Cellulose, 75 pcr EVA, et 120 pcr d'hydroxyde de magnésium 25 271 9 100 pcr Amidon NF03A, et 120 pcr d'hydroxyde de magnésium 14 241 10 100 pcr EVA, et 120 pcr d'hydroxyde de magnésium 29 410 11 100 pcr PE, et 120 pcr d'hydroxyde de magnésium 30 227 12 100 pcr Amidon NF03, et 150 pcr d'hydroxyde de magnésium 13 238 13 100 pcr Amidon NF03, et 150 pcr d'hydroxyde d'aluminium 13 129 14 100 pcr Amidon NF03, et 150 pcr de mélange de carbonate de magnésium hydraté et carbonate de calcium et de magnésium 12 142 15 100 pcr de PLA-polyester 219F, et 150 pcr d'hydroxyde de magnésium 14 232 16 100 pcr de PLA-polyester 219F, et 150 pcr d'hydroxyde d'aluminium 13 101 17 100 pcr de PLA-polyester 219F, et 150 pcr de le carbonate de calcium et de magnésium hydraté 13 161 18 100 pcr d'Amidon NF08, et 40 pcr d'hydroxyde d'aluminium 17 289 In this regard, it is noted that the amounts mentioned in Table 4 are expressed in parts by weight (phr) per 100 parts of polymer. <u> Table 4 </ u> Sample constituents Heat release rate (MJ / kg) Peak of heat released (kW / m 2 ) 8 25 μl Cellulose, 75 μl EVA, and 120 μl magnesium hydroxide 25 271 9 100 pcr Starch NF03A, and 120 pcr magnesium hydroxide 14 241 10 100 pcr EVA, and 120 pcr magnesium hydroxide 29 410 11 100 phr PE, and 120 phr magnesium hydroxide 30 227 12 100 pcr starch NF03, and 150 pcr magnesium hydroxide 13 238 13 100 pcr Starch NF03, and 150 pcr aluminum hydroxide 13 129 14 100 pcr Starch NF03, and 150 pcr of mixture of hydrated magnesium carbonate and calcium carbonate and magnesium 12 142 15 100 phr of PLA-polyester 219F, and 150 phr of magnesium hydroxide 14 232 16 100 phr of PLA-polyester 219F, and 150 phr of aluminum hydroxide 13 101 17 100 phr of PLA-polyester 219F, and 150 phr of hydrated calcium and magnesium carbonate 13 161 18 100 phr of starch NF08, and 40 phr of aluminum hydroxide 17 289

L'origine des charges ignifugeantes utilisées dans les échantillons 8 à 18 est la suivante :

  • l'hydroxyde de magnésium et l'hydroxyde d'aluminium sont commercialisés par la société Martinswerk respectivement sous la référence Magnifin H10 et OL104 ; et
  • le mélange de carbonate de magnésium hydraté et carbonate de calcium et de magnésium est commercialisé par la société Minelco sous la référence Ultracarb U5.
The origin of the flame retardant fillers used in samples 8 to 18 is as follows:
  • magnesium hydroxide and aluminum hydroxide are marketed by Martinswerk respectively under the reference Magnifin H10 and OL104; and
  • the mixture of hydrated magnesium carbonate and calcium and magnesium carbonate is marketed by Minelco under the reference Ultracarb U5.

Au regard des résultats du Tableau 4, les échantillons conformes à l'invention présentent de meilleures propriétés ignifugeantes puisque le taux de chaleur dégagée des échantillons 8, 9 et 12 à 18 conforme à l'invention sont bien inférieurs à ceux des échantillons 10 et 11 pour des valeurs de pic de chaleur dégagée inférieures ou équivalentes.With regard to the results in Table 4, the samples in accordance with the invention have better flame-retarding properties since the heat content released from samples 8, 9 and 12 to 18 according to the invention are much lower than those of samples 10 and 11. for lower or equivalent peak heat values.

Afin de montrer les avantages obtenus selon une autre réalisation particulière de la présente invention et à titre d'exemple, deux biopolymères différents, à savoir 75 pcr d'Amidon et 25 pcr de Cellulose, sont mélangés et moulés sous presse dans les mêmes conditions qu'énoncées précédemment.In order to show the advantages obtained according to another particular embodiment of the present invention and by way of example, two different biopolymers, namely 75 phr of Starch and 25 phr of Cellulose, are mixed and molded in press under the same conditions as previously stated.

L'échantillon 12 ainsi obtenu permet d'obtenir une résistance à la traction de 19 MPa et un allongement à la rupture de 70 %.The sample 12 thus obtained makes it possible to obtain a tensile strength of 19 MPa and an elongation at break of 70%.

Ainsi, le mélange de ces deux biopolymères présente avantageusement des propriétés mécaniques bien équilibrées, dont la résistance à la traction est supérieure à celle de l'échantillon 2 et l'allongement à la rupture est supérieur à celui de l'échantillon 1.Thus, the mixture of these two biopolymers advantageously has well-balanced mechanical properties, whose tensile strength is greater than that of the sample 2 and the elongation at break is greater than that of the sample 1.

Enfin, pour valider l'utilisation des compositions selon la présente invention pour une application câble, les compositions 1, 2, 5 et 5 bis du Tableau 1 sont extrudées sur un conducteur métallique de 1,03 mm de diamètre en une couche d'environ 0,50 mm, afin d'obtenir les fils électriques respectifs 1, 2, 5 et 5 bis.Finally, to validate the use of the compositions according to the present invention for a cable application, the compositions 1, 2, 5 and 5 bis of Table 1 are extruded on a metal conductor of 1.03 mm diameter in a layer of approximately 0.50 mm, in order to obtain the respective electrical wires 1, 2, 5 and 5 bis.

Le profil d'extrusion pour la composition 1 s'étend de 145°C à 200°C sous une pression de 150 Bar, celui de la composition 2 s'étend de 100°C à 135°C sous une pression de 135 Bar, et celui des compositions 5 et 5 bis s'étend de 120 à 150°C sous une pression de 190 bars, ces profils d'extrusion étant bien connus de l'homme du métier.The extrusion profile for the composition 1 extends from 145 ° C. to 200 ° C. under a pressure of 150 bar, that of the composition 2 extends from 100 ° C. to 135 ° C. under a pressure of 135 bar. and that of compositions 5 and 5a extends from 120 to 150 ° C under a pressure of 190 bars, these extrusion profiles being well known to those skilled in the art.

Ces compositions extrudées sont soumises à des tests d'isolation. Le test d'isolation selon la norme IEC 60502-1 consiste à immerger les fils électriques dans de l'eau pendant au moins une heure avant ledit test.These extruded compositions are subjected to insulation tests. The insulation test according to IEC 60502-1 consists in immersing the electric wires in water for at least one hour before said test.

Une tension continue comprise entre 80V et 500V est alors appliquée pendant une durée suffisante (entre 1 et 5 min) puis la résistance de la couronne est mesurée. Celle-ci permet de déterminer la constante d'isolement.A continuous voltage of between 80V and 500V is then applied for a sufficient duration (between 1 and 5 min) then the resistance of the crown is measured. This is used to determine the insulation constant.

Les constantes d'isolement (Ki) à 20°C obtenues pour les compositions extrudées des fils électriques 1, 2, 5 et 5bis sont rassemblées dans le Tableau 5 ci-après. Tableau 5 Composition extrudée Ki à 20°C 1 850 2 5 5 2,2 5 bis 10,8 The insulation constants (Ki) at 20 ° C obtained for the extruded compositions of the electrical wires 1, 2, 5 and 5a are collated in Table 5 below. <u> Table 5 </ u> Extruded composition Ki at 20 ° C 1 850 2 5 5 2.2 5 bis 10.8

Ces valeurs de Ki sont avantageusement supérieures à celles préconisées pour certains matériaux, notamment pour le polychlorure de vinyle.These Ki values are advantageously greater than those recommended for certain materials, especially for polyvinyl chloride.

L'extrusion de ladite composition permet de réaliser des épaisseurs de couche importantes de l'ordre d'au moins 0,3-0,5 mm, contrairement aux revêtements filmogènes, et permet ainsi d'obtenir des propriétés isolantes optimisées. Plus l'épaisseur extrudée est importante, meilleure est l'isolation électrique.The extrusion of said composition makes it possible to achieve significant layer thicknesses of the order of at least 0.3-0.5 mm, unlike film-forming coatings, and thus makes it possible to obtain optimized insulating properties. The higher the extruded thickness, the better the electrical insulation.

On précise que les compositions en question sont utilisées dans la réalisation des matériaux extrudés isolants et/ou de gainage et/ou de bourrage pour les câbles d'énergie et/ou de télécommunication.It is specified that the compositions in question are used in the production of extruded insulating and / or sheathing and / or stuffing materials for energy and / or telecommunication cables.

La composition peut par ailleurs comprendre d'autres additifs, notamment des agents antioxydants, des agents stabilisants UV, des agents plastifiants, des agents de pigmentation ou des agents colorants.The composition may furthermore comprise other additives, especially antioxidants, UV stabilizing agents, plasticizing agents, pigmentation agents or coloring agents.

Avantageusement, les agents plastifiants peuvent être ajoutés à la composition conforme à la présente invention afin d'améliorer l'allongement à la rupture de ladite composition.Advantageously, the plasticizing agents may be added to the composition according to the present invention in order to improve the elongation at break of said composition.

A titre d'exemple, on peut citer comme agent plastifiant l'huile de ricin, le crodamide ou le triéthyle citrate.By way of example, mention may be made, as a plasticizer, of castor oil, crodamide or triethyl citrate.

La présente invention n'est pas limitée aux exemples de compositions qui viennent d'être décrit et porte dans sa généralité sur tous les câbles envisageables à partir des indications générales fournies dans l'exposé de l'invention.The present invention is not limited to the examples of compositions which have just been described and generally relates to all the cables that can be envisaged from the general indications given in the description of the invention.

Claims (9)

Câble d'énergie et/ou de télécommunication, comportant au moins un élément constitutif réalisé en un matériau extrudé issu d'une composition extrudable, caractérisé en ce que ladite composition extrudable comprend un biopolymère du type polymère d'acide polylactique comprenant un mélange d'acide polylactique et de polyester.Energy and / or telecommunication cable comprising at least one constituent element made of an extruded material derived from an extrudable composition, characterized in that said extrudable composition comprises a biopolymer of the polylactic acid polymer type comprising a mixture of polylactic acid and polyester. Câble d'énergie et/ou de télécommunication selon la revendication 1, caractérisé en ce que ladite composition extrudable comprend en outre un polymère synthétique.An energy and / or telecommunication cable according to claim 1, characterized in that said extrudable composition further comprises a synthetic polymer. Câble d'énergie et/ou de télécommunication selon la revendication 2, caractérisé en ce que ledit polymère synthétique est choisi parmi le polyéthylène, le polypropylène, le copolymère d'éthyle vinyle acétate, le polychlorure de vinyle et le polyester, ou leur mélange.Energy and / or telecommunication cable according to claim 2, characterized in that said synthetic polymer is chosen from polyethylene, polypropylene, ethyl vinyl acetate copolymer, polyvinyl chloride and polyester, or their mixture. Câble d'énergie et/ou de télécommunication selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ledit élément constitutif est choisi parmi un revêtement isolant, une gaine de protection et une matière de remplissage.Energy and / or telecommunication cable according to any one of claims 1 to 3, characterized in that said constituent element is selected from an insulating coating, a protective sheath and a filler. Câble d'énergie et/ou de télécommunication selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les polymères d'acide polylactique comprennent au moins environ 40 % en poids d'acide polylactique.An energy and / or telecommunication cable according to any one of claims 1 to 4, characterized in that the polylactic acid polymers comprise at least about 40% by weight of polylactic acid. Câble d'énergie et/ou de télécommunication selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les polymères d'acide polylactique comprennent environ 40 % en poids d'acide polylactique et environ 60 % en poids de polyester.An energy and / or telecommunication cable according to any one of claims 1 to 5, characterized in that the polylactic acid polymers comprise about 40% by weight of polylactic acid and about 60% by weight of polyester. Câble d'énergie et/ou de télécommunication selon l'une quelconque des revendications précédentes, caractérisé en ce que ladite composition extrudable comprend en outre une charge ignifugeante.Energy and / or telecommunication cable according to any one of the preceding claims, characterized in that said extrudable composition further comprises a flame retardant filler. Câble d'énergie et/ou de télécommunication selon la revendication 7, caractérisé en ce que la charge ignifugeante est choisie parmi le trihydroxyde d'aluminium Al(OH)3, le dihydroxyde de magnésium Mg(OH)2, un mélange de carbonate de magnésium hydraté et carbonate de calcium et de magnésium, le borate de zinc, et/ou de la poudre de liège.Energy and / or telecommunication cable according to claim 7, characterized in that the flame retardant filler is chosen from aluminum trihydroxide Al (OH) 3 , magnesium dihydroxide Mg (OH) 2 , a mixture of magnesium hydrate and calcium carbonate and magnesium, zinc borate, and / or cork powder. Câble d'énergie et/ou de télécommunication selon l'une quelconque des revendications précédentes, caractérisé en ce que la composition extrudable comprend en outre d'autres biopolymères choisis parmi les polymères d'ester de cellulose, les polymères d'amidon complexés avec un polyester biodégradable, et/ou les polymères de polyhydroxyalkanoate.Energy and / or telecommunication cable according to any one of the preceding claims, characterized in that the extrudable composition further comprises other biopolymers selected from cellulose ester polymers, starch polymers complexed with a biodegradable polyester, and / or polyhydroxyalkanoate polymers.
EP10167309A 2006-12-26 2007-12-26 Bipolymer-based composition for a cable and/or a telecommunication cable Withdrawn EP2244267A1 (en)

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