WO1998044286A1 - Conduits formes d'un tube metallique gaine - Google Patents

Conduits formes d'un tube metallique gaine

Info

Publication number
WO1998044286A1
WO1998044286A1 PCT/EP1998/001918 EP9801918W WO9844286A1 WO 1998044286 A1 WO1998044286 A1 WO 1998044286A1 EP 9801918 W EP9801918 W EP 9801918W WO 9844286 A1 WO9844286 A1 WO 9844286A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyvinyl chloride
parts
conduits according
composition
weight
Prior art date
Application number
PCT/EP1998/001918
Other languages
French (fr)
Inventor
Bernard Bourseau
Original Assignee
Solvay (Societe Anonyme)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay (Societe Anonyme) filed Critical Solvay (Societe Anonyme)
Priority to AU70429/98A priority Critical patent/AU7042998A/en
Publication of WO1998044286A1 publication Critical patent/WO1998044286A1/en

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
    • F16L58/109—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being an extruded layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
    • F16L9/147—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups comprising only layers of metal and plastics with or without reinforcement

Definitions

  • the invention relates to conduits formed of a metal tube covered with a protective layer, used for hot water or cold water circuits, in particular for sanitary installations or for water circuits of heating systems. . It is known to cover the conduits used for water circuits by means of a protective layer.
  • Polyvinyl chloride compositions have already been used for this purpose.
  • compositions based on polyvinyl chloride comprising a lead-free stabilizer have been proposed as a thermal and acoustic insulation layer for copper tubes (EP 0732533-A1).
  • This layer nevertheless has the disadvantage of not being characterized by a low density. In addition, it does not have good thermal and acoustic insulation.
  • the quantities of plastic material to be used can be significant, which is not economically viable and unnecessarily weighs down the tube.
  • the present invention relates to conduits formed by a metal tube covered with a layer of plastic material which ensures the protection of the metal tube against any external agent, which adheres well to the tube and which does not have the disadvantages above.
  • the invention relates to conduits formed by a metal tube covered with a protective layer consisting of a composition based on polyvinyl chloride comprising at least one primary heat stabilizer free of lead, according to which the composition based of polyvinyl chloride comprises at least one blowing agent.
  • metal tube is intended to denote any metal tube but also an alloy tube such as for example the different types of steel (mild steel, hard steel, stainless steel, galvanized steel, etc.).
  • the metal tube is preferably a copper tube.
  • polyvinyl chloride is intended to denote, for the purposes of the present invention, both the homopolymers of vinyl chloride and its copolymers containing monomeric units derived from one or more comonomers. These copolymers can be random, block copolymers, or copolymers grafted onto any trunk.
  • comonomers of vinyl chloride mention may be made of olefins such as ethylene, propylene and styrene, esters such as vinyl acetate and alkyl acrylates and methacrylates, derivatives vinylidene such as vinylidene chloride and fluoride.
  • compositions according to the invention are based on vinyl chloride homopolymers.
  • the method of manufacturing the polymers of vinyl chloride used can be arbitrary. It is therefore possible to use polymers of vinyl chloride obtained by mass polymerization, in the gas phase, in solution, in emulsion or in aqueous suspension.
  • the vinyl chloride polymers used for the manufacture of the compositions according to the invention are polymers prepared in aqueous suspension.
  • the blowing agent used for the purposes of the present invention, is chosen from the blowing agents usually used to generate cells in plastic materials as described in the work entitled Encyclopedia of Polymer Science and Engineering, second edition, vol. 2, 1985, p. 434-446.
  • the blowing agent is a blowing agent of the chemical type.
  • chemical type blowing agent is meant a blowing agent which produces a gas following a chemical reaction. This can be a thermal decomposition or, in some cases, a reaction between the blowing agent and another compound introduced for this purpose ("Kicker").
  • sulfonyl hydrazides such as, for example, p-toluenesulfonyl hydrazide and 4,4'-oxybis (benzenesulfonyl) hydrazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, diisopropylhydrazodicarboxylate, 5-phenyl-3,6-dihydro-l, 3,4-oxadiazin-2- one, trihydrazinotriazine, azobisisobutyronitrile, borohydride sodium and their mixtures.
  • sodium bicarbonate dinitrosopentamethylene-tetramine
  • sulfonyl hydrazides such as, for example, p-toluenesulfonyl hydrazide and 4,4'-oxybis (benzenesulfonyl) hydrazide
  • the amount of blowing agent is generally at least 0.01 part, preferably at least 0.1 part, very particularly preferably at least 0.3 part per 100 parts by weight of polychloride of vinyl.
  • the amount of blowing agent present in the composition is usually at more equal to 15 parts, preferably at most equal to 10 parts, very particularly preferably at most equal to 5 parts per 100 parts by weight of polyvinyl chloride.
  • All of the primary lead-free thermal stabilizers usually used in vinyl chloride polymer compositions are generally suitable for producing the compositions according to the invention.
  • Examples of such lead-free primary stabilizers include organotins, barium-cadmium and calcium-zinc systems.
  • calcium-zinc systems As the primary lead-free thermal stabilizer, it is preferred to use calcium-zinc systems.
  • examples of calcium-zinc systems mention may be made of the zinc and calcium salts of aliphatic monocarboxylic acids having from 6 to 30 carbon atoms such as, for example, stearic, hydroxystearic, palmitic, 2- ethylhexanoic etc. Preference is given to calcium and zinc hydroxystearate or stearate.
  • the relative proportion of calcium to zinc is generally from 1 to 5 atoms of calcium per 1 atom of zinc.
  • the doses of lead-free primary thermal stabilizers are those conventionally used for vinyl chloride polymer compositions.
  • the polyvinyl chloride composition generally comprises an amount of at least 0.1 part, preferably at least 0.3 part, very particularly preferably at least 0.5 part of primary thermal stabilizer lead-free in 100 parts of polyvinyl chloride.
  • the polyvinyl chloride composition generally comprises an amount less than or equal to 10 parts, preferably less than or equal to 5 parts, very particularly preferably less than or equal to 3 parts of a lead-free primary thermal stabilizer for 100 parts by weight of polyvinyl chloride.
  • the polyvinyl chloride composition may contain a plasticizer. All the plasticizers usually used in polyvinyl chloride compositions are generally suitable for producing the compositions according to the invention. As examples of such plasticizers, mention may be made of phthalates, adipates, azelates, sebacates, esters of straight chain alcohols, hydrocarbons, chlorinated paraffins, phosphates and their mixtures.
  • the polyvinyl chloride composition generally comprises at least 15 parts, preferably at least 30 parts of at least one plasticizer for 100 parts by weight of polyvinyl chloride. In general, the composition comprises at most 100 parts, preferably at most 70 parts of at least one plasticizer per 100 parts by weight of polyvinyl chloride.
  • composition based on polyvinyl chloride may comprise certain other ingredients usually used for the processing of polyvinyl chloride such as cost-stabilizers, agents facilitating the processing and fillers. These ingredients are present in the usual concentrations.
  • costabilizers those which are usually used in polyvinyl chloride compositions can be used.
  • the composition based on polyvinyl chloride contains a calcium-zinc system as primary thermal stabilizer, it is possible to use the usual costabilizations of such compositions.
  • hydrotalcite epoxidized derivatives such as epoxy resins, epoxidized esters such as epoxidized soybean oil and octyl epoxystearate; beta-diketones such as stearoylbenzoylmethane, dibenzoylmethane, lauroylbenzoylmethane, myristoylbenzoylmethane, palmitoylbenzoylmethane; polyols such as pentaerytritol, trimethylolpropane and their dimers, trihydroxyethylisocyanurate, pentaerythritol derivatives such as bis (alkyl) or bis (alkylphenyl) diphosphites of pentaerythrirol; partial pentaerythritol esters; alphaphenylindol; indol; ⁇ , ⁇ - ⁇ , ⁇ alkadienoic acids; metal acetylacetonate
  • the composition comprises at least 0.01 part, preferably at least 0.1 part, very particularly preferably at least 0.3 part of at least one cost-effective agent per 100 parts by weight of polyvinyl chloride.
  • the composition comprises at most 8 parts, preferably at most 5 parts, very particularly preferably at most 2 parts of at least one cost-effective agent per 100 parts by weight of polyvinyl chloride.
  • agents which facilitate processing those which are usually used for the production of polyvinyl chloride compositions can be used.
  • acrylic copolymers such as copolymers of methyl methacrylate and of ethyl acrylate.
  • the polyvinyl chloride composition comprises at most 6 parts of at least one agent facilitating the implementation per 100 parts by weight of polyvinyl chloride. Preferably, it comprises at most 5 parts, very particularly preferably at most 3 parts of at least one agent facilitating the implementation per 100 parts by weight of polyvinyl chloride.
  • the composition generally comprises at least 0.1 parts, preferably at least 0.5 parts of at least one agent which facilitates processing per 100 parts by weight of polyvinyl chloride.
  • the composition may not contain an agent which facilitates processing.
  • fillers there can be used those usually used for the production of polyvinyl chloride compositions.
  • mineral fillers such as silica; silicates such as asbestos, talc, woUastonite and mica; alkaline earth metal sulfates; fillers of the calcium carbonate type such as chalk, precipitated calcium carbonate, calcite, dolomite and limestone as well as their mixtures. The most frequently used filler is chalk.
  • the polyvinyl chloride composition comprises at most 80 parts, preferably at most 60 parts of filler per 100 parts by weight of polyvinyl chloride.
  • the polyvinyl chloride composition generally comprises at least 3 parts, preferably at least 5 parts of filler per 100 parts by weight of polyvinyl chloride.
  • the composition may not contain a filler.
  • the polyvinyl chloride composition may further comprise ingredients such as flame retardants, pigments or fungicides. These ingredients are present in the usual concentrations.
  • the protective layer is preferably deposited on the metal tube by coextrusion.
  • the invention also relates to a method for obtaining the conduits according to the invention.
  • the method according to the invention consists in depositing the protective layer on the metal tube by the coextrusion technique.
  • the invention has multiple advantages. In particular, it provides protection for metal tubes which are arranged visibly vis-à-vis external agents responsible for the appearance of corrosion such as oxygen in the air, ambient humidity or chemical agents. used nearby (cleaning products for example).
  • the plastic layer also provides protection for metal tubes that are embedded, for example in concrete screeds, which, in the absence of it, corrode quickly.
  • the thickness of the plastic layer is such that it also very effectively protects the metal tube from any type of claw.
  • the plastic layer provides efficient thermal and acoustic insulation of the metal tube, even for small quantities of plastic used.
  • the plastic layer is advantageously characterized by a low density. Another advantage of the plastic layer is its cost, which is low compared to the protective layers known from the prior art.
  • the plastic layer also has perfect adhesion to the metal tube. It also has the advantage of being respectful towards the environment.
  • the conduits formed by covering the metal tubes with the layer of plastic material according to the invention are very easy to install and arrange, even for an inexperienced person, and this without the need for sophisticated tools. . It is also very easy to replace a defective piece without having to replace a whole part of the installation. These conduits can also be painted without any difficulty. These conduits are usually used for hot water or cold water circuits in homes. In particular, they are used for sanitary installations or for the water circuits of heating systems.
  • a mixture of the components indicated in Table I is prepared at a temperature of the order of 100 ° C., the quantities being expressed in parts by weight.
  • the entire composition is then gelled in an extruder with twin corotative screws in which the temperature remains below 150 ° C.
  • the extruded rods are then granulated at the exit of the extruder and the granules cooled.
  • the protective layer on the tubes the granules obtained are coextruded on the copper tubes in a Nokia single screw extruder Grind at a temperature of 180 ° C, with a coextrusion rate of 250 to 400 kg / h.
  • the hose pulling speed is around 40 to 70 m / minute.

Abstract

The invention concerns metal, preferably copper, tubes coated with a protective film consisting of a composition based on polyvinyl chloride, stabilised with a lead free primary heat-stabiliser and comprising at least a blowing agent.

Description

Conduits formés d'un tube métallique gainé Conduits formed by a sheathed metal tube
L'invention concerne des conduits formés d'un tube métallique recouvert d'une couche de protection, utilisés pour les circuits d'eau chaude ou d'eau froide, notamment pour les installations sanitaires ou pour les circuits d'eau des systèmes de chauffage. II est connu de recouvrir les conduits utilisés pour les circuits d'eau au moyen d'une couche de protection.The invention relates to conduits formed of a metal tube covered with a protective layer, used for hot water or cold water circuits, in particular for sanitary installations or for water circuits of heating systems. . It is known to cover the conduits used for water circuits by means of a protective layer.
Des compositions à base de polychlorure de vinyle ont déjà été utilisées à cette fin.Polyvinyl chloride compositions have already been used for this purpose.
Plus récemment, pour des raisons environnementales, des compositions à base de polychlorure de vinyle comprenant un stabilisant exempt de plomb ont été proposées comme couche d'isolation thermique et acoustique pour des tubes en cuivre (EP 0732533-A1).More recently, for environmental reasons, compositions based on polyvinyl chloride comprising a lead-free stabilizer have been proposed as a thermal and acoustic insulation layer for copper tubes (EP 0732533-A1).
Cette couche présente néanmoins le désavantage de ne pas se caractériser par une densité faible. En outre, elle ne présente pas une bonne isolation thermique et acoustique. Les quantités de matière plastique à mettre en oeuvre peuvent être importantes, ce qui n'est pas économiquement viable et alourdit inutilement le tube.This layer nevertheless has the disadvantage of not being characterized by a low density. In addition, it does not have good thermal and acoustic insulation. The quantities of plastic material to be used can be significant, which is not economically viable and unnecessarily weighs down the tube.
La présente invention a pour objet des conduits formés d'un tube métallique recouvert d'une couche de matière plastique qui assure la protection du tube métallique vis-à-vis de tout agent extérieur, qui adhère bien au tube et qui ne présente pas les inconvénients ci-dessus.The present invention relates to conduits formed by a metal tube covered with a layer of plastic material which ensures the protection of the metal tube against any external agent, which adheres well to the tube and which does not have the disadvantages above.
A cet effet, l'invention concerne des conduits formés d'un tube métallique recouvert d'une couche de protection constituée d'une composition à base de polychlorure de vinyle comprenant au moins un stabilisant thermique primaire exempt de plomb selon lesquels la composition à base de polychlorure de vinyle comprend au moins un agent gonflant.To this end, the invention relates to conduits formed by a metal tube covered with a protective layer consisting of a composition based on polyvinyl chloride comprising at least one primary heat stabilizer free of lead, according to which the composition based of polyvinyl chloride comprises at least one blowing agent.
Par tube métallique, on entend désigner, aux fins de la présente invention, tout tube en métal mais également en alliage comme par exemple les différents types d'acier (acier doux, acier dur, acier inoxydable, acier galvanisé etc.). Le tube métallique est de préférence un tube en cuivre.For the purpose of the present invention, the term “metal tube” is intended to denote any metal tube but also an alloy tube such as for example the different types of steel (mild steel, hard steel, stainless steel, galvanized steel, etc.). The metal tube is preferably a copper tube.
Par polychlorure de vinyle, on entend désigner, aux fins de la présente invention, aussi bien les homopolymères du chlorure de vinyle que ses copolymères contenant des unités monomériques dérivées d'un ou de plusieurs comonomères. Ces copolymères peuvent être des copolymères statistiques, séquences, ou encore des copolymères greffés sur un tronc quelconque. A titre d'exemples de comonomères du chlorure de vinyle, on peut citer les oléfines telles que l'éthylène, le propylène et le styrène, les esters tels que l'acétate de vinyle et les acrylates et les méthacrylates d'alkyle, les dérivés vinylidéniques tels que le chlorure et de fluorure de vinylidène.The term polyvinyl chloride is intended to denote, for the purposes of the present invention, both the homopolymers of vinyl chloride and its copolymers containing monomeric units derived from one or more comonomers. These copolymers can be random, block copolymers, or copolymers grafted onto any trunk. As examples of comonomers of vinyl chloride, mention may be made of olefins such as ethylene, propylene and styrene, esters such as vinyl acetate and alkyl acrylates and methacrylates, derivatives vinylidene such as vinylidene chloride and fluoride.
De préférence, les compositions suivant l'invention sont à base d' homopolymères du chlorure de vinyle. Le mode de fabrication des polymères du chlorure de vinyle mis en oeuvre peut être quelconque. On peut donc utiliser des polymères du chlorure de vinyle obtenus par polymérisation en masse, en phase gazeuse, en solution, en émulsion ou en suspension aqueuse.Preferably, the compositions according to the invention are based on vinyl chloride homopolymers. The method of manufacturing the polymers of vinyl chloride used can be arbitrary. It is therefore possible to use polymers of vinyl chloride obtained by mass polymerization, in the gas phase, in solution, in emulsion or in aqueous suspension.
De préférence, les polymères du chlorure de vinyle utilisés pour la fabrication des compositions selon l'invention sont des polymères préparés en suspension aqueuse.Preferably, the vinyl chloride polymers used for the manufacture of the compositions according to the invention are polymers prepared in aqueous suspension.
L'agent gonflant, utilisé aux fins de la présente invention, est choisi parmi les agents gonflants habituellement utilisés pour générer des cellules dans les matières plastiques tels que décrits dans l'ouvrage intitulé Encyclopedia of Polymer Science and Engineering, second édition, vol. 2, 1985, p. 434-446. De préférence, l'agent gonflant est un agent gonflant du type chimique. Par agent gonflant du type chimique, on entend désigner un agent gonflant qui produit un gaz suite à une réaction chimique. Celle-ci peut être une décomposition thermique ou, dans certains cas, une réaction entre l'agent gonflant et un autre composé introduit à cette fin ("Kicker"). Parmi les agents gonflants du type chimique, on peut citer le bicarbonate de sodium, le dinitrosopentaméthylène- tétramine, les hydrazides de sulfonyle comme par exemple l'hydrazide de p-toluènesulfonyle et l'hydrazide de 4,4'-oxybis(benzènesulfonyle), l'azodicarbonamide, le semicarbazide de p-toluènesulfonyle, le 5-phényltétrazole, le diisopropylhydrazodicarboxylate, le 5-phényl-3,6-dihydro-l,3,4-oxadiazin-2- one , le trihydrazinotriazine, azobisisobutyronitrile, le borohydrure de sodium et leurs mélanges.The blowing agent, used for the purposes of the present invention, is chosen from the blowing agents usually used to generate cells in plastic materials as described in the work entitled Encyclopedia of Polymer Science and Engineering, second edition, vol. 2, 1985, p. 434-446. Preferably, the blowing agent is a blowing agent of the chemical type. By chemical type blowing agent is meant a blowing agent which produces a gas following a chemical reaction. This can be a thermal decomposition or, in some cases, a reaction between the blowing agent and another compound introduced for this purpose ("Kicker"). Among the chemical blowing agents, mention may be made of sodium bicarbonate, dinitrosopentamethylene-tetramine, sulfonyl hydrazides such as, for example, p-toluenesulfonyl hydrazide and 4,4'-oxybis (benzenesulfonyl) hydrazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, diisopropylhydrazodicarboxylate, 5-phenyl-3,6-dihydro-l, 3,4-oxadiazin-2- one, trihydrazinotriazine, azobisisobutyronitrile, borohydride sodium and their mixtures.
La quantité d'agent gonflant est en général d'au moins 0,01 partie, de préférence d'au moins 0,1 partie, de manière tout particulièrement préférée d'au moins 0,3 partie pour 100 parties en poids de polychlorure de vinyle. De même, la quantité d'agent gonflant présente dans la composition est habituellement au plus égale à 15 parties, de préférence au plus égale à 10 parties, de manière tout particulièrement préférée au plus égale à 5 parties pour 100 parties en poids de polychlorure de vinyle.The amount of blowing agent is generally at least 0.01 part, preferably at least 0.1 part, very particularly preferably at least 0.3 part per 100 parts by weight of polychloride of vinyl. Likewise, the amount of blowing agent present in the composition is usually at more equal to 15 parts, preferably at most equal to 10 parts, very particularly preferably at most equal to 5 parts per 100 parts by weight of polyvinyl chloride.
Tous les stabilisants thermiques primaires exempts de plomb usuellement utilisés dans les compositions de polymères du chlorure de vinyle conviennent généralement à la réalisation des compositions selon l'invention. A titre d'exemples de pareils stabilisants primaires exempts de plomb, on peut citer les organo-étains, les systèmes baryum-cadmium et calcium-zinc.All of the primary lead-free thermal stabilizers usually used in vinyl chloride polymer compositions are generally suitable for producing the compositions according to the invention. Examples of such lead-free primary stabilizers include organotins, barium-cadmium and calcium-zinc systems.
Comme stabilisant thermique primaire exempt de plomb, on préfère utiliser des systèmes calcium-zinc. A titre d'exemples de systèmes calcium-zinc, on peut citer les sels de zinc et de calcium d'acides aliphatiques monocarbo- xyliques ayant de 6 à 30 atomes de carbone tels que par exemple les acides stéarique, hydroxystéarique, palmitique, 2-éthylhexanoïque etc. On donne la préférence aux hydroxystéarate ou stéarate de calcium et de zinc. La proportion relative du calcium au zinc est généralement de 1 à 5 atomes de calcium pour 1 atome de zinc.As the primary lead-free thermal stabilizer, it is preferred to use calcium-zinc systems. As examples of calcium-zinc systems, mention may be made of the zinc and calcium salts of aliphatic monocarboxylic acids having from 6 to 30 carbon atoms such as, for example, stearic, hydroxystearic, palmitic, 2- ethylhexanoic etc. Preference is given to calcium and zinc hydroxystearate or stearate. The relative proportion of calcium to zinc is generally from 1 to 5 atoms of calcium per 1 atom of zinc.
Les doses des stabilisants thermiques primaires exempts de plomb sont celles utilisées usuellement pour les compositions de polymères du chlorure de vinyle. La composition à base de polychlorure de vinyle comprend en général une quantité d'au moins 0,1 partie, de préférence d'au moins 0,3 partie, de manière tout particulièrement préférée d'au moins 0,5 partie de stabilisant thermique primaire exempt de plomb dans 100 parties de polychlorure de vinyle. La composition à base de polychlorure de vinyle comprend en général une quantité inférieure ou égale à 10 parties, de préférence inférieure ou égale à 5 parties, de manière tout particulièrement préférée inférieure ou égale à 3 parties d'un stabilisant thermique primaire exempt de plomb pour 100 parties en poids de polychlorure de vinyle.The doses of lead-free primary thermal stabilizers are those conventionally used for vinyl chloride polymer compositions. The polyvinyl chloride composition generally comprises an amount of at least 0.1 part, preferably at least 0.3 part, very particularly preferably at least 0.5 part of primary thermal stabilizer lead-free in 100 parts of polyvinyl chloride. The polyvinyl chloride composition generally comprises an amount less than or equal to 10 parts, preferably less than or equal to 5 parts, very particularly preferably less than or equal to 3 parts of a lead-free primary thermal stabilizer for 100 parts by weight of polyvinyl chloride.
La composition à base de polychlorure de vinyle peut contenir un plastifiant. Tous les plastifiants usuellement utilisés dans les compositions de polychlorure de vinyle conviennent généralement à la réalisation des compositions selon l'invention. A titre d'exemples de pareils plastifiants, on peut citer les phtalates, les adipates, les azélates, les sébaçates, les esters d'alcools à chaînes droites, les hydrocarbures, les paraffines chlorées, les phosphates et leurs mélanges. La composition à base de polychlorure de vinyle comprend en général au moins 15 parties, de préférence au moins 30 parties d'au moins un plastifiant pour 100 parties en poids de polychlorure de vinyle. En général, la composition comprend au plus 100 parties, de préférence au plus 70 parties d'au moins un plastifiant pour 100 parties en poids de polychlorure de vinyle.The polyvinyl chloride composition may contain a plasticizer. All the plasticizers usually used in polyvinyl chloride compositions are generally suitable for producing the compositions according to the invention. As examples of such plasticizers, mention may be made of phthalates, adipates, azelates, sebacates, esters of straight chain alcohols, hydrocarbons, chlorinated paraffins, phosphates and their mixtures. The polyvinyl chloride composition generally comprises at least 15 parts, preferably at least 30 parts of at least one plasticizer for 100 parts by weight of polyvinyl chloride. In general, the composition comprises at most 100 parts, preferably at most 70 parts of at least one plasticizer per 100 parts by weight of polyvinyl chloride.
Outre les additifs définis précédemment, la composition à base de polychlorure de vinyle peut comprendre certains autres ingrédients usuellement utilisés pour la mise en oeuvre du polychlorure de vinyle tels que des costabi- lisants, des agents facilitant la mise en oeuvre et des charges. Ces ingrédients sont présents dans les concentrations usuelles.In addition to the additives defined above, the composition based on polyvinyl chloride may comprise certain other ingredients usually used for the processing of polyvinyl chloride such as cost-stabilizers, agents facilitating the processing and fillers. These ingredients are present in the usual concentrations.
Comme costabilisants, on peut mettre en oeuvre ceux qui sont habituel- lement utilisés dans les compositions de polychlorure de vinyle. Ainsi lorsque la composition à base de polychlorure de vinyle contient un système calcium-zinc comme stabilisant thermique primaire, on peut mettre en oeuvre les costabilisatns habituels de telles compositions. A titre d'exemples, on peut citer l'hydrotalcite, les dérivés époxydés tels que les résines époxyde, les esters époxydés comme l'huile de soja époxydée et l'époxystéarate d'octyle; les béta-dicétones telles que le stéaroylbenzoylméthane, le dibenzoylméthane, le lauroylbenzoylméthane, le myristoylbenzoylméthane, le palmitoylbenzoylméthane; les polyols tels que le pentaérytritol, le triméthylolpropane et leurs dimères, le trihydroxyéthylisocya- nurate, les dérivés du pentaérythritol tels que les diphosphites de bis(alkyl) ou de bis(alkylphényl) de pentaérythrirol; les esters partiels de pentaérythritol; l'alphaphénylindol; l'indol; les acides α,β-γ,δ alkadiénoïques; les dérivés du type acétylacétonate métalliques; les dérivés alkylés et carboxylés de la 1,4-dihydro- pyridine et leurs mélanges.As costabilizers, those which are usually used in polyvinyl chloride compositions can be used. Thus, when the composition based on polyvinyl chloride contains a calcium-zinc system as primary thermal stabilizer, it is possible to use the usual costabilizations of such compositions. By way of examples, mention may be made of hydrotalcite, epoxidized derivatives such as epoxy resins, epoxidized esters such as epoxidized soybean oil and octyl epoxystearate; beta-diketones such as stearoylbenzoylmethane, dibenzoylmethane, lauroylbenzoylmethane, myristoylbenzoylmethane, palmitoylbenzoylmethane; polyols such as pentaerytritol, trimethylolpropane and their dimers, trihydroxyethylisocyanurate, pentaerythritol derivatives such as bis (alkyl) or bis (alkylphenyl) diphosphites of pentaerythrirol; partial pentaerythritol esters; alphaphenylindol; indol; α, β-γ, δ alkadienoic acids; metal acetylacetonate derivatives; alkylated and carboxylated derivatives of 1,4-dihydropyridine and mixtures thereof.
En général, la composition comprend au moins 0,01 partie, de préférence au moins 0, 1 partie, de manière tout particulièrement préférée au moins 0,3 partie d'au moins un costabilisant pour 100 parties en poids de polychlorure de vinyle. En général, la composition comprend au plus 8 parties, de préférence au plus 5 parties, de manière tout particulièrement préférée au plus 2 parties d'au moins un costabilisant pour 100 parties en poids de polychlorure de vinyle. Comme agents facilitant la mise en oeuvre, on peut mettre en oeuvre ceux qui sont habituellement utilisés pour la réalisation de compositions de polychlorure de vinyle. A titre d'exemple, on peut citer les copolymères acryliques tels les copolymères de méthacrylate de méthyle et d'acrylate d'éthyle.In general, the composition comprises at least 0.01 part, preferably at least 0.1 part, very particularly preferably at least 0.3 part of at least one cost-effective agent per 100 parts by weight of polyvinyl chloride. In general, the composition comprises at most 8 parts, preferably at most 5 parts, very particularly preferably at most 2 parts of at least one cost-effective agent per 100 parts by weight of polyvinyl chloride. As agents which facilitate processing, those which are usually used for the production of polyvinyl chloride compositions can be used. By way of example, mention may be made of acrylic copolymers such as copolymers of methyl methacrylate and of ethyl acrylate.
En général, la composition de polychlorure de vinyle comprend au plus 6 parties d'au moins un agent facilitant la mise en oeuvre pour 100 parties en poids de polychlorure de vinyle. De préférence, elle comprend au plus 5 parties, de manière tout particulièrement préférée au plus 3 parties d'au moins un agent facilitant la mise en oeuvre pour 100 parties en poids de polychlorure de vinyle. La composition comprend en général au moins 0, 1 partie, de préférence au moins 0,5 partie d'au moins un agent facilitant la mise en oeuvre pour 100 parties en poids de polychlorure de vinyle. La composition peut ne pas contenir d'agent facilitant la mise en oeuvre.In general, the polyvinyl chloride composition comprises at most 6 parts of at least one agent facilitating the implementation per 100 parts by weight of polyvinyl chloride. Preferably, it comprises at most 5 parts, very particularly preferably at most 3 parts of at least one agent facilitating the implementation per 100 parts by weight of polyvinyl chloride. The composition generally comprises at least 0.1 parts, preferably at least 0.5 parts of at least one agent which facilitates processing per 100 parts by weight of polyvinyl chloride. The composition may not contain an agent which facilitates processing.
Comme charges, on peut mettre en oeuvre celles habituellement utilisées pour la réalisation de compositions de polychlorure de vinyle. A titre d'exemples, on peut citer les charges minérales telles la silice; les silicates comme l'asbeste, le talc, la woUastonite et le mica; les sulfates de métaux alcalino-terreux; les charges de type carbonate de calcium comme la craie, le carbonate de calcium précipité, la calcite, la dolomite et le calcaire ainsi que leurs mélanges. La charge la plus fréquemment utilisée est la craie.As fillers, there can be used those usually used for the production of polyvinyl chloride compositions. By way of examples, mention may be made of mineral fillers such as silica; silicates such as asbestos, talc, woUastonite and mica; alkaline earth metal sulfates; fillers of the calcium carbonate type such as chalk, precipitated calcium carbonate, calcite, dolomite and limestone as well as their mixtures. The most frequently used filler is chalk.
En général, la composition de polychlorure de vinyle comprend au plus 80 parties, de préférence au plus 60 parties de charge pour 100 parties en poids de polychlorure de vinyle. La composition de polychlorure de vinyle comprend en général au moins 3 parties, de préférence au moins 5 parties de charge pour 100 parties en poids de polychlorure de vinyle. La composition peut ne pas contenir de charge. La composition à base de polychlorure de vinyle peut en outre comprendre des ingrédients tels des retardateurs de flamme, des pigments ou des fongicides. Ces ingrédients sont présents dans les concentrations usuelles.In general, the polyvinyl chloride composition comprises at most 80 parts, preferably at most 60 parts of filler per 100 parts by weight of polyvinyl chloride. The polyvinyl chloride composition generally comprises at least 3 parts, preferably at least 5 parts of filler per 100 parts by weight of polyvinyl chloride. The composition may not contain a filler. The polyvinyl chloride composition may further comprise ingredients such as flame retardants, pigments or fungicides. These ingredients are present in the usual concentrations.
La couche de protection est de préférence déposée sur le tube métallique par coextrusion. L'invention concerne également un procédé pour l'obtention des conduits selon l'invention. Le procédé selon l'invention consiste à déposer la couche de protection sur le tube métallique par la technique de coextrusion.The protective layer is preferably deposited on the metal tube by coextrusion. The invention also relates to a method for obtaining the conduits according to the invention. The method according to the invention consists in depositing the protective layer on the metal tube by the coextrusion technique.
L'invention présente de multiples avantages. En particulier, elle assure la protection des tubes métalliques qui sont disposés de manière apparente vis-à-vis d'agents extérieurs responsables de l'apparition de corrosion tels que l'oxygène de l'air, l'humidité ambiante ou les agents chimiques utilisés à proximité (produits d'entretien par exemple). La couche de matière plastique assure également la protection des tubes métalliques se trouvant noyés, par exemple dans les chapes en béton, qui, en l'absence de celle-ci, se corrodent rapidement. L'épaisseur de la couche de matière plastique est telle qu'elle protège par ailleurs très efficacement le tube métallique de tout type de griffes. De manière inattendue, la couche de matière plastique assure de manière performante l'isolation thermique et l'isolation acoustique du tube métallique et cela même pour des quantités de matière plastique mises en oeuvre peu élevées. La couche de matière plastique se caractérise avantageusement par une densité faible. Un autre avantage de la couche de matière plastique est son coût qui est peu élevé par rapport aux couches de protection connues de l'art antérieur. La couche de matière plastique présente également une adhérence parfaite au tube métallique. Elle présente de plus l'avantage d'être respectueuse vis-à-vis de l'environnement. Les conduits formés en recouvrant les tubes métalliques de la couche de matière plastique selon l'invention sont très faciles à installer et à agencer, même pour une personne non-expérimentée, et cela sans qu'il soit nécessaire de disposer d'un outillage sophistiqué. Il est par ailleurs très facile d'en remplacer un morceau défectueux sans pour cela devoir remplacer toute une partie de l'installation. Ces conduits peuvent par ailleurs être peints sans aucune difficulté. Ces conduits sont habituellement utilisés pour les circuits d'eau chaude ou d'eau froide dans les habitations. En particulier, ils sont utilisés pour les installations sanitaires ou pour les circuits d'eau des systèmes de chauffage.The invention has multiple advantages. In particular, it provides protection for metal tubes which are arranged visibly vis-à-vis external agents responsible for the appearance of corrosion such as oxygen in the air, ambient humidity or chemical agents. used nearby (cleaning products for example). The plastic layer also provides protection for metal tubes that are embedded, for example in concrete screeds, which, in the absence of it, corrode quickly. The thickness of the plastic layer is such that it also very effectively protects the metal tube from any type of claw. Unexpectedly, the plastic layer provides efficient thermal and acoustic insulation of the metal tube, even for small quantities of plastic used. The plastic layer is advantageously characterized by a low density. Another advantage of the plastic layer is its cost, which is low compared to the protective layers known from the prior art. The plastic layer also has perfect adhesion to the metal tube. It also has the advantage of being respectful towards the environment. The conduits formed by covering the metal tubes with the layer of plastic material according to the invention are very easy to install and arrange, even for an inexperienced person, and this without the need for sophisticated tools. . It is also very easy to replace a defective piece without having to replace a whole part of the installation. These conduits can also be painted without any difficulty. These conduits are usually used for hot water or cold water circuits in homes. In particular, they are used for sanitary installations or for the water circuits of heating systems.
Les exemples qui suivent sont destinés à illustrer la présente invention sans toutefois en limiter la portée. Dans l'exemple comparatif 1, la composition à base de polychlorure de vinyle ne comprend pas d'agent gonflant. Les exemples 2 et 3 sont réalisés selon l'invention. Exemples 1 à 3The examples which follow are intended to illustrate the present invention without however limiting its scope. In Comparative Example 1, the composition based on polyvinyl chloride does not comprise a swelling agent. Examples 2 and 3 are carried out according to the invention. Examples 1 to 3
Les exemples qui suivent ont été réalisés en utilisant comme polymère, un polychlorure de vinyle obtenu par polymérisation en suspension aqueuse et caractérisé par un indice de viscosité de 128 mesuré dans la cyclohexanone à 25 °C selon la norme ISO R 174-1961(E), soit un nombre K de 71 selon la norme DIN 53726.The examples which follow were carried out using, as polymer, a polyvinyl chloride obtained by polymerization in aqueous suspension and characterized by a viscosity index of 128 measured in cyclohexanone at 25 ° C according to standard ISO R 174-1961 (E) , i.e. a number K of 71 according to DIN 53726.
Dans un mélangeur rapide, on prépare, à une température de l'ordre de 100 °C, un mélange des composants indiqués au tableau I, les quantités étant exprimées en parties en poids. L'ensemble de la composition est ensuite gélifié dans une extrudeuse à double vis corotatives dans laquelle la température reste inférieure à 150 °C. Les joncs extrudés sont ensuite granulés à la sortie de l' extrudeuse et les granulés refroidis. Pour déposer la couche de protection sur les tubes, les granulés obtenus sont coextrudés sur les tubes en cuivre dans une extrudeuse monovis Nokia Maillefer à une température de 180 °C, avec un débit de coextrusion de 250 à 400 kg/h. La vitesse de tirage du tuyau est de l'ordre de 40 à 70 m/minute.In a rapid mixer, a mixture of the components indicated in Table I is prepared at a temperature of the order of 100 ° C., the quantities being expressed in parts by weight. The entire composition is then gelled in an extruder with twin corotative screws in which the temperature remains below 150 ° C. The extruded rods are then granulated at the exit of the extruder and the granules cooled. To deposit the protective layer on the tubes, the granules obtained are coextruded on the copper tubes in a Nokia single screw extruder Grind at a temperature of 180 ° C, with a coextrusion rate of 250 to 400 kg / h. The hose pulling speed is around 40 to 70 m / minute.
La densité, mesurée à 23 °C selon la norme ISO 1183 A, de la couche de protection préparée selon la procédure décrite ci-dessus mais en l'absence d'un tube en cuivre, est donnée au tableau I.The density, measured at 23 ° C according to ISO 1183 A, of the protective layer prepared according to the procedure described above but in the absence of a copper tube, is given in Table I.
Tableau ITable I
Figure imgf000009_0001
Figure imgf000009_0001
Comme le montre le tableau I, l'ajout d'un agent gonflant à une composition à base de polychlorure de vinyle stabilisée par un composé organique contenant du calcium et du zinc, provoque une diminution de la densité. Par ailleurs, on observe une amélioration de l'isolation thermique et acoustique des tubes métalliques lorsque la composition à base de polychlorure de vinyle, utilisée pour les protéger, comprend un agent gonflant. As shown in Table I, the addition of a blowing agent to a composition based on polyvinyl chloride stabilized by an organic compound containing calcium and zinc, causes a decrease in density. Furthermore, an improvement in the thermal and acoustic insulation of the metal tubes is observed when the composition based on polyvinyl chloride, used to protect them, comprises a swelling agent.

Claims

R E V E N D I C A T I O N S R E V E N D I C A T I O N S
1 - Conduits formés d'un tube métallique recouvert d'une couche de protection constituée d'une composition à base de polychlorure de vinyle comprenant un stabilisant thermique primaire exempt de plomb, caractérisé en ce que la composition à base de polychlorure de vinyle comprend au moins un agent gonflant.1 - Ducts formed of a metal tube covered with a protective layer consisting of a composition based on polyvinyl chloride comprising a lead-free primary thermal stabilizer, characterized in that the composition based on polyvinyl chloride comprises at least minus a blowing agent.
2 - Conduits selon la revendication 1, caractérisés en ce que le tube métallique est un tube en cuivre.2 - Conduits according to claim 1, characterized in that the metal tube is a copper tube.
3 - Conduits selon l'une quelconque des revendications 1 à 2, caractérisés en ce que l'agent gonflant est choisi parmi les agents gonflants du type chimique et leurs mélanges.3 - Conduits according to any one of claims 1 to 2, characterized in that the blowing agent is chosen from blowing agents of the chemical type and their mixtures.
4 - Conduits selon l'une quelconque des revendications 1 à 3, caractérisés en ce que la quantité d'agent gonflant dans la composition est de 0,01 partie à4 - Conduits according to any one of claims 1 to 3, characterized in that the amount of swelling agent in the composition is 0.01 part to
15 parties pour 100 parties en poids de polychlorure de vinyle.15 parts per 100 parts by weight of polyvinyl chloride.
5 - Conduits selon l'une quelconque des revendications 1 à 4, caractérisés en ce que la composition à base de polychlorure de vinyle comprend de 0, 1 partie à 10 parties d'un stabilisant thermique primaire exempt de plomb pour 100 parties en poids de polychlorure de vinyle.5 - Conduits according to any one of claims 1 to 4, characterized in that the polyvinyl chloride-based composition comprises from 0.1 part to 10 parts of a lead-free primary thermal stabilizer per 100 parts by weight of polyvinyl chloride.
6 - Conduits selon l'une quelconque des revendications 1 à 5, caractérisés en ce que la composition à base de polychlorure de vinyle comprend également un plastifiant.6 - Conduits according to any one of claims 1 to 5, characterized in that the composition based on polyvinyl chloride also comprises a plasticizer.
7 - Conduits selon l'une quelconque des revendications 1 à 6, caractérisés en ce que la composition à base de polychlorure de vinyle comprend de 0,01 à7 - Conduits according to any one of claims 1 to 6, characterized in that the composition based on polyvinyl chloride comprises from 0.01 to
8 parties d'au moins un costabilisant pour 100 parties en poids de polychlorure de vinyle.8 parts of at least one cost-effective agent per 100 parts by weight of polyvinyl chloride.
8 - Conduits selon l'une quelconque des revendications 1 à 7, caractérisés en ce que la composition à base de polychlorure de vinyle comprend au plus8 - Conduits according to any one of claims 1 to 7, characterized in that the composition based on polyvinyl chloride comprises at most
6 parties d'au moins un agent facilitant la mise en oeuvre pour 100 parties en poids de polychlorure de vinyle.6 parts of at least one agent facilitating the implementation per 100 parts by weight of polyvinyl chloride.
9 - Conduits selon l'une quelconque des revendications 1 à 8, caractérisés en ce que la composition à base de polychlorure de vinyle comprend au plus 80 parties de charge pour 100 parties en poids de polychlorure de vinyle.9 - Conduits according to any one of claims 1 to 8, characterized in that the polyvinyl chloride composition comprises at most 80 parts of filler per 100 parts by weight of polyvinyl chloride.
10 - Procédé pour l'obtention de conduits selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on dépose la couche de protection sur le tube métallique par coextrusion. 10 - Process for obtaining conduits according to any one of claims 1 to 9, characterized in that the protective layer is deposited on the metal tube by coextrusion.
PCT/EP1998/001918 1997-03-28 1998-03-25 Conduits formes d'un tube metallique gaine WO1998044286A1 (en)

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BE9700290A BE1011075A3 (en) 1997-03-28 1997-03-28 Forms duct metal jacket tube.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1036975A1 (en) * 1999-03-18 2000-09-20 Boliden Cuivre & Zinc S.A. Copper pipe sheathed with a stabilised resin

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1078560A (en) * 1965-04-14 1967-08-09 Ct De Rech S De Pont A Mousson Improvements in and relating to improved method and apparatus for covering tubular metal bodies
FR2400160A1 (en) * 1977-08-10 1979-03-09 Kabel Metallwerke Ghh COPPER TUBE EQUIPPED WITH A SYNTHETIC SHEATH
FR2432670A1 (en) * 1978-08-03 1980-02-29 Amengual Rotger PROCESS FOR PRODUCING INTERNALLY REINFORCED TUBES
US4345363A (en) * 1978-09-08 1982-08-24 Kabel Und Metallwerke Gutehoffnungshutte Ag Method of continuously making flexible, heat insulated metal tubing
EP0732533A1 (en) * 1995-03-16 1996-09-18 KM Europa Metal Aktiengesellschaft Conduit having a thermally and/or acoustically insulating sleeve

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1078560A (en) * 1965-04-14 1967-08-09 Ct De Rech S De Pont A Mousson Improvements in and relating to improved method and apparatus for covering tubular metal bodies
FR2400160A1 (en) * 1977-08-10 1979-03-09 Kabel Metallwerke Ghh COPPER TUBE EQUIPPED WITH A SYNTHETIC SHEATH
FR2432670A1 (en) * 1978-08-03 1980-02-29 Amengual Rotger PROCESS FOR PRODUCING INTERNALLY REINFORCED TUBES
US4345363A (en) * 1978-09-08 1982-08-24 Kabel Und Metallwerke Gutehoffnungshutte Ag Method of continuously making flexible, heat insulated metal tubing
EP0732533A1 (en) * 1995-03-16 1996-09-18 KM Europa Metal Aktiengesellschaft Conduit having a thermally and/or acoustically insulating sleeve

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1036975A1 (en) * 1999-03-18 2000-09-20 Boliden Cuivre & Zinc S.A. Copper pipe sheathed with a stabilised resin

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