EP0197975A1 - Method for proofing a surface comprised of a polymer, its application to the fabrication of objects made of polymer, and apparatus for implementing such method - Google Patents

Method for proofing a surface comprised of a polymer, its application to the fabrication of objects made of polymer, and apparatus for implementing such method

Info

Publication number
EP0197975A1
EP0197975A1 EP19850904829 EP85904829A EP0197975A1 EP 0197975 A1 EP0197975 A1 EP 0197975A1 EP 19850904829 EP19850904829 EP 19850904829 EP 85904829 A EP85904829 A EP 85904829A EP 0197975 A1 EP0197975 A1 EP 0197975A1
Authority
EP
European Patent Office
Prior art keywords
polymer
burner
fluorinated compound
waterproofed
implementing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19850904829
Other languages
German (de)
French (fr)
Inventor
Alain De La Rocheterie
Marie-Hélène LEGAY
Pascal Bouard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0197975A1 publication Critical patent/EP0197975A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/08—Conditioning or physical treatment of the material to be shaped by using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/08—Surface shaping of articles, e.g. embossing; Apparatus therefor by flame treatment ; using hot gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/08—Surface shaping of articles, e.g. embossing; Apparatus therefor by flame treatment ; using hot gases
    • B29C59/085—Surface shaping of articles, e.g. embossing; Apparatus therefor by flame treatment ; using hot gases of profiled articles, e.g. hollow or tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0068—Permeability to liquids; Adsorption
    • B29K2995/0069—Permeability to liquids; Adsorption non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7172—Fuel tanks, jerry cans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • the present invention relates to a method for waterproofing a surface made of a polymer.
  • waterproofing means the increase in barrier properties with respect to one or more fluids.
  • the invention applies in particular to the manufacture of polyethylene tanks intended to contain a hydrocarbon.
  • the object of the invention is to provide a simple and economical waterproofing process which is harmless and which can be integrated into a production line at a high rate.
  • the subject of the invention is a process for waterproofing a surface made up of a polymer, characterized in that a gaseous fluorinated compound stable at room temperature is brought to decomposition temperature, then sends it to said surface.
  • said compound is carbon tetrafluoride or sulfur hexafluoride, and its temperature is raised by means of an oxy-propane flame.
  • the invention also proposes a method of manufacturing an object from a polymer in which, after having molded the object, its external surface is waterproofed by means of a method as defined above. .
  • the surface of the polymer granules can also be waterproofed, by means of said method, then molding of the object from the granules thus treated.
  • the external surface of the parison is waterproofed by means of said method, during its path from the extruder to the blow mold.
  • the invention also relates to an apparatus for implementing the last two variants defined above.
  • this device is characterized in that it comprises a movable grid, means for depositing on this grid said granules, and at least one burner disposed above and / or below the grid, this burner being provided with means for supplying fuel, oxidizer and said fluorinated compound.
  • the apparatus is characterized in that it comprises an annular burner disposed between the extruder and the blowing mold, this burner being provided with means for supplying fuel, by combustion and by said fluorinated compound.
  • the wall 1 of an enclosure 2 for treating automobile tanks 3 made of polyethylene has been shown schematically in FIG. 1.
  • the enclosure 2 is disposed at least one burner-mixer 4 provided with three supply lines: a supply line 5 for supplying gas, for example oxygen, a supply line 6 for supplying combustible gas, for example in propane, and a line 7 for supplying a gaseous fluorinated compound stable at room temperature, for example carbon tetrafluoride (CF 4 ) or sulfur hexafluoride (SF 6 ).
  • CF 4 carbon tetrafluoride
  • SF 6 sulfur hexafluoride
  • the enclosure 2 also includes suitable means (not shown) for scrolling the entire external surface of the tank 3 opposite the burner-mixer 4.
  • suitable means for scrolling the entire external surface of the tank 3 opposite the burner-mixer 4.
  • these means can animate it by a helical movement with an axis parallel to the gas outlet surface 8 of the burner-mixer.
  • the mixture of three gases produced in the burner-mixer forms at the outlet of the latter a set of flames 9 containing the gaseous fluorinated compound.
  • the flame temperature is preferably chosen so as to ensure an almost total decomposition of this compound; for example, the oxy-propane flame has a temperature of the order of 3000 K, which causes the total deccn ⁇ position of CF 4 and SF 6 .
  • the gas mixture can be produced at least partially at the outlet of the burner; through example, with an oxyhydric flame (oxygen-hydrogen), the fluorinated compound would only be mixed with the oxygen in the burner.
  • oxyhydric flame oxygen-hydrogen
  • the decamping products of the fluorinated compound then reach the surface of the reservoir 3 and form therein a surface layer 10 impermeable in particular to hydrocarbon vapors. It is believed that this result is mainly due to the fluorination effect resulting from the presence of free fluorine atoms in the flame, and also, in the case where SF 6 is used , to a sulfonation effect, the SF 6 generating in the flame SO 2 and SO 3 species favorable to waterproofing. It should be noted that due to the presence of hydrogen in propane and in the humidity of the air, the decenoposition of CF 4 like that of SF 6 causes the appearance in flames of hydrogen fluoride (HF ), especially as the temperature of the flame is lower.
  • HF hydrogen fluoride
  • the wall 1 of the working enclosure must therefore be made of a material compatible with this body, for example polypropylene.
  • the effluent gases are sucked in by a hood 11 with which the wall 1 of the enclosure is equipped, then treated appropriately before being discharged into the atmosphere.
  • the entire apparatus can be easily automated and integrated into a production line for tanks (or other objects made of a polymer) at high speed.
  • the granules intended to be split and then molded are treated in a similar manner, for example by extrusion blow molding, to constitute objects such as tanks.
  • the device comprises an endless grid 12 embracing two pulleys 13, one of which is driving.
  • a burner 4 such as that of FIG. 1 is disposed between the two strands of the grid 12, face 8 upwards, and another burner 4 is disposed above the upper strand of the grid, face 8 downwards.
  • Each burner extends over the entire width of the grate, and the two burners are offset in the longitudinal direction of the latter.
  • the polymer granules 14 are delivered by a hopper 15 to the upstream end of the upper strand of the grid, preferably on a single thickness.
  • the surface of each grain is waterproofed as before with the passage of the burners, and the treated grains are poured at the other end of the grid into a tank 16. The molding of objects from such grains makes it possible to obtain waterproofed objects in their mass.
  • the polymer material leaves a extruder 17 at a relatively high temperature in the form of a tubular parison 18 and penetrates between the two halves 19 , 20 of an open blow mold. Then the mold closes, pinching the parison, and a blowing head (not shown) injects a gas into the parison to achieve shaping.
  • an annular burner 4A provided with the power supplies 5, 6, 7 that the burner 4 of Figures 1 and 2, is arranged coaxially between the extruder and the mold.
  • the external surface of the parison is waterproofed by the flames 9 during its path from the extruder to the mold, and we obtain again, after blowing, tanks waterproofed in their mass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

Suivant ce procédé, on porte à une température de décomposition un composé fluoré gazeux stable à la température ambiante, puis on l'envoie sur la surface à imperméabiliser. L'invention s'applique notamment à la fabrication de réservoirs (3) en polyéthylène destinés à contenir un hydrocarbure, tels que les réservoirs pour véhicules automobiles.According to this process, a gaseous fluorinated compound is brought to a decomposition temperature stable at room temperature, then it is sent to the surface to be waterproofed. The invention is particularly applicable to the manufacture of polyethylene tanks (3) intended to contain a hydrocarbon, such as tanks for motor vehicles.

Description

" PROCEDE D'IMPERMEABILISATION D'UNE SURFACE CONSTITUEE D'UN POLYMERE,SON APPLICATION A LA FABRICATION D'OBJETS EN POLYMERE, ET APPAREIL DE MISE EN OEUVRE ""PROCESS FOR WATERPROOFING A SURFACE CONSISTING OF A POLYMER, ITS APPLICATION TO THE MANUFACTURE OF POLYMER OBJECTS, AND APPARATUS FOR IMPLEMENTING IT"
La présente invention est relative à un procédé d'imperméabilisation d'une surface constituée d'un polymère. Dans le présent mémoire, en entend par le terme "imperméabilisation" l'augmentation des propriétés de barrière vis-à-vis d'un ou de plusieurs fluides. L'invention s'applique en particulier à la fabrication de réservoirs en polyéthylène destinés à contenir un hydrocarbure.The present invention relates to a method for waterproofing a surface made of a polymer. In the present specification, the term "waterproofing" means the increase in barrier properties with respect to one or more fluids. The invention applies in particular to the manufacture of polyethylene tanks intended to contain a hydrocarbon.
On sait que les polymères usuels (polyéthylène, polypropylène) sont perméables à différents gaz, et en particulier aux vapeurs d'essence. Ceci freine actuellement le développement des réservoirs d'automobile en polyethylene, matériau qui offre pourtant des avantages du point de vue de la résistance aux chocs et au feu.It is known that the usual polymers (polyethylene, polypropylene) are permeable to various gases, and in particular to gasoline vapors. This is currently hampering the development of automobile tanks made of polyethylene, a material which nevertheless offers advantages from the point of view of impact and fire resistance.
Divers procédés ont été proposés pour imperméabiliser les polymères. Cependant, du fait soit de la longueur ou de la complexité de leur mise en oeuvre, soit de leur danger ou de leur coût élevé, aucun n'a donné entière satisfaction.Various methods have been proposed for waterproofing polymers. However, either because of the length or complexity of their implementation, or their danger or high cost, none has been entirely satisfactory.
L'invention a pour but de fournir un procédé d'imperméabilisation simple et êconoique, sans danger et pouvant s'intégrer à une chaîne de fabrication à cadence élevée.The object of the invention is to provide a simple and economical waterproofing process which is harmless and which can be integrated into a production line at a high rate.
A cet effet, l'invention a pour objet un procédé d'imperméabilisation d'une surface constituée d'un polymère, caractérisé en ce qu'on porte à une température de déc omposition un composé fluoré gazeux stable à la température ambiante, puis on l'envoie sur ladite surface.To this end, the subject of the invention is a process for waterproofing a surface made up of a polymer, characterized in that a gaseous fluorinated compound stable at room temperature is brought to decomposition temperature, then sends it to said surface.
De préférence, ledit composé est le tétrafluorure de carbone ou l'hexafluorure de soufre, et on élève sa température au moyen d'une flamme oxy-propane.Preferably, said compound is carbon tetrafluoride or sulfur hexafluoride, and its temperature is raised by means of an oxy-propane flame.
Comme application d'un tel procédé, l'invention propose également un procédé de fabrication d'un objet en un polymère dans lequel, après avoir moulé l'objet, on imperméabilise sa surface externe au moyen d'un procédé tel que défini plus haut.As an application of such a method, the invention also proposes a method of manufacturing an object from a polymer in which, after having molded the object, its external surface is waterproofed by means of a method as defined above. .
En variante, on peut également imperméabiliser, au moyen audit procédé, la surface des granulés du polymère, puis effectuer le moulage de l'objet à partir des granulés ainsi traités.As a variant, the surface of the polymer granules can also be waterproofed, by means of said method, then molding of the object from the granules thus treated.
Dans une autre variante, qui s'applique à la fabrication d'objets en polymère par extrusion-soufflage, on imperméabilise au moyen dudit procédé la surface externe de la paraison, pendant son trajet de l'extrudeuse au moule de soufflage.In another variant, which applies to the manufacture of polymer objects by extrusion blow molding, the external surface of the parison is waterproofed by means of said method, during its path from the extruder to the blow mold.
L'invention a également pour objet un appareil pour la mise en oeuvre des deux dernières variantes définies ci-dessus. En ce qui concerne la première variante, cet appareil est caractérisé en ce qu'il comprend une grille mobile, des moyens pour déposer sur cette grille lesdits granulés, et au moins un brûleur disposé au-dessus et/ou au-dessous de la grille, ce brûleur étant pourvu de moyens d'alimentation en combustible, en comburant et en ledit composé fluoré. En ce qui concerne la seconde variante, l'appareil est caractérisé en ce qu'il comprend un brûleur annulaire disposé entre l'extrudeuse et le moule de soufflage, ce brûleur étant pourvu de moyens d'cdimentation en ccπbustible, en comburant et en ledit composé fluoré. Quelques exemples de mise en oeuvre de l'invention vont maintenant être décrits en regard des dessins annexés, sur lesquels les figures 1 à 3 illustrent schématiquement trois modes de mise en oeuvre du procédé d'imperméabilisation conforme à l'invention.The invention also relates to an apparatus for implementing the last two variants defined above. In what relates to the first variant, this device is characterized in that it comprises a movable grid, means for depositing on this grid said granules, and at least one burner disposed above and / or below the grid, this burner being provided with means for supplying fuel, oxidizer and said fluorinated compound. As regards the second variant, the apparatus is characterized in that it comprises an annular burner disposed between the extruder and the blowing mold, this burner being provided with means for supplying fuel, by combustion and by said fluorinated compound. Some examples of implementation of the invention will now be described with reference to the accompanying drawings, in which Figures 1 to 3 schematically illustrate three modes of implementation of the waterproofing process according to the invention.
On a représenté schérratiquement à la figure 1 la paroi 1 d'une enceinte 2 de traitement de réservoirs d'automobile 3 en polyethylene. Dans l'enceinte 2 est disposé au moins un brûleur-mélangeur 4 muni de trois conduites d'alimentation : une conduite 5 d'alimentation en gaz ccnnburant, par exemple en oxygène, une conduite 6 d'alimentation en gaz ccambustible, par exemple en propane, et une conduite 7 d'alimentation en un composé fluoré gazeux stable à la température ambiante, par exemple en tétrafluorure de carbone (CF4) ou en hexafluorure de soufre (SF6). Les conduites 5 à 7 débouchent dans une chambre commune du brûleur.The wall 1 of an enclosure 2 for treating automobile tanks 3 made of polyethylene has been shown schematically in FIG. 1. In the enclosure 2 is disposed at least one burner-mixer 4 provided with three supply lines: a supply line 5 for supplying gas, for example oxygen, a supply line 6 for supplying combustible gas, for example in propane, and a line 7 for supplying a gaseous fluorinated compound stable at room temperature, for example carbon tetrafluoride (CF 4 ) or sulfur hexafluoride (SF 6 ). Lines 5 to 7 open into a common chamber of the burner.
L'enceinte 2 comporte également des moyens appropriés (non représentés) pour faire défiler la totalité de la surface extérieure du réservoir 3 en regard du brûleur-mélangeur 4. Par exemple, en supposant le réservoir cylindrique, ces moyens peuvent l'animer d'un mouvement hélicoïdal d'axe parallèle à la surface 8 de sortie des gaz du brûleur-mélangeur.The enclosure 2 also includes suitable means (not shown) for scrolling the entire external surface of the tank 3 opposite the burner-mixer 4. For example, assuming the cylindrical tank, these means can animate it by a helical movement with an axis parallel to the gas outlet surface 8 of the burner-mixer.
En fonctionnem ent, le mélange de trois gaz réalisé dans le brûleur-mélangeur forme à la sortie de ce dernier un ensemble de flammes 9 contenant le composé gazeux fluoré. La température des flammes est choisie de préférence de manière à assurer une décomposition à peu près totale de ce composé ; par exemple, la flamme oxy-propane possède une température de l'ordre de 3000 K, qui provoque la déccnπposition totale du CF4 et du SF6.In operation, the mixture of three gases produced in the burner-mixer forms at the outlet of the latter a set of flames 9 containing the gaseous fluorinated compound. The flame temperature is preferably chosen so as to ensure an almost total decomposition of this compound; for example, the oxy-propane flame has a temperature of the order of 3000 K, which causes the total deccnπposition of CF 4 and SF 6 .
En variante, avec d'autres types de flarrmes, on peut réaliser le mélange de gaz au moins partiellement à la sortie du brûleur ; par exemple, avec une flarme oxhydrique (oxygène-hydrogène), on ne mélangerait le composé fluoré qu'avec l'oxygène dans le brûleur.As a variant, with other types of flares, the gas mixture can be produced at least partially at the outlet of the burner; through example, with an oxyhydric flame (oxygen-hydrogen), the fluorinated compound would only be mixed with the oxygen in the burner.
Les produits de la déccampositiσn du composé fluoré atteignent ensuite la surface du réservoir 3 et y forment une couche superficielle 10 imperméable notamment aux vapeurs d'hydrocarbures. On pense que ce résultat est essentiellement dû à l'effet de fluoration résultant de la présence d'atomes libres de fluor dans la flamme, et également, dans le cas où l'on utilise du SF6, à un effet de sulfonation, le SF6 engendrant dans la flamme des espèces SO2 et SO3 favorables à l'imperméabilisation. II est à noter que du fait de la présence d'hydrogène dans le propane et dans l'humidité de l'air, la décœnposition du CF4 comme celle du SF6 provoque l'apparition dans les flamres de fluorure d'hydrogène (HF), d'autant plus que la température de la flamme est moins élevée. La paroi 1 de l'enceinte de travail doit donc être réalisée dans un matériau compatible avec ce corps, par exemple en polyprcpylene. On peut, en variante, éviter l'apparition de fluorure d'hydrogène en utilisant, pour décomposer le gaz fluoré, un milieu à température élevée ne contenant pas d'hydrogène, par exemple un plasma d'argon, et en travaillant en atmosphère sèche. Les gaz effluents sont aspirés par une hotte 11 dont est équipée la paroi 1 de l'enceinte, puis traités de façon appropriée avant d'être rejetés à l'atmosphère.The decamping products of the fluorinated compound then reach the surface of the reservoir 3 and form therein a surface layer 10 impermeable in particular to hydrocarbon vapors. It is believed that this result is mainly due to the fluorination effect resulting from the presence of free fluorine atoms in the flame, and also, in the case where SF 6 is used , to a sulfonation effect, the SF 6 generating in the flame SO 2 and SO 3 species favorable to waterproofing. It should be noted that due to the presence of hydrogen in propane and in the humidity of the air, the decenoposition of CF 4 like that of SF 6 causes the appearance in flames of hydrogen fluoride (HF ), especially as the temperature of the flame is lower. The wall 1 of the working enclosure must therefore be made of a material compatible with this body, for example polypropylene. One can, as a variant, avoid the appearance of hydrogen fluoride by using, to decompose the fluorinated gas, a medium at high temperature not containing hydrogen, for example an argon plasma, and by working in a dry atmosphere. . The effluent gases are sucked in by a hood 11 with which the wall 1 of the enclosure is equipped, then treated appropriately before being discharged into the atmosphere.
On comprend que l'ensemble de l'appareil peut être facilement automatisé et intégré dans une chaîne de fabrication de réservoirs (ou d'autres objets en un polymère) à cadence élevée.It is understood that the entire apparatus can be easily automated and integrated into a production line for tanks (or other objects made of a polymer) at high speed.
Dans l'exemple de la figure 2, on traite de façon analogue les granulés destinés à être fendus puis moulés, par exemple par extrusion-soufflage, pour constituer des objets tels que des réservoirs. Pour cela, l'appareil comprend une grille sans fin 12 embrassant deux poulies 13 dont une est motrice. Un brûleur 4 tel que celui de la figure 1 est disposé entre les deux brins de la grille 12, face 8 vers le haut, et un autre brûleur 4 est disposé au-dessus du brin supérieur de la grille, face 8 vers le bas. Chaque brûleur s'étend sur toute la largeur de la grille, et les deux brûleurs sont décalés suivant la direction longitudinale de cette dernière.In the example of FIG. 2, the granules intended to be split and then molded are treated in a similar manner, for example by extrusion blow molding, to constitute objects such as tanks. For this, the device comprises an endless grid 12 embracing two pulleys 13, one of which is driving. A burner 4 such as that of FIG. 1 is disposed between the two strands of the grid 12, face 8 upwards, and another burner 4 is disposed above the upper strand of the grid, face 8 downwards. Each burner extends over the entire width of the grate, and the two burners are offset in the longitudinal direction of the latter.
Les granulés 14 de polymère sont délivrés par une trémie 15 à l'extrémité amont du brin supérieur de la grille, de préférence sur une seule épaisseur. La surface de chaque grain est imperméabilisée comme précédemment au passage des brûleurs, et les grains traités sont déversés à l'autre extrânité de la grille dans un bac 16. Le moulage d'objets à partir de tels grains permet d'obtenir des objets imperméabilisés dans leur masse.The polymer granules 14 are delivered by a hopper 15 to the upstream end of the upper strand of the grid, preferably on a single thickness. The surface of each grain is waterproofed as before with the passage of the burners, and the treated grains are poured at the other end of the grid into a tank 16. The molding of objects from such grains makes it possible to obtain waterproofed objects in their mass.
En variante, dans certains cas, on peut se contenter d'utiliser un seul des deux brûleurs 4.As a variant, in certain cases, it is possible to be satisfied with using only one of the two burners 4.
Dans l'exemple de la figure 3, qui concerne la fabrication de réservoirs par extrusion-soufflage, la matière polymère sort d'une éxtrudeuse 17 à une température relativement élevée sous la forme d'une paraison tubulaire 18 et pénètre entre les deux moitiés 19, 20 d'un moule de soufflage ouvert. Puis le moule se referme, en pinçant la paraison, et une tête de soufflage (non représentée) vient injecter un gaz dans la paraison pour réaliser la mise en forme. Suivant l'invention, un brûleur annulaire 4A, pourvu des mânes alimentations 5, 6, 7 que le brûleur 4 des figures 1 et 2, est disposé coaxialement entre l'éxtrudeuse et le moule. Ainsi, la surface externe de la paraison est imperméabilisée par les flarmes 9 au cours de son trajet de l'éxtrudeuse au moule, et l'on obtient de nouveau, après soufflage, des réservoirs imperméabilisés dans leur masse. In the example of FIG. 3, which relates to the manufacture of tanks by extrusion blow molding, the polymer material leaves a extruder 17 at a relatively high temperature in the form of a tubular parison 18 and penetrates between the two halves 19 , 20 of an open blow mold. Then the mold closes, pinching the parison, and a blowing head (not shown) injects a gas into the parison to achieve shaping. According to the invention, an annular burner 4A, provided with the power supplies 5, 6, 7 that the burner 4 of Figures 1 and 2, is arranged coaxially between the extruder and the mold. Thus, the external surface of the parison is waterproofed by the flames 9 during its path from the extruder to the mold, and we obtain again, after blowing, tanks waterproofed in their mass.

Claims

REVENDICATIONS 1 - Procédé d 'imperméabilisation d'une surface constituée d'un polymère, caractérisé en ce qu'on porte à une température de décomposition un composé fluoré gazeux stable à la température ambiante, puis on l'envoie sur ladite surface. CLAIMS 1 - Method for waterproofing a surface made of a polymer, characterized in that a gaseous fluorinated compound stable at room temperature is brought to a decomposition temperature, then it is sent to said surface.
2 - Procédé suivant la revendication 1, caractérisé en ce que ledit composé fluoré est le tétrafluorure de carbone ou l'hexafluorure de soufre.2 - Process according to claim 1, characterized in that said fluorinated compound is carbon tetrafluoride or sulfur hexafluoride.
3 - Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on élève la température dudit composé fluoré au moyen d'une flamme oxy-propane (9).3 - Method according to one of claims 1 and 2, characterized in that the temperature of said fluorinated compound is raised by means of an oxy-propane flame (9).
4 - Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on élève la température dudit composé fluoré au moyen d'un plasma, de préférence en atmosphère sèche.4 - Method according to one of claims 1 and 2, characterized in that the temperature of said fluorinated compound is raised by means of a plasma, preferably in a dry atmosphere.
5. - Procédé de fabrication d'un objet en un polymère, caractérisé en ce qu'après avoir moulé l'objet, on imperméabilise sa surface externe au moyen d'un procédé suivant l'une quelconque des revendications 1 à 4.5. - A method of manufacturing an object from a polymer, characterized in that after having molded the object, its external surface is waterproofed by means of a method according to any one of claims 1 to 4.
6. - Procédé de fabrication d'un objet en un polymère, caractérisé en ce qu'on imperméabilise la surface des granulés du polymère au moyen d'un procédé suivant l'une quelconque des revendications 1 à 4, puis on effectue le moulage de l'objet à partir des granulés ainsi traités.6. - A method of manufacturing an object from a polymer, characterized in that the surface of the polymer granules is waterproofed by means of a method according to any one of claims 1 to 4, then the molding of the object from the granules thus treated.
7. - Procédé de fabrication d'un objet en un polymère par extrusion-soufflage, caractérisé en ce qu'on imperméabilise la surface externe de la paraison (18), pendant son trajet de l'éxtrudeuse (17) au moule de soufflage (19,20), au moyen d'un procédé suivant l'une quelconque des revendications 1 à 4.7. - A method of manufacturing an object in a polymer by extrusion blow molding, characterized in that the external surface of the parison (18) is waterproofed, during its path from the extruder (17) to the blow mold ( 19,20), by means of a method according to any one of Claims 1 to 4.
8 - Appareil pour la mise en oeuvre d'un procédé suivant la revendication 6, caractérisé en ce qu'il comprend une grille mobile (12), des moyens (15) pour déposer sur cette grille lesdits granulés (14), et au moins un brûleur (4) disposé au-dessus et/ou au-dessous de la grille, ce brûleur étant pourvu de moyens (5,6,7) d'alimentation en combustible, en comburant et en ledit composé fluoré.8 - Apparatus for implementing a method according to claim 6, characterized in that it comprises a movable grid (12), means (15) for depositing on this grid said granules (14), and at least a burner (4) disposed above and / or below the grate, this burner being provided with means (5,6,7) for supplying fuel, oxidizer and said fluorinated compound.
9 - Appareil pour la mise en oeuvre d'un procédé suivant la revendication 7, caractérisé en ce qu'il comprend un brûleur annulaire9 - Apparatus for implementing a method according to claim 7, characterized in that it comprises an annular burner
(4A) disposé entre l'éxtrudeuse (17) et le moule de soufflage (19, 20), ce brûleur étant pourvu de moyens (5, 6, 7) d'alim entation en combustible, en comburant et en ledit composé fluoré. (4A) disposed between the extruder (17) and the blow mold (19, 20), this burner being provided with means (5, 6, 7) for supplying fuel, oxidizer and said fluorinated compound.
EP19850904829 1984-10-03 1985-10-02 Method for proofing a surface comprised of a polymer, its application to the fabrication of objects made of polymer, and apparatus for implementing such method Withdrawn EP0197975A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8415153A FR2570964B1 (en) 1984-10-03 1984-10-03 METHOD AND APPARATUS FOR WATERPROOFING A SURFACE CONSISTING OF A POLYMER.
FR8415153 1984-10-03

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DE3739994A1 (en) * 1987-11-25 1989-06-08 Linde Ag METHOD FOR FLUORINATING PLASTIC OBJECTS
BE1006436A3 (en) 1992-12-08 1994-08-30 Solvay Thermoplastic multi tank for storage of oil.
BE1007817A3 (en) * 1992-12-08 1995-10-31 Solvay Multi-layer tank made of thermoplastic material for hydrocarbon storage
DE59408011D1 (en) * 1994-04-13 1999-04-29 Inpro Innovations Gmbh Process for the production of workpieces or components using a polymeric starting substance, in particular plastic fuel tanks
DE4445048C2 (en) * 1994-12-08 1997-03-13 Gvu Mbh Process for the chemical modification of thermoplastics containing alkyl groups and thermoplastics obtainable by the process
GB9608061D0 (en) * 1996-04-16 1996-06-19 Boc Group Plc Removal of noxious substances from gas streams
DE19700426C2 (en) * 1997-01-09 2002-03-21 Inpro Innovations Gmbh Process for the production of layers and layers that block permeation against liquids and / or gases on the inner surfaces of hollow plastic containers, in particular plastic fuel containers (KKB), by means of plasma polymerization
DE19731771A1 (en) * 1997-07-24 1999-01-28 Bultykhanova Natalia Sealing plastic containers, especially fuel tanks

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Publication number Priority date Publication date Assignee Title
GB1050251A (en) * 1963-05-25
DE1905094B2 (en) * 1968-02-02 1978-01-05 British Resin Products Ltd, London RESERVOIR FOR FUEL
US3862284A (en) * 1973-05-10 1975-01-21 Air Prod & Chem Process for producing blow molded thermoplastic articles having improved barrier properties
US4264750A (en) * 1979-08-01 1981-04-28 Massachusetts Institute Of Technology Process for fluorinating polymers
DE3027531C2 (en) * 1980-07-19 1982-05-19 Volkswagenwerk Ag, 3180 Wolfsburg Method and device for treating surfaces of parts, in particular the inner surfaces of plastic fuel tanks

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Title
See references of WO8602023A1 *

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WO1986002023A1 (en) 1986-04-10
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