US20010008663A1 - Pipes for conveying drinking water - Google Patents
Pipes for conveying drinking water Download PDFInfo
- Publication number
- US20010008663A1 US20010008663A1 US09/274,034 US27403499A US2001008663A1 US 20010008663 A1 US20010008663 A1 US 20010008663A1 US 27403499 A US27403499 A US 27403499A US 2001008663 A1 US2001008663 A1 US 2001008663A1
- Authority
- US
- United States
- Prior art keywords
- layer
- impervious
- pipes
- hydrocarbons
- polyolefin
- 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.)
- Granted
Links
- 239000003651 drinking water Substances 0.000 title claims abstract description 8
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 8
- 229920000098 polyolefin Polymers 0.000 claims abstract description 42
- -1 for example Chemical class 0.000 claims abstract description 38
- 239000004952 Polyamide Substances 0.000 claims abstract description 27
- 229920002647 polyamide Polymers 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 229920000573 polyethylene Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 14
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical class NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical class CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- 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
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/121—Rigid pipes of plastics with or without reinforcement with three layers
-
- 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
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S138/00—Pipes and tubular conduits
- Y10S138/07—Resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/9682—Miscellaneous
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31746—Polymer of monoethylenically unsaturated hydrocarbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/3192—Next to vinyl or vinylidene chloride polymer
Definitions
- the present invention relates to pipes for conveying drinking water and more particularly polyolefin pipes.
- Mains for distributing drinking water, in particular buried mains are made of polyolefin pipes such as polyethylene or polypropylene. These pipes have many advantages. They do not corrode, they are delivered as coils of great length; it suffices to unroll them.
- Polyethylene and polypropylene have no need of plasticizers; they are highly suitable for drinking water. However, some soils can be contaminated or risk being contaminated by essentially nonpolar hydrocarbons like toluene, benzene, fuel or motor spirit.
- polyolefins are nonpolar materials, they are permeable to these contaminants, which migrate through the wall of the pipe and contaminate the water.
- the present invention relates to pipes including a main layer made of polyolefin covered externally with a layer of a thermoplastic polymer which is impervious or substantially impervious to hydrocarbons and relatively nonpolar organic molecules.
- a thermoplastic polymer which is impervious or substantially impervious to hydrocarbons and relatively nonpolar organic molecules.
- the term “impervious” shall indicate “impervious or substantially impervious”.
- the invention includes pipes for conveying drinking water, comprised of a plurality of layers, wherein a main layer comprising a polyolefin is covered externally with a second layer comprising a thermoplastic polymer which is impervious to hydrocarbons.
- the polyolefin of the main layer may be chosen from polyethylene, polypropylene, copolymers of ethylene and of an alpha-olefin, copolymers of ethylene and of esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates, copolymers of ethylene and of vinyl derivatives of saturated carboxylic acids such as vinyl acetate, or mixtures of these polymers.
- Low density, high density or intermediate density polyethylene is advantageously employed.
- the polyethylene is usually filled with carbon black.
- polyolefin layer consisted of a number of layers, for example a layer of recycled polyolefin between two layers of virgin polyolefin.
- the thickness of this polyolefin layer is a function of the mechanical stresses.
- a thickness of 30 to 60 mm is suitable for external diameters up to 800 mm, while thicknesses of 2 to 6 mm are employed for external diameters of 20 mm (see, for example, NFT standard 54-063 for HDPE pipes).
- thermoplastic polymer which is impervious to hydrocarbons can be defined as a polymer which, in similar conditions and in the case of measurements performed on films of 100 ⁇ m thickness, is 15 to 100 times less permeable than polyethylene. Examples which may be mentioned are:
- PVDF polyvinylidene fluoride
- VF 2 vinylidene fluoride
- polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET),
- the pipes of the invention can be manufactured very simply by coextrusion of the polyolefin and of the impervious thermoplastic polymer. It is recommended to place a binder between the polyolefin of the main layer and the layer of impervious polymer.
- thermoplastic polymers are poorly compatible with polyolefins and, even in the course of coextrusion, where the two polymers are placed in contact near their melting points, the adhesion is bad. This bad adhesion can be troublesome when the pipe is cut to make junctions, couplings or side connections.
- the pipes of the invention can therefore be in the following form, starting from the interior: polyolefin/binder/impervious thermoplastic polymer.
- the thickness of the layer of impervious thermoplastic polymer may be between 50 and 1000 ⁇ m and that of the optional layer of binder between 5 and 300 ⁇ m.
- polyethylene, polypropylene, copolymers of ethylene and of at least one alpha-olefin and mixtures of these polymers are grafted with anhydrides of unsaturated carboxylic acids, such as maleic anhydride, or unsaturated epoxides such as glycidyl methacrylate. It is also possible to employ mixtures of these graft polymers and of ungrafted polymers;
- Particularly advantageous binders are:
- copolymers of ethylene and of alkyl(s) (meth)acrylate(s) or vinyl acetate which are grafted or copolymerized with maleic anhydride or glycidyl (meth)acrylate, optionally mixed with polyethylene or ethylene copolymers;
- copolymers of ethylene and of (meth)acrylic acid partially neutralized with metals.
- PVDF is involved as the impervious thermoplastic polymer
- a binder based on a mixture of polyalkyl methacrylate, elastomer and PVDF This binder is described in U.S. Pat. Nos. 4,317,860 and 5,242,976.
- binders described in Patent Application FR 94-15052, the content of which is incorporated in the present invention. These are mixtures of aliphatic polyester, preferably polycaprolactone, and of a halogenated, preferably. chlorinated, polyolefin.
- At least one product chosen from the following may also be grafted onto the aliphatic polyester:
- vinyl esters for example vinyl acetate
- the quantity of grafted monomer is generally lower than 15% by weight of the ungrafted aliphatic polyester.
- Chlorinated polyethylene (PE) and chlorinated polypropylene (PP) may be mentioned among the halogenated polyolefins, and especially those in which the chlorine content is between 10 and 50% by weight.
- the main layer of polyolefin and/or the layer of impervious thermoplastic polymer contain a product which permits their adhesion without having to employ a layer of binder.
- This product may be the binder described above. This product is advantageously put only into the polyolefin layer.
- thermoplastic polymers preference is given to polyamides, copolyamides or their mixtures with polyolefins.
- Polyamide is intended to mean the products of condensation:
- amino acids such as aminocaproic, 7-aminoheptanoic, 11-aminoundecanoic and 12-aminododecanoic acids and of one or more lactams such as caprolactam, oenantholactam and lauryllactam;
- salts or mixtures of diamines such as hexamethylenediamine, dodecamethylenediamine, meta-xylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids;
- Polyamide mixtures may be employed.
- PA-6, PA-11 and PA-12 and amorphous polyamides are advantageously employed.
- PA-11 and PA-12 are preferred because of their melting temperature which is lower than that of PA-6 and by virtue of which they are easier to coextrude with a binder and a polyolefin.
- polyamides and polyolefins it is advantageous that these mixtures should be based on a polyamide matrix.
- these polyolefins dispersed in this polyamide matrix these are polymers including olefin units such as, for example, ethylene, propylene, 1-butene and similar units.
- polyethylene, polypropylene and copolymers of ethylene with alpha-olefins may be grafted with anhydrides of unsaturated carboxylic acids, such as maleic anhydride or unsaturated epoxides such as glycidyl methacrylate;
- SEBS styrene/ethylene-butene/styrene
- the compatibilizing agent is a product known per se for compatibilizing polyamides and polyolefins.
- polyethylene with polypropylene or ethylene propylene copolymers, these polymers being grafted with a product exhibiting a site which is reactive with amines; these graft copolymers being subsequently condensed with polyamides or polyamide oligomers which have only one amine end.
- Patents FR 2 291 225 U.S. Pat. No. 3,972,961; U.S. Pat. No. 3,976,720
- EP 342 066 U.S. Pat. No. 5,342,886
- the quantity of polyamide forming the matrix may be between 55 and 95 parts per 5 to 45 parts of polyolefins.
- the quantity of compatibilizing agent is the quantity which is sufficient for the polyolefin to be dispersed in the form of nodules in the polyamide matrix. It may represent up to 20% by weight of the polyolefin.
- These polymers of the internal layer are manufactured by mixing polyamide, polyolefin and optionally compatibilizing agent according to the usual techniques.
- a compatibilizing agent is added which is advantageously an ethylene/propylene copolymer predominating in the number of propylene units, grafted with maleic anhydride and then optionally subsequently condensed with monoamine caprolactam oligomers.
- polyamides or their mixtures with polyolefins may also contain fillers such as carbon black, antioxidants and the like.
- the permeability to hydrocarbons is superior to that of the polyamides or of the polyamide matrices, but it may be sufficient.
- One advantage of this form of the invention is that the adhesiveness between this layer and the main layer is sufficient and may be produced without any binder. This advantage is employed in particular in the case of a main layer of polyethylene and an impervious layer with a polyethylene matrix.
Abstract
Description
- The present invention relates to pipes for conveying drinking water and more particularly polyolefin pipes. Mains for distributing drinking water, in particular buried mains are made of polyolefin pipes such as polyethylene or polypropylene. These pipes have many advantages. They do not corrode, they are delivered as coils of great length; it suffices to unroll them.
- Polyethylene and polypropylene have no need of plasticizers; they are highly suitable for drinking water. However, some soils can be contaminated or risk being contaminated by essentially nonpolar hydrocarbons like toluene, benzene, fuel or motor spirit.
- Since polyolefins are nonpolar materials, they are permeable to these contaminants, which migrate through the wall of the pipe and contaminate the water.
- The applicants have now found new pipes for conveying drinking water, which are impervious or substantially impervious to hydrocarbons and to relatively nonpolar organic molecules containing oxygen, sulfur and/or nitrogen while retaining the advantages of the polyolefin pipes.
- The present invention relates to pipes including a main layer made of polyolefin covered externally with a layer of a thermoplastic polymer which is impervious or substantially impervious to hydrocarbons and relatively nonpolar organic molecules. Hereinafter, the term “impervious” shall indicate “impervious or substantially impervious”. The invention includes pipes for conveying drinking water, comprised of a plurality of layers, wherein a main layer comprising a polyolefin is covered externally with a second layer comprising a thermoplastic polymer which is impervious to hydrocarbons.
- The polyolefin of the main layer may be chosen from polyethylene, polypropylene, copolymers of ethylene and of an alpha-olefin, copolymers of ethylene and of esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates, copolymers of ethylene and of vinyl derivatives of saturated carboxylic acids such as vinyl acetate, or mixtures of these polymers.
- Low density, high density or intermediate density polyethylene is advantageously employed. The polyethylene is usually filled with carbon black.
- It would not constitute a departure from the scope of the invention if the polyolefin layer consisted of a number of layers, for example a layer of recycled polyolefin between two layers of virgin polyolefin.
- The thickness of this polyolefin layer is a function of the mechanical stresses. To give an example, a thickness of 30 to 60 mm is suitable for external diameters up to 800 mm, while thicknesses of 2 to 6 mm are employed for external diameters of 20 mm (see, for example, NFT standard 54-063 for HDPE pipes).
- The thermoplastic polymer which is impervious to hydrocarbons can be defined as a polymer which, in similar conditions and in the case of measurements performed on films of 100 μm thickness, is 15 to 100 times less permeable than polyethylene. Examples which may be mentioned are:
- polyvinylidene fluoride (PVDF) homopolymer or copolymers of vinylidene fluoride (VF2) which have sufficient VF2 units for the layer to be impervious,
- copolymers of ethylene and vinyl alcohol (EVOH),
- polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET),
- polyamides, copolyamides, their mixtures with polyolefins,
- a mixture of one or more of the above with other polymers, provided that the layer is thermoplastic and impervious.
- The pipes of the invention can be manufactured very simply by coextrusion of the polyolefin and of the impervious thermoplastic polymer. It is recommended to place a binder between the polyolefin of the main layer and the layer of impervious polymer.
- In fact, impervious thermoplastic polymers are poorly compatible with polyolefins and, even in the course of coextrusion, where the two polymers are placed in contact near their melting points, the adhesion is bad. This bad adhesion can be troublesome when the pipe is cut to make junctions, couplings or side connections.
- The pipes of the invention can therefore be in the following form, starting from the interior: polyolefin/binder/impervious thermoplastic polymer.
- It would not constitute a departure from the scope of the invention to cover the layer of impervious thermoplastic polymer with another layer such as a polyolefin, a rubber or another polymer which is impervious to water. In fact, EVOH or polymers containing EVOH can be sensitive to water and can partially lose their properties of imperviousness in the presence of water.
- The thickness of the layer of impervious thermoplastic polymer may be between 50 and 1000 μm and that of the optional layer of binder between 5 and 300 μm.
- Examples of binders which may be mentioned are:
- polyethylene, polypropylene, copolymers of ethylene and of at least one alpha-olefin and mixtures of these polymers. All these polymers are grafted with anhydrides of unsaturated carboxylic acids, such as maleic anhydride, or unsaturated epoxides such as glycidyl methacrylate. It is also possible to employ mixtures of these graft polymers and of ungrafted polymers;
- copolymers of ethylene with at least one product chosen from (i) unsaturated carboxylic acids, their salts and their esters, (ii) vinyl esters of saturated carboxylic acids, (iii) unsaturated dicarboxylic acids, their salts, their esters, their half-esters and their anhydrides and (iv) unsaturated epoxides; the monomers (I) to (iv) being grafted or copolymerized.
- Particularly advantageous binders are:
- polyethylene, polypropylene or copolymers of ethylene and of at least one alpha-olefin which are grafted with maleic anhydride and optionally mixed with other ethylene or propylene copolymers;
- copolymers of ethylene and of alkyl(s) (meth)acrylate(s) or vinyl acetate which are grafted or copolymerized with maleic anhydride or glycidyl (meth)acrylate, optionally mixed with polyethylene or ethylene copolymers;
- copolymers of ethylene and of (meth)acrylic acid partially neutralized with metals.
- Where PVDF is involved as the impervious thermoplastic polymer, and if a very high adhesion is desired, that is to say that the separation of the PVDF from the polyolefin cannot be produced by peeling but only by rupture of the PVDF, it is recommended to employ a binder based on a mixture of polyalkyl methacrylate, elastomer and PVDF. This binder is described in U.S. Pat. Nos. 4,317,860 and 5,242,976.
- In the case of PDVF it is also possible to employ the binders described in Patent Application FR 94-15052, the content of which is incorporated in the present invention. These are mixtures of aliphatic polyester, preferably polycaprolactone, and of a halogenated, preferably. chlorinated, polyolefin.
- At least one product chosen from the following may also be grafted onto the aliphatic polyester:
- unsaturated carboxylic acids, their salts, their esters and their anhydrides; for example maleic anhydride;
- unsaturated products carrying epoxide functional groups, for example glycidyl (meth)acrylate;
- vinyl esters, for example vinyl acetate;
- styrene and its derivatives.
- The quantity of grafted monomer is generally lower than 15% by weight of the ungrafted aliphatic polyester.
- Chlorinated polyethylene (PE) and chlorinated polypropylene (PP) may be mentioned among the halogenated polyolefins, and especially those in which the chlorine content is between 10 and 50% by weight.
- According to a particular form of the invention the main layer of polyolefin and/or the layer of impervious thermoplastic polymer contain a product which permits their adhesion without having to employ a layer of binder. This product may be the binder described above. This product is advantageously put only into the polyolefin layer.
- Among the impervious thermoplastic polymers preference is given to polyamides, copolyamides or their mixtures with polyolefins.
- Polyamide is intended to mean the products of condensation:
- of one or more amino acids, such as aminocaproic, 7-aminoheptanoic, 11-aminoundecanoic and 12-aminododecanoic acids and of one or more lactams such as caprolactam, oenantholactam and lauryllactam;
- of one or more salts or mixtures of diamines such as hexamethylenediamine, dodecamethylenediamine, meta-xylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids;
- or of mixtures of all these monomers, which results in copolyamides.
- Polyamide mixtures may be employed. PA-6, PA-11 and PA-12 and amorphous polyamides are advantageously employed.
- PA-11 and PA-12 are preferred because of their melting temperature which is lower than that of PA-6 and by virtue of which they are easier to coextrude with a binder and a polyolefin.
- As for the mixtures of polyamides and polyolefins, it is advantageous that these mixtures should be based on a polyamide matrix. As for the polyolefins dispersed in this polyamide matrix, these are polymers including olefin units such as, for example, ethylene, propylene, 1-butene and similar units.
- Examples which may be mentioned are:
- polyethylene, polypropylene and copolymers of ethylene with alpha-olefins. These products may be grafted with anhydrides of unsaturated carboxylic acids, such as maleic anhydride or unsaturated epoxides such as glycidyl methacrylate;
- copolymers of ethylene with at least one product chosen from (i) unsaturated carboxylic acids, their salts and their esters, (ii) vinyl esters of saturated carboxylic acids, (iii) unsaturated dicarboxylic acids, their salts, their esters, their half esters and their anhydrides and (iv) unsaturated epoxides, it being possible for the units (i) to (iv) to be grafted or copolymerized;
- styrene/ethylene-butene/styrene (SEBS) block copolymers, optionally maleinized.
- Mixtures of two or more of these polyolefins may be employed.
- The following are advantageously employed:
- polyethylene,
- copolymers of ethylene and of an alpha-olefin,
- copolymers of ethylene/of alkyl(s) (meth)acrylate(s),
- copolymers of ethylene/of alkyl(s) (meth)acrylate(s)/of maleic anhydride, the maleic anhydride being grafted or copolymerized,
- copolymers of ethylene/of alkyl(s) (meth)acrylate(s)/of glycidyl methacrylate, the glycidyl methacrylate being grafted or copolymerized,
- polypropylene.
- To facilitate the formation of the polyamide matrix, and if the polyolefins have few or no functional groups that can facilitate the compatibilization, it is recommended to add a compatibilizing agent.
- The compatibilizing agent is a product known per se for compatibilizing polyamides and polyolefins.
- The following may be mentioned, for example:
- optionally neutralized ethylene/(meth)acrylic acid copolymers;
- polyethylene, polypropylene, ethylene propylene copolymers and copolymers of ethylene and of an alpha-olefin, all these products being grafted with maleic anhydride or glycidyl methacrylate,
- ethylene/alkyl (meth)acrylate/maleic anhydride copolymers, the maleic anhydride being grafted or copolymerized,
- ethylene/vinyl acetate/maleic anhydride copolymers, the maleic anhydride being grafted or copolymerized,
- the two preceding copolymers, in which the maleic anhydride is replaced with glycidyl methacrylate,
- polyethylene, with polypropylene or ethylene propylene copolymers, these polymers being grafted with a product exhibiting a site which is reactive with amines; these graft copolymers being subsequently condensed with polyamides or polyamide oligomers which have only one amine end.
- These products are described in Patents FR 2 291 225 (U.S. Pat. No. 3,972,961; U.S. Pat. No. 3,976,720) and EP 342 066 (U.S. Pat. No. 5,342,886), the contents of which are incorporated by reference in the present application.
- The quantity of polyamide forming the matrix may be between 55 and 95 parts per 5 to 45 parts of polyolefins.
- The quantity of compatibilizing agent is the quantity which is sufficient for the polyolefin to be dispersed in the form of nodules in the polyamide matrix. It may represent up to 20% by weight of the polyolefin. These polymers of the internal layer are manufactured by mixing polyamide, polyolefin and optionally compatibilizing agent according to the usual techniques.
- In the case of polypropylene, a compatibilizing agent is added which is advantageously an ethylene/propylene copolymer predominating in the number of propylene units, grafted with maleic anhydride and then optionally subsequently condensed with monoamine caprolactam oligomers.
- Such mixtures of polyamide and of polypropylene are described in U.S. Pat. No. 5,342,886.
- These polyamides or their mixtures with polyolefins may also contain fillers such as carbon black, antioxidants and the like.
- It would not constitute a departure from the scope of the invention to employ, as impervious thermoplastic polymer, mixtures of polyamide and of polyolefins with a polyolefin matrix. The polyamides and the polyolefins are chosen from the above products.
- The permeability to hydrocarbons is superior to that of the polyamides or of the polyamide matrices, but it may be sufficient. One advantage of this form of the invention is that the adhesiveness between this layer and the main layer is sufficient and may be produced without any binder. This advantage is employed in particular in the case of a main layer of polyethylene and an impervious layer with a polyethylene matrix.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/274,034 US6413602B2 (en) | 1995-03-10 | 1999-03-22 | Pipes for conveying drinking water |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FRFR9502813 | 1995-03-10 | ||
FR9502813A FR2731497B1 (en) | 1995-03-10 | 1995-03-10 | TUBE FOR TRANSPORTING DRINKING WATER |
FR9502813 | 1995-03-10 | ||
US08/612,694 US6511724B1 (en) | 1995-03-10 | 1996-03-08 | Pipes for conveying drinking water |
US09/274,034 US6413602B2 (en) | 1995-03-10 | 1999-03-22 | Pipes for conveying drinking water |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/612,694 Continuation US6511724B1 (en) | 1995-03-10 | 1996-03-08 | Pipes for conveying drinking water |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010008663A1 true US20010008663A1 (en) | 2001-07-19 |
US6413602B2 US6413602B2 (en) | 2002-07-02 |
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ID=9476930
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/612,694 Expired - Fee Related US6511724B1 (en) | 1995-03-10 | 1996-03-08 | Pipes for conveying drinking water |
US09/274,034 Expired - Fee Related US6413602B2 (en) | 1995-03-10 | 1999-03-22 | Pipes for conveying drinking water |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/612,694 Expired - Fee Related US6511724B1 (en) | 1995-03-10 | 1996-03-08 | Pipes for conveying drinking water |
Country Status (8)
Country | Link |
---|---|
US (2) | US6511724B1 (en) |
EP (1) | EP0731307B1 (en) |
JP (2) | JP3339614B2 (en) |
AU (1) | AU712890B2 (en) |
BR (1) | BR9600965A (en) |
CA (1) | CA2171353A1 (en) |
DE (1) | DE69606567T2 (en) |
FR (1) | FR2731497B1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040028860A1 (en) * | 2002-07-23 | 2004-02-12 | Dalal Girish T. | Polyefinic pipe having a chlorinated polyolefinic hollow core |
WO2006123260A2 (en) * | 2005-03-24 | 2006-11-23 | Sanjay Agarwal | Solvent weldable / adhesive bondable polyolefin pipe and pipe-fitting |
DE202007008719U1 (en) * | 2007-06-19 | 2008-10-30 | Rehau Ag + Co | Trinkwasserschlauch |
FR2955585A1 (en) * | 2010-01-28 | 2011-07-29 | Ass Pour Les Transferts De Technologies Du Mans | Mixture having continuous/co-continuous polyamide phase, useful for preparing extruded or injection molded shaped parts, comprises a minor proportion of polyamide and a maleic anhydride grafted polyolefin as a compatibility agent |
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Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19648858A1 (en) * | 1996-11-26 | 1998-06-04 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of allyl ether-modified unsaturated polyester resins for use in drinking water pipes |
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KR101064920B1 (en) * | 2011-03-14 | 2011-09-20 | 송병규 | A manufacture method of water saving device body and water saving device body |
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Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3561493A (en) * | 1965-04-21 | 1971-02-09 | Paul Maillard | Composite tubes and method of manufacturing same |
JPS51125466A (en) | 1974-11-13 | 1976-11-01 | Du Pont | Process for preparing graftcopolymer |
IT1119928B (en) | 1978-09-25 | 1986-03-19 | Ugine Kuhlmann | COMPOSITE MATERIAL OF VINYLIDENE POLYFLUORIDE AND INCOMPATIBLE THERMOPLASTIC POLYMER AND PROCEDURE FOR ITS MANUFACTURE |
FR2477463A1 (en) * | 1980-03-07 | 1981-09-11 | Ugine Kuhlmann | PROCESS FOR PRODUCING VINYLIDENE POLYFLUORIDE COMPOSITE AND NON-COMPATIBLE POLYMER BY COEXTRUSION-MOLDING |
US4634615A (en) * | 1984-04-06 | 1987-01-06 | Versteegh Willem M | Heat recoverable coextruded articles |
JPH01141047A (en) * | 1987-11-28 | 1989-06-02 | Tokai Rubber Ind Ltd | Refrigerant transport hose |
US5342886A (en) | 1988-03-24 | 1994-08-30 | Atochem | α-monoolefinic graft copolymers |
FR2629090B1 (en) | 1988-03-24 | 1990-11-23 | Atochem | GRAFT COPOLYMER BASED ON ALPHA-MONO-OLEFIN, ITS MANUFACTURING PROCESS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED |
DE4001125C1 (en) * | 1989-11-20 | 1990-12-13 | Technoform Caprano + Brunnhofer Kg, 3501 Fuldabrueck, De | |
FR2659085B1 (en) | 1990-03-02 | 1992-05-15 | Atochem | COMPOSITION COEXTRUDABLE WITH VINYLIDENE POLYFLUORIDE ALLOWING THE ADHESION OF THE SAME WITH A NON-COMPATIBLE POLYMERIC RESIN - COMPOSITE OBTAINED WITH THIS COMPOSITION. |
EP1120594A3 (en) * | 1992-04-14 | 2003-03-05 | Itt Manufacturing Enterprises, Inc. | Multi-layer fuel and vapor tube |
FR2701303B1 (en) * | 1993-02-05 | 1995-04-28 | Nobel Plastiques | Multilayer plastic pipe. |
DK0635108T3 (en) * | 1993-02-05 | 1997-12-08 | Nobel Plastiques | Multilayer pipe system made of plastic material |
-
1995
- 1995-03-10 FR FR9502813A patent/FR2731497B1/en not_active Expired - Fee Related
-
1996
- 1996-02-28 EP EP96400422A patent/EP0731307B1/en not_active Expired - Lifetime
- 1996-02-28 DE DE69606567T patent/DE69606567T2/en not_active Expired - Lifetime
- 1996-03-07 JP JP07954196A patent/JP3339614B2/en not_active Expired - Fee Related
- 1996-03-08 US US08/612,694 patent/US6511724B1/en not_active Expired - Fee Related
- 1996-03-08 CA CA002171353A patent/CA2171353A1/en not_active Abandoned
- 1996-03-08 BR BR9600965A patent/BR9600965A/en not_active IP Right Cessation
- 1996-03-08 AU AU48011/96A patent/AU712890B2/en not_active Ceased
-
1999
- 1999-03-22 US US09/274,034 patent/US6413602B2/en not_active Expired - Fee Related
-
2002
- 2002-03-13 JP JP2002068791A patent/JP2002340242A/en not_active Withdrawn
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040028860A1 (en) * | 2002-07-23 | 2004-02-12 | Dalal Girish T. | Polyefinic pipe having a chlorinated polyolefinic hollow core |
US7160593B2 (en) * | 2002-07-23 | 2007-01-09 | Noveon, Inc. | Polyefinic pipe having a chlorinated polyolefinic hollow core |
WO2006123260A2 (en) * | 2005-03-24 | 2006-11-23 | Sanjay Agarwal | Solvent weldable / adhesive bondable polyolefin pipe and pipe-fitting |
WO2006123260A3 (en) * | 2005-03-24 | 2007-03-29 | Sanjay Agarwal | Solvent weldable / adhesive bondable polyolefin pipe and pipe-fitting |
DE202007008719U1 (en) * | 2007-06-19 | 2008-10-30 | Rehau Ag + Co | Trinkwasserschlauch |
FR2955585A1 (en) * | 2010-01-28 | 2011-07-29 | Ass Pour Les Transferts De Technologies Du Mans | Mixture having continuous/co-continuous polyamide phase, useful for preparing extruded or injection molded shaped parts, comprises a minor proportion of polyamide and a maleic anhydride grafted polyolefin as a compatibility agent |
CN105451991A (en) * | 2013-08-29 | 2016-03-30 | 三菱瓦斯化学株式会社 | Multilayer structure |
Also Published As
Publication number | Publication date |
---|---|
JP3339614B2 (en) | 2002-10-28 |
JP2002340242A (en) | 2002-11-27 |
DE69606567T2 (en) | 2000-07-27 |
FR2731497A1 (en) | 1996-09-13 |
US6413602B2 (en) | 2002-07-02 |
BR9600965A (en) | 1997-12-30 |
FR2731497B1 (en) | 1997-04-30 |
AU4801196A (en) | 1996-09-19 |
EP0731307A1 (en) | 1996-09-11 |
DE69606567D1 (en) | 2000-03-16 |
CA2171353A1 (en) | 1996-09-11 |
EP0731307B1 (en) | 2000-02-09 |
JPH08260526A (en) | 1996-10-08 |
AU712890B2 (en) | 1999-11-18 |
US6511724B1 (en) | 2003-01-28 |
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