Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/107—Ceramic
  • B32B2264/108—Carbon, e.g. graphite particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • 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]
• • 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
• • 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
  • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
• • 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
• • 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]

Definitions

• the present invention is directed to an improved multilayer polymer structure, to a process for the manufacture of said polymer structure, to a shaped article comprising said polymer structure and to a process for the manufacture of said shaped article.
• Polyolefms like ethylene based polymers are relatively cheap thermoplastic materials, showing good mechanical properties, dimensional stability and processability. Nevertheless such materials are characterized by poor barrier properties towards different types of chemical compounds (e.g. hydrocarbons, fuels, gases like oxygen, vapors like water vapor). That makes them unsuitable for certain applications like, for instance, fuel tanks, automotive fuel lines, food packaging, clean air ducts, etc.
• Prior art solutions which aim at limiting, at least to some extent, this problem consist in very complex five or six layer constructions which incorporate a barrier layer of poly (ethylene -vinyl alcohol) or aliphatic polyamide within a multilayer polyolefin (e.g. polyethylene) based structure.
• Such processes should be more suited than prior art processes, notably for the manufacture of multilayered shaped articles as complex and/or diversified as multilayered film in flat form and/or in tubing form (e.g. automotive fuel lines or hoses, vapor lines, heat exchanger tubings), and multilayered hollow-bodies, especially those having very complex cross-sectional configuration like fuel tanks. While it is true that some prior art multilayer polyolefin based structures have already been manufactured by co-extrusion, the viability of such process in the case of new multilayer structures comprising polymers different from those already used in the art is highly unpredictable.
• the present invention is directed to a multilayer structure comprising at least one couple (L1-L2) of adjacent layers (Ll) and (L2), wherein:
• ⁇ layer (Ll) comprises at least one polymer composition (Cl) comprising: (i) at least one semi-aromatic polyamide, and (ii) at least one impact modifier (II);
• ⁇ layer (L2) comprises at least one polymer composition (C2) comprising: (i) at least one un-functionalized polyolefm (PO2); and (ii) at least one functionalized polyolefm (FP02), said functionalized polyolefm comprising functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts.
• the multilayer structure comprises at least one polymer composition (C2) comprising: (i) at least one un-functionalized polyolefm (PO2); and (ii) at least one functionalized polyolefm (FP02), said functionalized polyolefm comprising functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts.
• the invented multilayer structure comprises at least one couple (L1-L2) of adjacent layers (Ll) and (L2).
• the multilayer structure comprises more than two layers.
• Examples of multilayer structures comprising more than two layers include multilayer structures comprising no more than one couple (L1-L2) and at least one additional layer, in particular trilayer and tetralayer structures in which the additional layer(s) can be the innermost layer and/or the outermost layer.
• the invented multilayer structure is advantageously a hollow body or a part thereof.
• layer (Ll) can be either more inner or more outer than layer (L2).
• layer (Ll) is more inner than layer (L2).
• a layer comprised in the multilayer structure is “more inner” than another when the first one is on the or closer to the inside of the multilayer structure, the inside of the multilayer structure being defined, for the purpose of the present invention, as the side directly facing the region of space which is partially or completely enclosed by the hollow body; a layer comprised in the multilayer structure of the hollow body is "more outer " than another, when the first one is on the or closer to the outside of the multilayer - A -
• the outside of the multilayer structure being defined as the side facing away from the inside of the multilayer structure.
• the multilayer structure comprises at most 4 layers.
• the multilayer structure is a bilayer structure.
• layers (Ll) and (L2) are the sole layers.
• layer (Ll) can be either the inner or the outer layer; preferably, layer (Ll) is the inner layer.
• layer (Ll) provides advantageously the multilayer structure, notably, with excellent chemical resistance and impermeability to fluid such as hydrocarbon fuels and alcohols, and in certain embodiments of the present invention, layer (Ll), if needed, also imparts the ability to dissipate static electrical charge.
• Layer (L2) provides advantageously the invented multilayer structure, notably, with dimensional stability, strength and cost effectiveness.
• Layer (Ll) may be used to further improve the overall performance level of the multilayer structure, in particular its mechanical strength, impermeability and its dimensional stability in order to meet the requirements of certain specific applications.
• Layer (Ll) may be used to further improve the overall performance level of the multilayer structure, in particular its mechanical strength, impermeability and its dimensional stability in order to meet the requirements of certain specific applications.
• layer (Ll) is not particularly limited. In certain preferred embodiments of the present invention, the thickness of layer (Ll) is of at least 0.002 mm, more preferably of at least 0.02 mm, still more preferably of at least 0.1 mm. In addition, in said embodiments, the thickness of layer (Ll) is smaller than 2 mm.
• the weight percent of polymer composition (Cl) to the total weight of layer (Ll), is advantageously of at least 10 wt.%, preferably of at least 40 wt.%, more preferably of at least 60 wt.%, still more preferably of at least 80 wt.%.
• layer (Ll) consists essentially of polymer composition (Cl).
• the semi-aromatic polyamide is a polymer of which more than 15 mole % of the recurring units comprise at least one amide group (-CONH-), at least one arylene group, such as phenylene, naphthalene, p-biphenylene and metaxylylene, and at least one non aromatic group, such as an alkylene group.
• Said recurring units can be obtained notably by (i) condensation reaction of an aromatic dicarboxylic acid monomer with an aliphatic diamine monomer, (ii) condensation reaction of an aliphatic dicarboxylic acid monomer with an aromatic diamine monomer, (iii) condensation reaction of an aromatic dicarboxylic acid monomer with an aromatic diamine monomer, (iv) auto-condensation of an aromatic amino-acid, and combinations thereof.
• Ortho-phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid are examples of aromatic dicarboxylic acid monomers
• meta-phenylene diamine, meta-xylylene diamine and para-xylylene diamine are examples of aromatic diamine monomers.
• Adipic acid and sebacic acid are examples of suitable aliphatic dicarboxylic acid monomers, while hexamethylene diamine, methylpentamethylene diamine and nonanediamine are examples of suitable aliphatic diamine monomers.
• the semi-aromatic polyamide may further comprise recurring units consisting of at least one amide group and at least one alkylene group. Said recurring units can be obtained notably by condensation reaction of an aliphatic dicarboxy acid monomer with an aliphatic diamine monomer, or by auto-condensation of an aliphatic amino-acid.
• the semi-aromatic polyamide comprises preferably more than 15 mole %, based on the total number of moles of recurring units, of recurring units obtained by (i) condensation reaction of an aliphatic dicarboxylic acid monomer with an aromatic diamine monomer and/or (ii) condensation reaction of an aromatic dicarboxylic acid monomer with an aliphatic diamine monomer.
• the semi-aromatic polyamide comprises preferably less than 15 mole %, based on the total number of moles of recurring units, of recurring units obtained by (iii) condensation reaction of an aromatic dicarboxylic acid monomer with an aromatic diamine monomer, and (iv) auto-condensation of an aromatic amino-acid.
• the semi-aromatic polyamide is a PMXDA, a polyphthalamide, or a mixture of a PMXDA and a polyphthalamide. Still more preferably the semi-aromatic polyamide is a PMXDA.
• PMXDA is herein intended to denote a semi-aromatic polyamide of which more than 50 mole % of the recurring units, based on the total number of moles of recurring units, are obtained by condensation reaction of an aliphatic dicarboxylic acid monomer, preferably adipic acid, with an aromatic diamine monomer, preferably meta-xylylene diamine.
• PMXDA useful for the present invention comprises preferably at least 70 mole %, more preferably at least 80 mole %, still more preferably at least 90 mole % and the most preferably at least 95 mole % of recurring units obtained by condensation reaction of adipic acid and meta-xylylene diamine .
• PMXDA as complying with these features are notably commercially available as IXEF ® polyamides from Solvay Advanced Polymers, L.L.C.
• the molecular weight of the PMXDA is not particularly limited.
• the PMXDA has number average molecular weight (M n ) of at least 3,000, more preferably of at least 7,000, still more preferably of at least 22,000.
• the PMXDA has number average molecular weight (M n ) of at most 60,000, more preferably of at most 50,000 and still more preferably of at most 30,000.
• M n is calculated according to the following formula
• Polyphthalamide herein is intended to denote any semi-aromatic polyamide of which at least 35 mole % of the recurring units, based on the total number of moles of recurring units, are formed by copolymerizing at least one phthalic acid monomer with at least one aliphatic diamine monomer.
• Phthalic acid monomer herein is intended to denote anyone of ortho-phthalic acid, isophthalic acid, terephthalic acid or mixtures thereof.
• the aliphatic diamine monomer is advantageously a C3-C12 aliphatic diamine, preferably a C6-C 9 aliphatic diamine, and more preferably, is hexamethylene- diamine.
• Polyphthalamides are commercially available as AMODEL ® polyamides from
• the polyphthalamide is preferably a polyterephthalamide.
• Polyterephthalamide herein is intended to denote a polyphthalamide of which at least 35 mole % of the recurring units, based on the total number of moles of recurring units, are formed by copolymerizing terephthalic acid with at least one aliphatic diamine.
• the polyphthalamide is more preferably a polyterephthalamide formed by copolymerizing terephthalic acid monomer, optionally isophthalic acid monomer, and at least one aliphatic dicarboxylic acid monomer, preferably adipic acid, with at least one aliphatic diamine monomer, preferably hexamethylene-diamine.
• the weight percent of the semi-aromatic polyamide to the total weight of the polymer composition (Cl) is advantageously of at least 50 wt.%, preferably of at least 60 wt.%, and more preferably of at least 70 wt.%. Besides, the weight percent of the semi-aromatic polyamide to the total weight of the polymer composition (Cl) is advantageously of at most 95 wt.%, and preferably of at most 90 wt.%.
• Impact modifiers suitable for the present invention are not particularly limited insofar as they impart useful mechanical properties to polymer composition (Cl), such as sufficient tensile elongation at yield and break.
• impact modifier (II) further improves the processability of composition (Cl), notably its aptitude to be co-extruded and/or co-blow molded.
• Impact modifier (II) is advantageously chosen from: (i) functionalized elastomeric and un- functionalized elastomeric polymers other than polyolefms; (ii) un- functionalized polyolefms (POl); (iii) functionalized polyolefms (FPOl); (iv) mixtures thereof.
• polyolefm is herein intended to denote a polymer the recurring units of which are obtained by polymerization of unsaturated aliphatic hydrocarbons.
• Functionalized elastomeric and un-functionalized elastomeric polymers other than polyolefms useful for the present invention are for example: ethylene (defined hereinafter shortly as “Ee") / 1-octene (defined hereinafter shortly as “1Oe”) / styrene terpolymers, Ee / 1Oe / acrylonitrile terpolymers, Ee / 1Oe / methylacrylate terpolymers, Ee / 1Oe / vinyl acetate terpolymers, Ee / 1Oe / methyl methacrylate terpolymers, propylene (defined hereinafter shortly as "Pe”) / 1Oe / styrene terpolymers, Pe / 1Oe / acrylonitrile terpolymers, Pe / 1Oe / methylacrylate terpolymers, Pe / 1Oe / vinyl acetate terpolymers, Pe / 1O
• Un-functionalized polyolefms (POl) useful for the present invention are for example: Ee homopolymers; copolymers and terpolymers of Ee with ⁇ -olefms like for instance: Ee/1-butene (IBe) copolymers, Ee/l-hexene(lH) copolymers, Ee / 1Oe copolymers, Ee/lBe/lH terpolymers, Ee /Pe / 1Oe terpolymers, Ee / IBe /1Oe terpolymers, Ee /1Oe / 1-pentene terpolymers; Pe / 1Oe copolymers; Pe /IBe /1Oe terpolymers; Ee / 1Oe / 1 ,4-hexadiene terpolymers; Pe / 1Oe / 1 ,4-hexadiene terpolymers; Ee / 1Oe / eth
• the un-functionalized polyolefm (POl) is advantageously chosen from the homopolymers of ethylene, the copolymers of ethylene with at least one ⁇ -olefm and the copolymers of ethylene with at least one ⁇ -olefm and at least one diene.
• the un-functionalized polyolefm (POl) is preferably a copolymer of ethylene with at least one ⁇ -olefm.
• the functionalized polyolefm (FPOl) advantageously comprises functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts.
• Impact modifier (II) is preferably chosen from: (i) un-functionalized polyolefins (POl); (ii) functionalized polyolefms (FPOl) comprising functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts; (iii) mixtures thereof.
• Impact modifier (II) is more preferably a functionalized polyolefm (FPOl) comprising functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts.
• the functionalized polyolefm (FPOl) can be obtained by any technique known in the art, for example by copolymerizing at least one olefin with at least one ethylenically unsaturated monomer bearing at least one suitable functional group.
• the functionalized polyolefm (FPOl) is obtained by grafting at least one grafting agent (Gl) onto at least one un-functionalized polyolefm (POl ').
• the grafting agent (Gl) is advantageously chosen from ethylenically unsaturated carboxylic acids, their esters, their anhydrides and their salts.
• the grafting agent (Gl) is preferably chosen from ethylenically unsaturated compounds comprising at most two carboxylic groups. More preferably, the grafting agent (Gl) further comprises from 3 to 20 carbon atoms, like acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride (MAH), succinic anhydride, itaconic anhydride, crotonic anhydride, citraconic anhydride and mixtures thereof.
• the grafting agent (Gl) is chosen from maleic anhydride (MAH), succinic anhydride, acrylic acid, methacrylic acid, maleic acid, succinic acid and mixtures thereof.
• MAH maleic anhydride
• succinic anhydride acrylic acid, methacrylic acid, maleic acid, succinic acid and mixtures thereof.
• MAH maleic anhydride
• MAH maleic anhydride
• the weight percent of grafting agent (Gl) to the total weight of the functionalized polyolefm (FPOl), is advantageously of at least 0.01 wt.%, preferably of at least 0.1 wt.%, more preferably of at least 0.2 wt.%, and still more preferably of at least 0.4 wt.%.
• it is advantageously of at most 5.0 wt.%, preferably of at most 3.0 wt.%, more preferably of at most 2 wt.% and still more preferably of at most 1.5 wt.%
• the un-functionalized polyolefms (POl ') is advantageously chosen from the homopolymers of ethylene, the copolymers of ethylene with at least one ⁇ -olefm and the copolymers of ethylene with at least one ⁇ -olefm and at least one diene.
• the un-functionalized polyolefm (POl ') is preferably a copolymer of ethylene with at least one ⁇ -olefm.
• ⁇ -olefm is advantageously chosen from the ⁇ -olefms comprising from 3 to 8 carbon atoms (e.g. propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and isomers thereof), and preferably from those comprising from 4 to 6 carbon atoms (e.g. 1-butene, 1-pentene, 1-hexene, and isomers thereof).
• 3 to 8 carbon atoms e.g. propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and isomers thereof
• 4 to 6 carbon atoms e.g. 1-butene, 1-pentene, 1-hexene, and isomers thereof.
• copolymers of ethylene with at least one ⁇ -olefm advantageously comprise at least 50 mole % of ethylene recurring units based on the total number of moles of recurring units.
• these copolymers comprise at least 60 mole % of ethylene recurring units based on the total number of moles of recurring units.
• these copolymers advantageously comprise at most 95 .mole % and preferably at most 90 mole % of ethylene recurring units based on the total number of moles of recurring units.
• the functionalized polyolefm (FPOl) has a crystalline melting point advantageously of at least 100 0 C, preferably of at least 110 0 C and more preferably of at least 115°C.
• the crystalline melting point is advantageously of at most 130 0 C, and preferably of at most 125°C. Crystalline melting point was measured according to ISO standard 11357.
• the melt flow index of the functionalized polyolefm (FPOl) is conventionally measured, according to ASTM 1238 or ISO standard 1133, at 190 or 230 0 C, and under a load of 2.16, 5 or 10 kg, (MI2, MI5 or MIlO), depending from its melt viscosity, as is well known in this art, taking these provisions into account, the MI of FPOl is generally of at least 0.1 g/10 min, preferably of at least 0.5 g/10 min, more preferably of at least 2.0 g/10 min, and most preferably of at least 5,0 g/10 min. In addition, MI is generally of at most 35 g/10 min, preferably of at most 25 g/10 min and, more preferably of at most 20 g/10min.
• the functionalized polyolefin (FPOl) is a maleated linear low density polyethylene (LLDPE) wherein the weight percent of the grafted maleic anhydride units to the total weight of the maleated linear low density polyethylene is of at least 0.3 wt.%.
• LLDPE linear low density polyethylene
• the expression "linear low density polyethylene (LLDPE)" is herein intended to denote copolymers of ethylene with ⁇ -olefms, wherein the ethylene recurring units are at least 50 mole % of the total number of recurring units and at most 90 mole %.
• the amount of impact modifier (II) is advantageously sufficient to impart notably desirable mechanical characteristics (e.g. tensile elongation at yield and break) and processability to polymer composition (Cl).
• the weight percent of impact modifier (II) to the total weight of polymer composition (Cl), is preferably of at least 5 wt.%, more preferably of at least 10 wt.%, still more preferably of at least 15 and the most preferably of at least 20 wt.%.
• the weight percent of impact modifier (II) to the total weight of polymer composition (Cl) is preferably less than 50 wt.%, more preferably less than 40 wt.%, and still more preferably less than 30 wt.%.
• polymer composition (Cl) further comprises an electrically conductive filler.
• the electrically conductive filler is chosen from carbon powder, carbon black, carbon nano-tubes and mixtures thereof.
• Carbon nano-tubes useful for the present invention are either multi-wall or single-wall nano-tubes.
• the electrically conductive filler is carbon black.
• Commercially available carbon blacks suitable for the purpose of the present invention are for instance electroconductive carbon blacks, available in the form of pellets from AKZO
• the electrically conductive filler has surface area of at least 500 m /g, preferably of at least 800 m /g, more preferably of at least 1000 m 2 /g, and still more preferably of at least 1300 m /g. The surface area was measured according to the BET method.
• the weight percent of the semi-aromatic polyamide to the total weight of polymer composition (Cl) is advantageously of at least 60 wt.%, and preferably of at least 65 wt.%. In addition, it is advantageously of at most 85 wt.%, preferably of at most 80 wt.% and more preferably of at most 75 wt.%.
• the weight percent of the impact modifier (II) to the total weight of the polymer composition (Cl) is advantageously of at least 15 wt.%, preferably of at least 20 w.%. In addition, it is advantageously of at most 45 wt.%, preferably of at most 35 wt.% and more preferably of at most 30 wt.%
• the weight percent of the semi-aromatic polyamide to the total weight of the polymer composition (Cl) is advantageously of at least 75 wt.%. Besides, it is advantageously of at most 90 wt.% and preferably of at most 85 wt.%.
• polymer composition (Cl) further comprises one or more additives like lubricants, pigments, antioxidants and process-stabilizing agents, heat stabilizers, dyes, flame retardants, plasticizers, mold release agents, light stabilizers, fillers other than the electrically conductive filler and polyamides other than the semi-aromatic polyamide.
• additives may be employed alone or in any combination. The levels of such additives can be determined for the particular use envisioned by one of ordinary skill in the art in view of this disclosure; very often, it does not exceed 10 wt. %; often, it is below 5 wt. %.
• polymer composition (Cl) further comprises at least one lubricant, at least one antioxidant and at least one process-stabilizing agent.
• Heat stabilizers possibly useful as ingredients of polymer composition (Cl) are notably copper-based stabilizers comprising a copper compound soluble in the polyamide and an alkali metal halide. Examples thereof are mixtures of copper iodide and/or copper bromide with an alkali bromide and/or iodide.
• Fillers other than electrically conductive filler possibly useful as ingredients of polymer composition (Cl) are notably glass fibers, carbon fibers, graphite fibers, silicon carbide fibers, aramide fibers, wollastonite, talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, boron nitride, aluminum oxide.
• Such fillers improve possibly notably mechanical strength (e.g. flexural modulus) and/or dimensional stability and/or friction and wear resistance.
• Semi-aromatic polyamide, impact modifier (II), optionally electrically conductive filler as well as the other additives previously mentioned may be mixed together in any manner known in the art. Mixing may be done preliminary to co- extrusion in a separate extruder or it may be done immediately before co-extrusion in the same extruder used to feed the co-extrusion die.
• layer (L2) are not particularly limited.
• the un-functionalized polyolefm (PO2) advantageously, comprises at least 70 mole % of ethylene recurring units based on the total number of moles of recurring units, and preferably at least 80 mole %.
• the un-functionalized polyolefm (PO2) is an ethylene homopolymer.
• the un-functionalized polyolefm (PO2) is a copolymer of ethylene with at least one ⁇ -olefm.
• Said ⁇ -olefm complies with all of the characteristics of the ⁇ -olefm previously described in the case of the un-functionalized polyolefm (POl '), at any level of preference.
• the weight percent of the recurring units derived from the copolymerized ⁇ -olefm(s) to the total weight of the un- functionalized polyolefin (PO2) is advantageously of at least 0.1 wt.%, preferably of at least 0.5 wt.% and more preferably of at least 1.0 wt.%. In addition, it is advantageously of at most 10 wt.% and preferably of at most 5 wt.%.
• the un-functionalized polyolefm (PO2) has melt viscosity, advantageously of at least 1000 Pa.s, preferably of at least 1500 Pa.s, and more preferably of at least 2000 Pa.s (at share rate of 100 s "1 and temperature of 190 0 C). Besides, melt viscosity is advantageously of at most 2800 Pa.s and preferably of at most 2500 Pa.s. In certain embodiments of the present invention, the un-functionalized polyolefin (PO2) has melt flow index MI5 of at most 1 dg/min and melt viscosity of at least 2000 Pa.s (at share rate of 100 s "1 and temperature of 190 0 C).
• the functionalized polyolefin (FPO2) likewise functionalized polyolefin (FPOl), advantageously comprises functional groups chosen from carboxylic groups, their esters, their anhydrides and their salts.
• the functionalized polyolefin (FPO2) can be obtained by any technique known in the art. For example, by copolymerizing at least one olefin with at least one ethylenically unsaturated monomer bearing at least one suitable functional group. Preferably it is obtained by grafting at least one suitable grafting agent (G2) onto at least one un-functionalized polyolefm (PO2').
• the un-functionalized polyolefin (PO2') complies with all of the structural features of the un-functionalized polyolefin (POl ') and the functionalized polyolefin (FP02) complies with all of the features of the functionalized polyolefin (FPOl), at any level of preference. In certain preferred embodiments, the un-functionalized polyolefin (PO2') complies with all of the structural features of the un-functionalized polyolefin (PO2), at any level of preference.
• Polymer composition (C2) optionally further comprises one or more additives like those previously described for (Cl).
• polymer composition (C2) further comprises at least one antioxidant. Addition of at least one antioxidant may be useful to improve thermal and chemical stability of polymer composition (C2) as well as long-term adhesion behavior of layer (L2).
• antioxidants which may be added to polymer composition (C2), besides those previously mentioned for (Cl), are for example phenolic antioxidants comprising one or more sterically hindered phenol groups and free from an ester group, or mixtures thereof.
• antioxidants mention may be made of: l,l,3-tris(2-methyl-4- hydroxy-5-t-butylphenyl) butane; 2,2'-isobutylidenebis (4,6-dimethylphenol); 2,2'- methylenebis (6-t-butyl-4-methylphenol); 2,6-bis( ⁇ -methylbenzyl)-4-methylphenol; 4,4'-thiobis-(6-t-butyl-m-cresol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 1 ,3,5- trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)benzene.
• the weight percent of the un-functionalized polyolefm (PO2) to the total weight of polymer composition (C2) is advantageously of at least 70 wt.%. In addition, it is advantageously of at most 99 wt.%.
• the weight percent of the functionalized polyolefm (FPO2) to the total weight of polymer composition (C2) is advantageously of at least 1 wt.%. In addition, it is advantageously of at most 30 wt.%.
• polymer composition (Cl) comprises an electrically conductive filler
• the weight percent of the un- functionalized polyolefm (PO2) to the total weight of polymer composition (C2) is of at least 85 wt.%, preferably of at least 90 wt.%.
• the weight percent of the functionalized polyolefm (FPO2) to the total weight of polymer composition (C2) is of at least 5 wt.% and preferably of at least 10 wt.%.
• the weight percent of the regrind to the total weight of polymer composition (C2) is advantageously of at least
• the un-functionalized polyolefm (PO2), the functionalized polyolefm (FPO2) and other optional components including additive(s) and/or a regrind of layer(s)(Ll) and/or (L2) may be mixed together in any manner known in the art. Mixing may be done preliminary to co-extrusion in a separate extruder or it may be done immediately before co-extrusion in the same extruder used to feed the co-extrusion die.
• the multilayer polymer structures of the invention generally have high tensile properties, high impact and tear strength and, in their conductive versions, dissipate static electrical charge very efficiently.
• invented multilayer structures may be used for: hot water applications where low permeation and higher temperature is required, low cost vapor lines, heat exchanger tubing, high temperature fuel system applications, and particularly at higher temperatures than conventional polyamide applications, fuel tanks, insulating devices in electric motors and other electronic devices, in industrial transformers for insulators and compressor motor coil insulators, packaging, coating.
• the present invention is also directed to a shaped article comprising the invented multilayer structure as above described.
• the invented shaped article is advantageously a hollow body chosen from the group of pipes, hoses, tubes, containers, fuel tanks and bottles.
• the hollow body is a hose the inner part of which is contacted with fuel.
• the present invention is also directed to a process for manufacturing the shaped article as above described, said process comprising co-extruding or co-blow molding polymer compositions (Cl) and (C2).
• Impact modifier II. a*: FUSABOND ® EMB226DE maleic anhydride grafted linear low density polyethylene (MAH-g-LLDPE), available from DuPont de Nemours, having melt flow index MI2 of 1.5 g/10min (190°C/2.16 kg) and grafted MAH content of 0.75 -1.0 wt.%.
• Impact modifier (II. b*): EXXELOR® VA 1201 maleic anhydride grafted medium viscosity ethylene copolymer, available from Exxon Mobil Chemical, having melt flow index MI2 of 1.5 g/10min (190°C/2.16 kg) and grafted MAH content of 0.75 -1.0 wt.%.
• Non-electrically conductive bilayer structure (Ll*-L2*) was fabricated by co- extrusion of unfilled polymer compositions (Cl*) with physical blend (B2*)5/95 A) Preparation of unfilled polymer composition (Cl*).
• IXEF PMXD6 was submitted to solid state polymerization treatment in order to increase its molecular weight.
• An oil-jacketed vessel with internal rotating screws was charged with 40 lbs poly(meta-xylylene adipamide) polymer pellets. After charging and closing the reactor, the screw rotation was set to 24 rpm.
• the reactor was purged with N 2 After several hours of nitrogen sparging, the side port plug of the exit vent was removed for the addition of 65 ml of water and then replaced. While keeping N 2 purge, the oil heater set point was set to 121°C. The oil was held at 121 0 C for one hour and then the set point was changed to 204 0 C. After the internal pellet temperate reached 150 0 C, heating of the oil was continued for 4 hours, as shown in Table 1. The pellets were allowed to cool down under nitrogen before the reactor was opened. The_starting and final pellet properties are described in Table 2.
• Physical blend (B2*)5/95 comprising un-functionalized polyolefm (PO2*) and functionalized polyolefm (FPO2*) was obtained by dry blending, by manual tumbling, pellets of ELTEX ® B6922 N1347 (HDPE) and PRIEX ® 11002 (MAH-g- HDPE) (Table 5).
• a modular cylindrical die comprising two stacked flow distributors (SFDl , SFD2) enabling to obtain two layer tubing with an external diameter (OD) of 8 mm and an internal diameter (ID) of 6 mm (Fig.l).
• the die nozzle had an OD of 16 mm and an ID of 11.5 mm.
• the calibrator had an ID of 8.3 mm.
• SFDl was used to obtain the inner layer.
• SFD2 was used to obtain the outer layer.
• Each of the stacked flow distributors SFDl and SFD2 was fed by one extruder.
• the extruder El was used to extrude and feed polymer composition (Cl*) forming the inner layer (Ll*) to the stacked flow distributor SFDl.
• the extruder E2 was used to extrude and feed physical blend (B2*)5/95 forming the outer layer (L2*) to the stacked flow distributor SFD2.
• the co-extrusion setup is shown in Fig.2.
• the extruder El had three barrel temperature zones: Zl, Z2 and Z3 respectively from inlet to outlet.
• the extruders E2 had three barrel temperature zones: Zl, Z2 and Z3 respectively from inlet to outlet.
• the modular cylindrical die had four different temperature zones as shown in Fig.3.
• TdI was the temperature of the back plate.
• Td2 was the temperature stacked flow distributor SFDl feeding layers (Ll*);
• Td3 was the temperature of the stacked flow distributor SFD2 feeding layer (L2*) and
• Td4 was the temperature of the die tip.
• D Co-extrusion of the tubular bilayer structure (Ll*-L2*) and adhesion tests.
• the parison of the tubular structure at the exit of the die was calibrated and cooled using a conventional system comprising a vacuum calibrator and a water spray bath also kept under vacuum. Table 6.
• Co-extrusion process parameters for tubular bilayer structure (Ll*-L2*), tubing's OD 8 mm
• Extruder El Collin® 20 mm.
• Extruder E2 Scamex® 30 mm.
• the adhesion between unfilled (Cl *) based layer (Ll *) and (B2*)5/95 based layer (L2*) was tested according to SAE J2260 (REV. November 2004, ⁇ 7.13, p.25 to 27) using four strips longitudinally cut in the tubing.
• the minimum and average peel strength measured for co-extruded tube is given in Table 7.
• Example 2 (Ll *-L2*V Electrically conductive bilayer structure (Ll*-L2*)' was fabricated by co- extrusion of filled polymer compositions (Cl *)' with physical blend (B2*)10/90 A) Preparation of filled electrically conductive polymer composition (Cl*)' and measurement of its electric conductivity.
• Polymer composition (Cl*)' was obtained by melt compounding the components shown in Table 8.
• pellet density for as compounded pellets was 1.11 g/cc.
• Table 9 Polymer composition (Cl*)' - Extruder operating conditions and temperature settings
• R is the resistance of a surface with width d and length / and R s is the surface resistivity. Results are given in Table 11.
• Physical blend (B2*) 10/90 comprising un-functionalized polyolefm (PO2*) and functionalized polyolefm (FPO2*) was obtained by dry blending, by manual tumbling, pellets of ELTEX ® B4922 N 1347 (HDPE) and PRIEX ® 11002 (MAH-g- HDPE) (Table 12)
• Extruder El Collin® 20 mm.
• Extruder E2 Collin® 30 mm.
• Co-extrusion equipment and process parameters were the same of Example 2. In this case there was no adhesion between layer (Ll*)' and layer ( ⁇ 2) (Table 15).
• Table 15 Peel strength between layers (Ll*)' and ( ⁇ 2) in co- extruded tubular bilayer structure (Ll*- ⁇ 2)'

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