Thermoplastic polymer compositions with excellent adhesion to polyolefin and fluoropolymer based materials - Patents.com

Abstract

The present invention relates to a thermoplastic polymer composition comprising: a) one or more functionalized polyolefins as component A; b) one or more functionalized fluoropolymers as component B; c) one or more non-functionalized polyolefins as component C; and d) one or more non-functionalized fluoropolymers as component D, wherein: the total amount of components A and B is 1-50% by weight of the total amount of components A, B, C and D; the total amount of components C and D is 50-99% by weight of the total amount of components A, B, C and D; the weight ratio of components A and B is 1:1.2-1:10; the weight ratio of components C and D is 1:1.2-1:5; the one or more functionalized fluoropolymers (B) comprise a functional group Y, and one of the following conditions i) or ii) is met: i) the functional groups X and Y are reactive with each other; ii) the functional groups are non-reactive with each other, the thermoplastic polymer composition comprises an additional component (E), the component (E) consisting of one or more reactive compatibilizer compounds, the reactive compatibilizer compounds comprising in each molecule of the reactive compatibilizer compound at least one free functional group reactive with functional group X and one free functional group reactive with functional group Y.

Description

[Technical field]

[0001] This application claims priority to European Patent Application No. 22158624.1, filed February 24, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to thermoplastic polymer compositions having excellent adhesion to both polyolefin-based and fluoropolymer-based materials, to methods for preparing these compositions, and to multi-layer structures in which one of the layers is made from the thermoplastic composition of the present invention. [Background technology]

[0003] Polyolefins, especially polymers of ethylene and propylene, are used to manufacture pipes, tanks, containers, and vessels for the transport and storage of water, chemicals, and liquid hydrocarbons, especially oils and fuels. However, the chemical resistance and impermeability of these polymers to these hydrocarbons is not always sufficient for all applications for which they are intended. To overcome this drawback, another polymeric barrier layer is placed between the hydrocarbon to be transported or stored and the polyolefin. Polymers that are often used for this purpose, combining chemical resistance and impermeability, are fluoropolymers, especially polymers and copolymers of vinylidene fluoride (VDF).

[0004] However, fluoropolymers do not adhere well to polyolefins, and compositions have therefore been developed with a view to improving the adhesive properties of fluoropolymers.

[0005] The present invention aims to provide a composition that allows for strong adhesion of a fluoropolymer layer to an incompatible polyolefin polymer layer in the form of a single adhesive layer.

[0006] EP-A-0650987 describes fluoropolymers with adhesive properties, whose backbone based on fluorine-containing hydrocarbons is grafted with compounds containing reactive or polar functional groups with adhesive properties. These functional groups may be carboxyl groups, carboxylic anhydride residues, epoxy groups, hydroxyl groups, isocyanate groups, ester groups, amide groups, amino groups and hydrolyzable groups including silyl or cyano radicals. However, these polymers do not adhere well to polyolefins.

[0007] EP-B-206689 relates to a laminate comprising at least two different contacting adhesive layers, composed of a fluoropolymer modified by carboxyl, anhydride, hydroxyl or epoxide groups and an α-olefin polymer modified by carboxyl, anhydride, hydroxyl or epoxide groups different from the aforementioned. These two different adhesive layers can be arranged on a substrate layer made of a material selected from various polymers such as polyvinylidene fluoride, polyethylene and nylon. Thus, a four-layer laminate is mentioned, comprising a polyvinylidene fluoride layer bonded to a polyethylene layer by two different adhesive layers. This multilayer structure has the disadvantage in particular of being composed of two adhesive layers, thus four layers in total, which causes technical problems during coextrusion on an industrial scale. A limitation to three layers and therefore one adhesive layer is technically easier to predict.

[0008] US 2009 / 324867 A describes a polymer composition with adhesive properties comprising a fluoropolymer A grafted with a functional group f1, a polyolefin B grafted with a functional group f2 selected from an acid group and an anhydride group, and an olefin copolymer C having a functional group f3 capable of reacting with the functional group f1. The composition is produced mainly using functionalized polymers.

[0009] US Patent No. 7,094,836 B2 describes a compatibilizer for blends of polyolefins and fluoropolymers, comprising a reaction product of a fluoropolymer and a polyolefin having functional groups that react with each other. This document also describes an alternative compatibilizer, comprising a fluoropolymer and a polyolefin having functional groups that do not react with each other, and a third component having at least two functional groups that react with the functional groups of the polyolefin and the fluoropolymer, respectively. In all examples, the weight ratio of functionalized polyolefin to functionalized fluoropolymer is 1 or more.

[0010] There remains a need for further improved thermoplastic compositions that are easy to prepare and process, and that have improved adhesion to both fluoropolymer-based and polyolefin-based materials. In particular, there is a need for thermoplastic compositions of this type that can include relatively high molecular weight polymers to withstand continuous application temperatures of 100° C. or higher, and that can be prepared by compounding the ingredients in standard extrusion equipment using relatively moderate temperatures and pressures. Summary of the Invention

[0011] The present invention relates to a) One or more functionalized polyolefins as component A b) One or more functionalized fluoropolymers as component B c) one or more non-functionalized polyolefins as component C d) one or more non-functionalized fluoropolymers as component D A thermoplastic polymer composition comprising: the total amount of components A and B is 1 to 50% by weight of the total amount of components A, B, C, and D, the total amount of components C and D is 50 to 99% by weight of the total amount of components A, B, C, and D, The weight ratio of components A and B is 1:1.2 to 1:10. The weight ratio of components C and D is 1:1.2 to 1:5; said one or more functionalized polyolefins (A) comprise a functional group X and said one or more functionalized fluoropolymers (B) comprise a functional group Y; Under any of the following conditions i) or ii): i) the functional groups X and Y are reactive with each other; ii) said functional groups are non-reactive with each other, said thermoplastic polymer composition comprising an additional component (E), said component (E) consisting of one or more reactive compatibilizer compounds, said reactive compatibilizer compounds comprising in each molecule of said reactive compatibilizer compound at least one free functional group reactive with functional group X and one free functional group reactive with functional group Y; The present invention relates to a thermoplastic polymer composition, in which one of the above requirements is satisfied. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The thermoplastic polymer composition of the present invention comprises a) One or more functionalized polyolefins as component A b) One or more functionalized fluoropolymers as component B c) one or more non-functionalized polyolefins as component C d) one or more non-functionalized fluoropolymers as component D It contains four essential ingredients:

[0013] The term "polyolefin" means a polymer having at least 50 mole percent of its repeat units (based on all repeat units of the polymer) derived from at least one linear olefin.

[0014] Examples of linear olefins include linear α-monoolefins containing 2 to 20, preferably 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Preferred linear α-monoolefins are ethylene and propylene. In the context of the present invention, the term "polyolefin" encompasses both functionalized and non-functionalized polyolefins.

[0015] The term "fluoropolymer" is understood to mean a polymer whose repeat units of at least 40 mol% (based on the total repeat units of the polymer) are derived from at least one fluoromonomer. The fluoropolymer may be a homopolymer, a copolymer formed by combining several fluoromonomers, or a copolymer formed by one or more fluoromonomers and one or more non-fluorinated monomers. These copolymers may in particular be random, block or graft copolymers. In the context of the present invention, the term "fluoropolymer" encompasses both functionalized and non-functionalized fluoropolymers.

[0016] The term "fluoromonomer" is understood to mean any monomer that contains at least one fluorine atom, and usually contains at least one ethylenic unsaturation. Examples of fluoromonomers include fluorinated vinyl monomers. The expression "fluorinated vinyl monomer" is understood to represent monoethylenically unsaturated fluorinated monomers that are aliphatic and have one or more fluorine atoms. Examples of fluorinated vinyl monomers include vinyl monomers that do not contain hydrogen atoms, such as tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene; perfluorovinyl ether monomers (PAVE), such as perfluoromethyl vinyl ether and perfluoropropyl vinyl ether; and partially hydrogenated fluorinated vinyl monomers, such as vinyl fluoride, trifluoroethylene, and 3,3,3-trifluoropropene; most specifically vinylidene fluoride.

[0017] The expression "non-fluorinated monomer" is understood to mean any monomer that does not contain a fluorine atom, which usually contains at least one ethylenic unsaturation. Examples of non-fluorinated monomers are α-monoolefins such as ethylene and propylene; styrene and non-fluorinated styrene derivatives; non-fluorinated chloromonomers such as vinyl chloride and vinylidene chloride; non-fluorinated vinyl ethers; non-fluorinated vinyl esters such as vinyl acetate; (meth)acrylic acid esters; nitriles; and amides such as acrylonitrile and acrylamide; anhydrides; unsaturated carboxylic acids (in acid or salt form) such as acrylic acid; sulfone monomers (in acid or salt form) such as vinylsulfonic acid.

[0018] The term "functionalized" in the present invention, when referring to a polyolefin polymer or a fluoropolymer, means a polymer that contains 0.05 mol % to 50 mol % (based on the total number of repeat units of the polymer, excluding functional groups that may be present as polymer chain ends) of functional groups available for reaction with other functional groups in the composition. In the context of the present invention, a "functional group" is conventionally defined in chemistry as a group of atoms in a molecule that has characteristic chemical properties and characterizes the reactivity of that molecule.

[0019] As known to those skilled in the art, non-functionalized polymers may contain functional groups as chain ends. These functional groups may originate from polymerization reactions and depend on the initiator and / or chain transfer agent used. In the functionalized polymers used in the present invention, instead, functional groups are distributed along the polymer chain, as in the case where such functional groups originate from copolymerization with functionalized comonomers and / or grafting of functionalized species. Without being bound by theory, it is believed that functional groups distributed along the polymer chain are more effective in compatibilizing the composition of the present invention than functional groups located as chain ends, due to the closer interconnection between functionalized polyolefins and functionalized fluoropolymers.

[0020] The amount of functional groups can be measured using NMR techniques, which also allow one skilled in the art to distinguish functional groups that have been inserted by grafting and / or copolymerization along the polymer backbone from those present as polymer chain ends. The two types of functional groups can be distinguished by their different chemical properties or, in the case of chemically similar moieties, by changes in NMR relaxation times.

[0021] Preferably, the functionalized fluoropolymers and functionalized polyolefins for use in the present invention contain functional groups selected from carboxylic acids and their salts, anhydrides, esters, hydroxyls, amides, amines / ammonium salts, aminophenols, carboimides, epoxies, Br, I, silanes, siloxanes, sulfonic acids and their salts, phosphonic acids and their salts, isocyanates, nitriles, oxazolines, lactams, C=C double bonds. Most preferred functionalized fluoropolymers and functionalized polyolefins for use in the present invention contain functional groups selected from carboxyls, hydroxyethyl carboxylates, and epoxides.

[0022] In some preferred embodiments, the functionalized fluoropolymers used in the present invention contain 0.1 mol % to 50 mol %, more preferably 0.5 to 30 mol %, and even more preferably 0.8 to 20 mol % of functional groups (based on all repeat units of the polymer), excluding any functional groups that may be present as polymer chain ends.

[0023] In some preferred embodiments, the functionalized polyolefin used in the present invention contains 0.1 mol % to 50 mol %, more preferably 0.5 to 30 mol %, and even more preferably 0.8 to 20 mol % of functional groups (based on all repeat units of the polymer), excluding any functional groups that may be present as polymer chain ends.

[0024] A polymer that contains 0 mole % or less than 0.05 mole % of functional groups, excluding any functional groups that may be present as polymer chain ends, is considered to be a non-functionalized polymer in the context of this invention.

[0025] The functionalized polymer in the present invention may be a functionalized polyolefin or a functionalized fluoropolymer, as described below. The functionalization of the polymer can be achieved by any method known in the art. Typically, functionalized polymers are obtained during polymerization by introducing functionalized monomers into the polymerization medium during the polymerization process, or after polymerization by a grafting process that grafts non-functionalized polymers with sites that have functional groups. Both of these methods of introducing functional groups are well known in the art for a variety of polymers and a variety of functional groups, and will not be described in detail here.

[0026] Suitable functionalizing comonomers or compounds to be grafted onto the polymer backbone are, for example: i) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one group selected from acid and anhydride groups as functional groups, such as unsaturated mono- or dicarboxylic acids and their salts, and / or unsaturated mono- or dicarboxylic anhydrides. Specific examples are maleic anhydride, itaconic anhydride, citraconic anhydride, bicyclo-2,2,1-hept-2-ene-5,6-dicarboxylic anhydride or acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, all acids may be in the form of acid or salt. ii) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one ester group as a functional group, such as vinyl acetate, vinyl propionate, monomethyl maleate, dimethyl maleate, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, n-propyl methacrylate, n-butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, diethyl fumarate, dimethyl itaconate, and diethyl citraconate. iii) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one amide group as a functional group, such as acrylamide and methacrylamide. iv) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one epoxy group as a functional group, such as allyl glycidyl ether. v) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one amino group as a functional group, such as allyl-amines. vi) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one halogen group selected from bromine or iodine as a functional group, which can react by a radical mechanism. vii) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one silane or alkoxysilane group as a functional group, such as vinyltrimethylsilane, vinyltris-trimethylsiloxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane. viii) Compounds comprising at least one organic group having at least one terminal α-β-unsaturated carbon-carbon bond and at least one sulfonic acid group or phosphonic acid group, such as vinyl sulfonic acid or vinyl phosphonic acid (including salts thereof).

[0027] Suitable polymers for use as non-functionalized polyolefins in the present invention are polyolefins, as defined above, having at least 50 mol %, preferably at least 60 mol %, particularly preferably at least 70 mol %, and most preferably at least 80 mol % of their repeat units (based on all repeat units of the polymer) derived from at least one linear olefin and containing less than 0.05 mol % (preferably 0%) (based on all repeat units of the polyolefin) of functional groups (excluding functional groups that may be present as polymer chain ends).

[0028] The non-functionalized polyolefins may in particular be chosen from the homopolymers of the aforementioned olefins or from the copolymers of these olefins, in particular of ethylene and propylene, with one another or with one or more comonomers.

[0029] The comonomers, if present, may preferably be chosen from the following: · linear α-monoolefins as mentioned above; · Branched α-monoolefins containing 4 to 12 carbon atoms, such as 3-methylbutene, 4-methylpentene, and 5-methylhexene; · Aryl vinyl monomers such as styrene type monomers; · Conjugated dienes such as butadiene, isoprene, and 1,3-pentadiene; Non-conjugated dienes such as 1,4-pentadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, and bicyclo[2.2.1]octo-2,5-diene.

[0030] The non-functionalized polyolefin may include a blend of different polyolefins as described above.

[0031] The functionalized polyolefin suitable for the present invention can be selected from polyolefins having the general structure (including preferred options) described for non-functionalized polyolefins, with the only difference being that a certain amount of functional group is introduced into the molecule. The functional group can be introduced into the molecule using any method known in the art. For example, a certain amount of monomer having a functional group can be added during polymerization to form a copolymer containing a functionalized monomer in the polymer chain, or a monomer having a functional group can be grafted onto the polymer chain using conventional polymer grafting procedures (see, for example, EP-A-0650987).

[0032] A preferred functionalized polyolefin is selected from polymers that contain at least 50 mol % of repeating units derived from at least one type of linear olefin, based on the total amount of repeating units of the polymer, and also contain 0.1 mol % to 50 mol % of functional groups, excluding functional groups that may be present as polymer chain terminals, based on the total amount of repeating units of the polymer.

[0033] Examples of functionalized polyolefins are copolymers of ethylene, propylene, or mixtures thereof with acrylic acid, acrylic acid esters, glycidyl (meth)acrylate, vinyl acetate, and polymers of ethylene, propylene, or mixtures thereof grafted with acrylic acid, acrylic acid esters, glycidyl (meth)acrylate, vinyl acetate.

[0034] The non-functionalized fluoropolymer for use in the present invention is any fluoropolymer as defined above, whose repeating units are derived from at least 40 mol%, preferably at least 50 mol%, particularly preferably at least 60 mol%, most preferably at least 70 mol% (based on the total repeating units of the polymer) of one or more fluoromonomers, and contain less than 0.05 mol% (preferably 0%) (based on the total repeating units of the fluoropolymer) of functional groups (excluding functional groups that may exist as polymer chain ends).Examples of non-functionalized fluoropolymers suitable for the present invention can in particular include homopolymers of vinylidene fluoride, vinyl fluoride, trifluoroethylene or chlorotrifluoroethylene, and copolymers formed by these fluoromonomers together or with at least one other fluoromonomer as defined above (including fluoromonomers that do not contain hydrogen atoms, such as tetrafluoroethylene, hexafluoropropylene, perfluorovinyl ether or perfluoroalkyloxyvinyl ether). Examples of such copolymers and terpolymers include copolymers and terpolymers of vinylidene fluoride, and copolymers and terpolymers of chlorotrifluoroethylene and at least one other fluoromonomer as defined above, including fluoromonomers that do not contain hydrogen atoms, such as tetrafluoroethylene, hexafluoropropylene, perfluorovinyl ether, or perfluoroalkyloxyvinyl ether. Also include copolymers and terpolymers of at least one of the above-mentioned fluoromonomers and at least one non-fluorinated monomer.

[0035] The non-functionalized fluoropolymer in the composition according to the invention is preferably chosen from vinylidene fluoride polymers.

[0036] For purposes of this invention, a vinylidene fluoride polymer is a fluoropolymer that contains at least 50 mole percent (based on the total number of repeat units of the polymer) of repeat units derived from vinylidene fluoride.

[0037] Examples of vinylidene fluoride polymers include, in particular, homopolymers of vinylidene fluoride and their copolymers with other ethylenically unsaturated monomers, fluorinated or non-fluorinated.

[0038] Preferred vinylidene fluoride polymers for use in the present invention are those in which at least 60 mol % of the repeat units (based on the total number of repeat units of the polymer) are derived from vinylidene fluoride. Preferred comonomers, when present, are hexafluoropropylene, trifluoroethylene, and chlorotrifluoroethylene.

[0039] The functionalized fluoropolymer suitable for the present invention can be selected from the fluoropolymers having the general structure (including preferred options) described for non-functionalized fluoropolymers, which differs only in that a certain amount of functional group is introduced into the molecule.The functional group can be introduced into the molecule by any method known in the art.For example, a certain amount of monomer having functional group can be added during polymerization to form a copolymer containing functionalized monomer in the polymer chain, or the monomer having functional group can be grafted into the polymer chain by using conventional polymer grafting procedures (see, for example, EP-A-0650987).

[0040] A preferred functionalized fluoropolymer is selected from vinylidene fluoride polymers that contain at least 50 mol % of repeating units derived from vinylidene fluoride and also contain 0.1 mol % to 50 mol % of functional groups, excluding functional groups that may be present as polymer chain ends, based on the total amount of repeating units of the polymer.

[0041] Examples of suitable functionalized fluoropolymers are acrylic acid (or its salts), acrylic acid esters, hydroxymethyl acrylate, hydroxyethyl acrylate, maleic anhydride, silane group-containing monomers, glycidyl (meth)acrylate, sulfonic acid-containing monomers such as vinylsulfonic acid in acid or salt form, monomers containing a labile halogen mojety (selected from Br and I), vinylidene fluoride copolymers with amine group-containing monomers, vinylidene fluoride homo- or copolymers grafted with the same compounds mentioned above as possible comonomers.

[0042] The thermoplastic polymer composition according to the invention comprises functionalized moieties (components A and B) and non-functionalized moieties (components C and D). For the invention to function as expected, it is essential that the functionalized moieties represent 1-50% by weight of the total amount of components A, B, C and D. An amount of components A and B less than 1% by weight is not sufficient to compatibilize the normally immiscible components C and D, resulting in poor adhesion properties of the mixture to polyolefin or fluoropolymer surfaces and reduced mechanical properties of the mixture.

[0043] Amounts of components A and B greater than 50% by weight are undesirable because the composition will have poor adhesion to fluoropolymers and polyolefins and poor processability. Also, functionalized polymers are typically more complicated and expensive to manufacture than non-functionalized polymers, so it is desirable to use them in the minimum amount necessary for the invention to function effectively. Preferably, the functionalized moiety A+B comprises 1-50% by weight, more preferably 2-40% by weight, even more preferably 3-30% by weight, and most preferably 4-13% by weight of the total amount of components A, B, C, and D.

[0044] Another essential feature of the present invention is that components A and B must be present in the thermoplastic polymer composition of the present invention in a selected weight ratio A:B of 1:1.2 to 1:10, preferably 1:1.5 to 1:6, more preferably 1:1.75 to 1:4.

[0045] The amount of functional groups present in the functionalized polymer of the present invention is also relevant: it can generally be said that if a functionalized polymer is used in which the amount of functional groups per mole is in the lower part of the range, it is preferred that the amount used is in the higher part of the range, and vice versa.

[0046] Usually, the ratio of the total amount (mol) of functional groups supplied by component A to the total amount (mol) of functional groups supplied by component B is preferably 1:4 to 4:1, more preferably 3:1 to 1:3.

[0047] For the present invention to function as expected, it is also essential that the non-functionalized portion, i.e. the total amount of components C and D, represents 50-99% by weight, preferably 60-99% by weight, more preferably 70-99% by weight, even more preferably 80-99% by weight, and most preferably 87-99% by weight of the total amount of components A, B, C, and D. Another essential feature of the present invention is that the weight ratio of components C and D is 1:1.2-1:5, preferably 1:1.3-1:4, and more preferably 1:1.6-1:3.5.

[0048] The required ratios between components A and B and between components C and D are essential to provide a composition with the desired properties, combining low cost, ease of manufacture and processing (low melt viscosity, low extruder residue / fouling), excellent mechanical properties, and excellent adhesion to a variety of surfaces, including especially polyolefin and fluoropolymer surfaces.

[0049] The fundamental principle underlying the present invention is that the functionalized components A and B must interact with one another through chemical reactions driven by the functional groups to form a composite phase that allows mixing of the otherwise immiscible non-functionalized components C and D. The resulting compositions are surprisingly easy to prepare by extrusion, are stable, and are highly effective at adhering to both fluoropolymer- and polyolefin-based surfaces.

[0050] The one or more functionalized polyolefins (component A) contain the functional group X. The one or more functionalized fluoropolymers (component B) contain the functional group Y.

[0051] The interaction between component A and component B can occur directly or indirectly. In one embodiment, functional groups X and Y are reactive with each other, in which case the presence of an additional component is not necessary.

[0052] In another embodiment, the functional groups X and Y are not reactive with each other. In this embodiment, the thermoplastic polymer composition of the present invention must include an additional component (E).

[0053] Component (E) consists of one or more reactive compatibilizer compounds. The reactive compatibilizer compounds are compounds that contain, for each molecule, at least one free functional group that reacts with functional group X and one free functional group that reacts with functional group Y. The amount of component E is typically 0.1-90%, preferably 0.5-75%, more preferably 1-50%, and most preferably 3-30%, based on the total weight of components A and B, as appropriate.

[0054] Preferably, the reactive compatibilizer, if present, is not a polymeric material, but may be an oligomer, and typically has a molecular weight of less than 10000 Daltons, preferably less than 2000 Daltons. Reactive compatibilizers suitable for use in component E of the present invention are, for example: These include polycarboxylic acids such as adipic acid and their salts, polyalcohols such as glycols, polyglycidyl ethers (DGEBA), polyamines (Jeffamine); allyl esters (TAIC); and multiolefins (bisolefins).

[0055] Additional examples of compounds that can be used as component E in the present invention are aminocyclohexanol, p-aminobenzoic acid, ethylenediamine, propylenediamine, 1,4 butanediamine, 1,5 pentanediamine, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, isocyanates having the formula R(NCO)m, where n is an integer from about 2 to 4, or diols having 2 to about 20 carbon atoms, optionally having an ether linkage.

[0056] For purposes of the present invention, functional groups are considered to be reactive with each other if they can undergo a chemical reaction, such as, for example, addition / substitution (e.g., amidation, imidization, esterification, concerted addition, urea formation, urethane formation), exchange reactions (e.g., aminolysis, transesterification, ester transfer, amide-transesterification), ring opening reactions (e.g., epoxide ring, oxazoline ring, lactam ring), or ionic bonding reactions (e.g., pyridine / amine, or vitrimer formation) during melt processing of the thermoplastic compositions of the present invention.

[0057] Examples of reactive pairs between functional groups are: Carboxylamine Carboxyl-epoxide Carboxyl-oxazoline Carboxyl-carbodiimide Carboxyl-Hydroxyl Epoxide-Hydroxyl Maleic anhydride-amine Maleic anhydride - hydroxyl Maleic anhydride - C=C double bond Maleate-C=C double bond Ester-amine Ester-amide Ester-ester Ester-Hydroxyl Oxazoline-phenol Lactam-amine Isocyanate-Hydroxyl Amine-hydroxyl Amine-Br, I selected from the halide Amine-epoxide ·Silane-Silane ·Silane-Hydroxyl / Halide ·Siloxane-Siloxane ·Siloxane-hydroxyl Siloxane-Br, I selected from the group consisting of halides Epoxides - Epoxides Nitrile-nitrile Nitrile-aminophenol Carboxyl - carboxyl in the presence of divalent cations Carboxylate - carboxylate in the presence of divalent cations Acrylates - acrylates in the presence of divalent cations ·Acrylates - Acrylates Carboxyl-Acrylates in the Presence of Divalent Cations C=C double bond-halides (selected from Br, I) ·C=C double bond-radical · Radical-radical.

[0058] It should be noted that in this application, and particularly in the list above, when referring to functional groups having acidic or basic properties, the reference to the acidic / basic form is intended to include the salt form, e.g., carboxyl includes carboxylate salts, amine includes ammonium salts, etc.

[0059] Preferably, in the present invention, when the groups X and Y are reactive with each other, they are selected from one or more of the reactive pairs described above. Also preferably, when the groups X and Y are reactive with each other and a reactive compatibilizer E is present, such reactive compatibilizer E comprises one functional group capable of forming one of the reactive pairs defined herein with the functional group X, and another functional group capable of forming one of the reactive pairs defined herein with the functional group Y.

[0060] In addition to components A, B, C, D and, optionally, E, the thermoplastic polymer composition of the present invention may contain one or more conventional additives for thermoplastic polymers, such as organic or inorganic colorants, fillers, stabilizers, antioxidants, acid scavengers, plasticizers, lubricants, tackifiers, etc. It may also contain compounds that act as catalysts to increase the rate of reaction between the functional groups of the functionalized polymer A and B and / or with the reactive compatibilizer E (if present).

[0061] In order to maintain the properties of the composition of the present invention, it is preferred that the total amount of all the above-mentioned additives that are not part of the essential components A to E of the present invention is less than 30%, preferably less than 10%, more preferably less than 5% based on the total weight of the composition. It is also preferred that the total amount of components A, B, C, d, and E (if present) represents at least 70% by weight, preferably 90% by weight, more preferably 95% by weight of the total weight of the composition.

[0062] The thermoplastic polymer composition of the present invention can be prepared by mixing the essential components A to E and the optional additives using any method available to the skilled person. Typically, the composition of the present invention can be prepared by melt processing, for example in an extruder. The term "extruder" is understood to mean a continuous device comprising at least one feed zone and at its outlet a discharge zone, which is preceded by a compression zone through which the molten mass passes. After the discharge zone, there may additionally be a granulator or a device for giving the extruded material its final shape. Advantageously, known extruders are used, based on the action of a single screw (including Buss extruders) or two screws, in the latter of which the screws can work together in co- or counter-rotation (same or opposite rotation).

[0063] The starting materials for obtaining the polymer composition of the present invention from components A, B, C, and D can be selected from individual polymers or pre-prepared polymer compositions in solid form, preferably in divided form such as pellets, granules, or powder. For example, the individual components A, B, C, and D in divided form are loaded into a twin-screw extruder, melted at a temperature higher than the highest melting point, mixed thoroughly to form a homogeneously molten polymer composition, extruded preferably trough one or more capillary dies, cooled, and made into divided form such as pellets, granules, or powder of the polymer composition of the present invention for subsequent use, or directly extruded into a finished product such as a film or pipe. When component E is present, it can simply be mixed with the other components in the extruder.

[0064] The thermoplastic polymer composition of the present invention is particularly useful in the construction of multi-layer structures, one of the layers being composed of the polymer composition of the present invention.

[0065] The multilayer structure includes at least one other layer that may be composed of various materials, both inorganic and organic. Inorganic materials that may be incorporated into the composition of this other layer may include metals and metal alloys, such as aluminum and steel. Organic materials that may be incorporated into the composition of this other layer may include thermoplastic polymers. Examples of thermoplastic polymers that may be incorporated into the composition of this other layer are fluoropolymer layers and polyolefin layers.

[0066] When used in articles such as multi-layer structures, the compositions of the present invention can be used as is or can be blended with reinforcing materials such as fillers, fibers, or fabrics to enhance mechanical resistance.

[0067] Typically in all multi-layer structures, all layers may contain fillers and / or fibers and / or fabrics blended with the thermoplastic polymer.

[0068] In particular, the compositions of the present invention can be utilized in a three-layer structure in which the central layer is composed of the composition of the present invention (optionally blended with fillers and / or fibers) and the upper and lower layers comprise a thermoplastic polymer as defined above.

[0069] In particular, the compositions of the present invention can be used as adhesives to promote adhesion between materials comprising one or more fluoropolymers and materials comprising one or more polyolefins.

[0070] A preferred multi-layer structure is a three-layer structure in which the central layer is composed of the polymer composition of the present invention, optionally blended with fillers and / or fibers and / or fabrics, and one of the upper or lower layers comprises one or more polyolefin polymers and the other comprises one or more fluoropolymers.

[0071] These multilayer structures can be manufactured according to any process known for this purpose and adapted to the nature of the constituent materials of each layer. The assembly of the layers can be carried out, for example, by bonding or hot pressing the constituent layers together, or by coating a solid layer with a powder or solution of the constituent material of the other layer, or by coextrusion, coextrusion blow molding, and coinjection molding, especially when the constituent materials of the layers are all thermoplastic.

[0072] Coextrusion is particularly suitable for producing the above-mentioned three-layered multilayer structure.In particular, the central layer comprises the polymer composition of the present invention, one of the upper and lower layers comprises one or more homopolymers or copolymers derived from ethylene and / or propylene, and the other comprises one or more fluoropolymers, such as homopolymers or copolymers derived from vinylidene fluoride.This coextrusion can be carried out, for example, in three extruders, preferably three single-screw extruders, feeding through a feed block to a die, or preferably feeding to a three-layered tubular die in the head that forms the final single pipe.

[0073] The multilayer structures thus produced can be manufactured in the final form of sheets and films, but also in the final form of hollow bodies such as pipes, hoses, flexible risers, cable coatings, etc.

[0074] The compositions of the present invention are particularly useful in the manufacture of pipes, tanks, containers and vessels for the transport and storage of gases or liquids, such as water or hydrocarbons, especially oils and fuels. In fact, polyolefin pipes, which are widely used due to their low cost and good mechanical properties, are relatively permeable to hydrocarbons. For this reason, it is desirable to have a barrier layer made of a fluoropolymer, such as a VDF polymer, as the inner layer of the pipe in direct contact with the hydrocarbons. However, such an inner fluoropolymer layer does not adhere well to the polyolefin layer due to the incompatibility of the materials. Introducing an intermediate layer made of the thermoplastic polymer composition of the present invention can effectively solve the problem of adhesion to both the fluoropolymer layer and the polyolefin layer.

[0075] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements in this application to the extent that any term may be unclear, the statements herein shall control.

[0076] Experimental section The present invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and is not intended to limit the scope of the invention.

[0077] raw materials Functionalized Polyolefin (Component A): Lotader® AX8840 is an ethylene copolymer in pellet form containing 8% by weight of glycidyl methacrylate obtained from SK functional polymers.

[0078] Functionalized fluoropolymer (component B): A VDF copolymer in powder form, containing 99 mol% VDF and 1 mol% acrylic acid monomer, with a melt index of 6 g / min (213°C / 2.16 Kg) and a melting point of 168°C, obtained from Solvay Specialty Polymers (hereinafter referred to as "POLYMER FF").

[0079] Non-functionalized polyolefin (Component C): Lupolen® 4261AG, a high molecular weight high density polyethylene from Lyondell Basell.

[0080] Non-functionalized fluoropolymer (component D): Solef® 6012 VDF homopolymer from Solvay Specialty Polymers.

[0081] Preparation of Thermoplastic Composition The blends were prepared by feeding the four component resins into the main gate of a ZSK 26Mc18 Coperion twin screw extruder (L / D=48).

[0082] The following temperature profile was used (see Table 1 below):

[0083] [Table 1]

[0084] The composition was then extruded through a die with two holes of 3 mm diameter. The extrudate was cooled in a water bath and granulated.

[0085] Adhesion Measurement A Carver auto Series plus press was used to make compression molded sheets of 1 mm thickness from the above thermoplastic compositions. After preheating at 230°C, the polymer was pressed at 16 tons for 1 minute and then pressure cooled in cold water. A thin Kapton film was placed in direct contact with the blend during molding to prevent it from sticking to the metal plate.

[0086] To evaluate the adhesion of the thermoplastic compositions to PVDF and PE, a three-layer structure was constructed from 1 mm thick sheets, sandwiched between equal sized samples of one polyolefin (Lupolen® 4261AG from Lyondell Basell) and one fluoropolymer (Solef® 6008 PVDF from Solvay Specialty Polymers), and the sandwich was overmolded at 230° C. / 4 bar.

[0087] Adhesion was evaluated by cutting 15 mm x 130 mm stripes from the three-layer structure and performing a 90° peel test using a Universal Instron 5500 dynamometer at a crosshead speed of 300 mm / min. The average peel strength is reported as the peel force normalized by the width of the stripe and is expressed in N / cm.

[0088] The following thermoplastic compositions according to the present invention were prepared as described below.

[0089] Example 1 Components A, B, C and D were melted, mixed and extruded at a screw speed of 60 rpm and a total output set at 5 kg / h. Component A: 340 g of Lotader® AX8840, Ingredient B: 660g of POLYMER FF Component C: 1020 g of Lupolen® 4261AG Ingredient D: 1980 g of Solef® 6012

[0090] Based on the total weight of the composition, the total amount of components A and B is 25% by weight, and the total amount of components C and D is 75% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:1.9.

[0091] Example 2 Components A, B, C, and D were melted, mixed, and extruded as in Example 1. Component A: 255 g of Lotader® AX8840, Ingredient B: 495g of POLYMER FF Ingredient C: 525 g of Lupolen® 4261AG Ingredient D: 1725 g of Solef® 6012

[0092] Based on the total weight of the composition, the total amount of components A and B is 25% by weight, and the total amount of components C and D is 75% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:3.3.

[0093] Example 3 Components A, B, C and D were melted, mixed and extruded at a screw speed of 100 rpm and a total output set at 15 kg / h. Component A: 232 g of Lotader® AX8840, Ingredient B: 448g of POLYMER FF Component C: 1208 g of Lupolen® 4261AG Component D: 2112 g of Solef® 6012

[0094] Based on the total weight of the composition, the total amount of components A and B is 17% by weight, and the total amount of components C and D is 83% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:1.7.

[0095] Example 4 Components A, B, C, and D were melted, mixed, and extruded as in Example 5. Component A: 136 g of Lotader® AX8840, Ingredient B: 264g of POLYMER FF Component C: 1304 g of Lupolen® 4261AG Component D: 2296 g of Solef® 6012

[0096] Based on the total weight of the composition, the total amount of components A and B is 10% by weight, and the total amount of components C and D is 90% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:1.8.

[0097] Example 1c Components A, B, C, and D were melted, mixed, and extruded as in Example 1. Component A: 255 g of Lotader® AX8840, Ingredient B: 495g of POLYMER FF Component C: 1065 g of Lupolen® 4261AG Ingredient D: 1,185 g of Solef® 6012

[0098] Based on the total weight of the composition, the total amount of components A and B is 25% by weight, and the total amount of components C and D is 75% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:1.1.

[0099] Example 2c Components A, B, C, and D were melted, mixed, and extruded as in Example 1. Component A: 255 g of Lotader® AX8840, Ingredient B: 495g of POLYMER FF Ingredient C: 285 g of Lupolen® 4261AG Component D: 1,965 g of Solef® 6012

[0100] Based on the total weight of the composition, the total amount of components A and B is 25% by weight, and the total amount of components C and D is 75% by weight. The weight ratio of components A and B is 1:1.9, and the weight ratio of components C and D is 1:6.8.

[0101] Adhesion to PVDF and HDPE was measured as described above, and the results are shown in Table 2, which show that examples of thermoplastic compositions according to the present invention provide excellent adhesion to both fluoropolymer and polyolefin surfaces.

[0102] [Table 2]

[0103] Data expressed as >x indicates that the sample mechanically failed when the instrument reached peel strength "x", meaning that the actual interlayer adhesion could not be precisely measured but was certainly higher than the indicated value "x".

Claims

1. 1. A thermoplastic polymer composition comprising: a) one or more functionalized polyolefins as component A b) one or more functionalized fluoropolymers as component B c) one or more non-functionalized polyolefins as component C d) one or more non-functionalized fluoropolymers as component D A thermoplastic polymer composition comprising: The total amount of components A and B is 1 to 50% by weight of the total amount of components A, B, C, and D, The total amount of components C and D is 50 to 99% by weight of the total amount of components A, B, C, and D, The weight ratio of components A and B is 1:1.2 to 1:10, The weight ratio of components C and D is 1:1.2 to 1:5, the one or more functionalized polyolefins (A) comprise a functional group X and the one or more functionalized fluoropolymers (B) comprise a functional group Y; - The following condition i) or ii): i) the functional groups X and Y are reactive with each other; ii) the functional groups are unreactive with each other, the thermoplastic polymer composition comprises an additional component (E), the component (E) consisting of one or more reactive compatibilizer compounds, the reactive compatibilizer compounds comprising in each molecule of the reactive compatibilizer compound at least one free functional group reactive with functional group X and one free functional group reactive with functional group Y; The thermoplastic polymer composition satisfies one of the following requirements:

2. 10. The thermoplastic polymer composition of claim 1, wherein the non-functionalized fluoropolymer is selected from vinylidene fluoride polymers containing at least 50 mole percent repeat units derived from vinylidene fluoride.

3. 2. The thermoplastic polymer composition of claim 1, wherein the functionalized fluoropolymer is selected from vinylidene fluoride polymers containing at least 50 mol% of repeat units derived from vinylidene fluoride, and the functionalized fluoropolymer also contains from 0.1 mol% to 50 mol% of functional groups Y, based on the total amount of repeat units of the polymer.

4. 2. The thermoplastic polymer composition of claim 1, wherein the unfunctionalized polyolefin is selected from polymers having at least 50 mole percent repeat units derived from at least one linear olefin, based on the total amount of repeat units of the polymer.

5. 2. The thermoplastic polymer composition of claim 1, wherein the functionalized polyolefin is selected from polymers having at least 50 mol % of repeat units derived from at least one linear olefin, based on the total amount of repeat units of the polymer, and also containing 0.1 mol % to 50 mol % of functional group Y, based on the total amount of repeat units of the polymer.

6. 2. The thermoplastic polymer composition of claim 1, wherein the functional groups X and Y are selected from carboxylic acids and their salts, anhydrides, esters, hydroxyls, amides, amines / ammonium salts, aminophenols, carboimides, epoxies, Br, I, silanes, siloxanes, sulfonic acids and their salts, phosphonic acids and their salts, isocyanates, nitriles, oxazolines, lactams, C=C double bonds.

7. 10. The thermoplastic polymer composition of claim 1, wherein the functional groups X and Y are reactive with each other and form one of the reactive pairs defined herein.

8. 2. The thermoplastic polymer composition of claim 1, wherein the functional groups X and Y are not reactive with each other and the additional component E comprises two functional groups, one of which is capable of forming one of the reactive pairs as defined herein with functional group X and the other of which is capable of forming one of the reactive pairs as defined herein with functional group Y.

9. A method for producing the thermoplastic polymer composition according to any one of claims 1 to 8, comprising the steps of: - Providing components A, B, C, D and optionally E; forming a homogeneous mixture by introducing the ingredients into an extruder; - extruding the homogeneous mixture; A method comprising:

10. Use of the thermoplastic polymer composition according to any one of claims 1 to 8 as an adhesive.

11. A multi-layer article, wherein at least one layer comprises the thermoplastic polymer composition of any one of claims 1 to 8.

12. 12. The multilayer article of claim 11 selected from a tube, a pipe, or a sheet.

13. Use of a pipe according to claim 12 for transporting gases or liquids, preferably oil.