Stock material or miscellaneous articles – Composite – Of fluorinated addition polymer from unsaturated monomers
Reexamination Certificate
2001-07-09
2004-05-25
Thibodeau, Paul (Department: 1773)
Stock material or miscellaneous articles
Composite
Of fluorinated addition polymer from unsaturated monomers
C428S422000, C428S476300, C428S516000, C525S072000, C525S199000, C524S504000, 15, C264S173120, C264S173140
Reexamination Certificate
active
06740412
ABSTRACT:
The present invention relates to a polymeric adhesive and to structures with multiple polymeric layers comprising a layer (A) made of thermoplastic halogenated hydrocarbon polymer bonded to a layer (C) made of thermoplastic non-halogenated polymer incompatible with (A) via a layer (B) based on a polymeric adhesive. The invention also relates to processes for the preparation of this adhesive and of these structures. The invention additionally relates to the use of this adhesive in the preparation of these structures and to the use of these structures in the manufacture of pipes, tubes, films, sheets, panels and hollow bodies.
Thermoplastic halogenated hydrocarbon polymers and more particularly thermoplastic fluorinated hydrocarbon polymers are polymers which exhibit an array of advantageous properties and in particular impermeability to liquids and gases, high chemical inertia and excellent behaviour towards ageing. For this reason, they have multiple applications in highly diverse fields and in particular in the transportation and storage of liquids and gases and in protection against corrosion. Nevertheless, they exhibit the disadvantage of being relatively expensive, with the risk of their outlets being restricted.
An appropriate means for reducing the cost of shaped articles made of this type of polymer consists in using these polymers in the form of structures with multiple polymeric layers (films, sheets, panels, pipes, hollow bodies, and the like) in which they are used in combination with other polymers, which furthermore contribute their own properties and advantages, such as, for example, mechanical strength, aptitude for sealing, resistance to scratching, and the like. However, thermoplastic halogenated hydrocarbon polymers and more particularly thermoplastic fluorinated hydrocarbon polymers are known to be materials which cannot easily be made to adhere to other polymers.
To solve this problem, numerous solutions have been provided and in particular to insert a layer of adhesive between the halogenated polymer and the incompatible polymer, in order to provide an adhesive bond between these two polymers.
This type of solution has been disclosed in particular in Patent Applications EP-A1-112,406, EP-A1-124,931 and EP-A1-484,053.
Thus, Patent Application EP-A1-112,406 relates to a multilayer hollow container composed of an internal layer made of thermoplastic fluorocarbon-comprising resin bonded to an external layer made of polyolefin via a layer made of a mixture of resins comprising a polyolefin grafted with an unsaturated glycidyl compound and a polyolefin.
Likewise, Patent Application EP-A1-124,931 discloses multiple-layer thermoplastic structures comprising a layer made of vinyl or vinylidene fluoride polymer bonded to a layer made of alpha-olefin polymer with the joint involvement of a vinyl acetate polymer and of a copolymer of ethylene and of vinyl acetate.
Patent Application EP-A1-484,053 mentions a process for the preparation of a 3-layer laminate composed of a layer of an olefinic polymer to which a layer of fluorinated resin is made to adhere by melting with the aid of an adhesive polymer which consists of a polymerization product of an olefinic polymer with a monomer comprising an alkyl (meth)acrylate and/or an unsaturated monomer comprising fluorine.
These types of adhesive layers provided as solutions in these specific cases do not, however, comprise a mixture of the two polymers which are to be made to adhere and for this reason exhibit adhesive properties which might be improved.
Provision has also been made to make a halogenated polymer, in this instance a fluorinated polymer, adhere to an incompatible polymer via two distinct layers of adhesive.
Thus, Patent EP-B1-206,689 relates to a laminate comprising at least two distinct layers of adhesive in contact, composed of a fluorinated hydrocarbon polymer modified by a carboxyl, acid anhydride, hydroxyl or epoxide group and of an alpha-olefin polymer modified by a carboxyl, acid anhydride, hydroxyl or epoxide group different from the preceding group. These two distinct layers of adhesive can be placed on a substrate layer prepared from a material chosen from various polymers, including poly(vinylidene fluoride), polyethylene and nylon. Thus, a 4-layer laminate is mentioned comprising a PVDF layer bonded to a PE layer via two distinct layers of adhesive. This multilayer structure exhibits the disadvantage of being composed of two layers of adhesive and thus a total of 4 layers, which presents technical problems during the industrial coextrusion, which can be more easily envisaged technically if it is limited to 3 layers, thus with a single layer of adhesive.
Due to their lower cost and to the technical considerations with regard to manufacture described above, structures having a single layer of adhesive are preferred to those comprising more than one layer of adhesive.
The problem which remains is therefore that of providing an adhesive which can satisfactorily bond to a layer of thermoplastic halogenated hydrocarbon polymer, on one side, and to a layer of incompatible thermoplastic polymer, on the other side, for the purpose of forming structures with multiple polymeric layers comprising only a single layer of adhesive.
In order to overcome the abovementioned disadvantage, the object of the present invention is to provide a homogeneous polymeric adhesive which comprises a mixture of the two polymers to be made to adhere and which thus makes it possible to provide good adhesion between a thermoplastic halogenated hydrocarbon polymer and an incompatible thermoplastic polymer.
Another subject-matter of the invention is, a process for the preparation of this adhesive and the use of this adhesive in the preparation of structures with multiple polymeric layers.
Another object of the invention is to provide structures with multiple polymeric layers comprising a layer (A) made of thermoplastic halogenated hydrocarbon polymer bonded to a layer (C) made of incompatible thermoplastic nonhalogenated polymer via a single layer (B) based on a homogeneous polymeric adhesive which makes it possible for these structures to combine good adhesion with good barrier properties and with a not excessively high cost, to be easily coextruded industrially and not to exhibit, for this reason, the abovementioned disadvantage.
Another subject-matter of the invention is a process for the preparation of these structures with multiple polymeric layers and the use of these structures with multiple polymeric layers in the manufacture of pipes, tubes, films, sheets, panels and hollow bodies.
The invention first of all relates to a polymeric adhesive which is particularly suitable for providing good adhesion between a thermoplastic halogenated hydrocarbon polymer and an incompatible thermoplastic polymer.
To this end, the invention relates to a polymeric adhesive which comprises a homogeneous mixture of at least three components: (a) at least one thermoplastic halogenated hydrocarbon polymer, (b) at least one copolymer of monoethylenic monomers which carry an alkyl carboxylate functional group and (c) at least one alpha-olefin polymer modified by the incorporation of at least one functional group chosen from a carboxyl, an acid anhydride, a hydroxyl and an epoxide.
The term “thermoplastic halogenated hydrocarbon polymer” is understood to denote homopolymers and copolymers obtained from monoethylenic monomers comprising at least two carbon atoms and at least one halogen atom chosen from fluorine and chlorine. It is also understood to denote mixtures of homopolymers and of copolymers. Mention may in particular be made, as examples of thermoplastic halogenated hydrocarbon polymer which can be used in the present invention, of homopolymers and copolymers of vinylidene fluoride, of vinyl fluoride, of trifluoroethylene, of chlorotrifluoroethylene, of tetrafluoroethylene, of hexafluoropropylene, of vinyl chloride and of vinylidene chloride, as well as copolymers of one of these monomers with another nonhalogenated monoethylenic monomer, such as
Declerck Fredy
Laurent Guy
Oreins Jean-Marie
Thulliez Vincent
Kruer Kevin R
Schulman B. Aaron
Solvay ( Societe Anonyme)
Stites & Harbison PLLC
Thibodeau Paul
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