FIELD OF INVENTION

[0001] The present invention relates to a blend of a fluoroelastomer and a semi-crystalline fluoroplastic which can be crosslinked for excellent heat resistance, chemical resistance and mechanical properties.

BACKGROUND OF THE INVENTION

[0002] Fluoropolymer compositions have been widely used in a variety of applications involving high temperatures and aggressive chemicals, such as heat-shrink products, seals, gaskets, O-rings, hoses and cable jackets in industrial, automotive, aerospace and/or oil well drilling equipment, for example.

[0003] Numerous efforts have been made to improve the mechanical properties of fluoropolymer-based materials. For example, US 2002/177664 A1 discloses fluoropolymer compositions, wherein particles of a semicrystalline fluoropolymer latex having a specific average particle size range are embedded in a fluoroelastomer matrix to provide favourable elastic retention properties and a smooth surface in the final product. US 2006/0142491 A1 discloses a processable rubber composition containing particles of a vulcanized fluorocarbon elastomer dispersed in a matrix of a thermoplastic polymeric material.

[0004] In order to advantageously combine the stability and chemical inertness of perfluorinated monomer units with enhanced elastomeric properties, US 7,476,711 B2 proposes melt blending of a perfluoroelastomer and a semi-crystalline copolymer with a particle size greater than 100 nm, adding a curative, and subsequently curing said composition to form a cured article. However, the mechanical properties of the thus obtained articles tend to deteriorate when exposed to high temperatures for prolonged periods of time. Therefore, it would be desirable to provide fluoropolymer compositions which exhibit further improved heat resistance.

[0005] In general, crosslinking of fluoroplastics via chemical or radiation crosslinking processes for developing higher temperature rated products such as moulded parts or tubings is challenging, particularly since sufficient compatibility of the initial components must be ensured.

[0006] In this context, US 5,409,997 A is specifically concerned with the provision of thermally stable fluoropolymer compositions and discloses a radiation-crosslinkable composition comprising a fluoropolymer of ethylene, tetrafluoroethylene and at least one monomer having at least one polyvalent atom in one or more side chains, as well as a coagent comprising a difunctional compound selected from the group consisting of an acrylate or salt of an acrylic acid and compounds wherein the difunctionality is provided by the presence of vinyl, epoxide, peroxide, or glycidal groups. However, the heat resistance of these fluoropolymer compositions, particularly at long-term exposure to temperatures above 240°C, still leaves room for improvement.

[0007] In view of the above, it remains desirable to provide fluoropolymer compositions which enable manufacturing articles which maintain favorable mechanical properties (e.g. tensile strength, elongation properties) when continuously exposed to extreme temperatures, both in the low temperature range (e.g. between -75°C and 0°C) and high temperature range (e.g. higher than 240°C).

SUMMARY OF THE INVENTION

[0008] The present invention solves this problem with the subject matter of the claims as defined herein. Further advantages of the present invention will be further explained in detail in the section below.

[0009] According to a first aspect of the present invention as specified in claims 1 to 11, a cross-linkable composition comprising a blend of (a) an elastomeric fluoropolymer and (b) a semi-crystalline fluoroplastic is provided. As has been found by the present inventors, said blend provides an improved combination of properties, with the components (a) and (b) being compatible to each other, and may be used for further processing to the final product by moulding or extrusion, for example, and subsequent cross-linking.

[0010] A second aspect of the present invention as specified in claim 12 relates to a cross- linked product obtained by subjecting the composition according to the first aspect to ionizing radiation, resulting in toughened, flexible and high temperature rated products. [0011] In further aspects, the present invention relates to heat-shrinkable articles (according to claim 13) and cable jackets or sealing elements (according to claim 14) comprising the cross-linked product according to the second aspect.

[0012] In another aspect, the present invention as specified in claim 15 relates to a process of manufacturing a cross-linked product, comprising the steps of: (i) mixing an elastomeric fluoropolymer and a semi-crystalline fluoroplastic to prepare a crosslinkable composition; (ii) optionally subjecting the crosslinkable composition to a forming step; and (iii) subjecting the crosslinkable composition to ionizing radiation to obtain the cross-linked product. [0013] Preferred embodiments of the cross-linkable composition according to the present invention and other aspects of the present invention are described in the following description and the claims.

DETAILED DESCRIPTION OF THE INVENTION

[0014] For a more complete understanding of the present invention, reference is now made to the following description of the illustrative embodiments thereof:

Cross-Linkable Fluoropolvmer Composition

[0015] In a first embodiment, the present invention relates to a cross-linkable composition comprising a blend of: (a) an elastomeric fluoropolymer, and (b) a semi-crystalline fluoroplastic.

[0016] In a preferred embodiment, the composition is cross-linkable by ionizing radiation as will be further explained below with respect to the second embodiment.

[0017] The terms “polymer” or “fluoropolymerTfluoroplastic”, as used herein, generally refer to a polymeric material or fluorine-containing polymeric material having one or more monomer species, including homopolymers, copolymers, terpolymers, and the like.

[0018] The term “semi-crystalline fluoroplastic” refers to a fluorine-containing polymeric material with detectable crystalline order (by differential scanning calorimetry, x-ray diffraction, density, and other methods), i.e. having areas of crystallinity with amorphous areas existing between the crystalline areas.

[0019] In terms of improved mechanical properties, it is preferred that the elastomeric fluoropolymer is not perfluorinated, but only partially fluorinated. More preferably, the elastomeric fluoropolymer is a copolymer comprising copolymerized units of a perfluorinated monomer and a non-fluorinated or partially fluorinated monomer, optionally with one or more additional types of monomers. The elastomeric fluoropolymer used in the present invention preferably contains between 20 to 80 wt.-%, based on the total weight of the elastomeric fluoropolymer, of copolymerized units of perfluorinated monomer and 5 to 80 wt.-% of non-fluorinated or partially fluorinated monomer. Further preferably, the perfluorinated monomer is a perfluoroalkylene, such as hexafluoropropylene (HFP) or tetrafluoroethylene (TFE), for example, of which tetrafluoroethylene (TFE) is particularly preferred. The non-fluorinated or partially fluorinated monomer is preferably selected from partially fluorinated hydrocarbon olefins (such as one or more of vinylidene fluoride, 1,2,3,3,3-pentafluoropropene (1-HPFP), 1,1,3,3,3-pentafluoropropene (2-HPFP), and vinyl fluoride) and non-fluorinated hydrocarbon olefins (such as ethylene, propylene or isobutylene, for example), the latter being further preferred. As non-fluorinated or partially fluorinated monomer, propylene is especially preferred. As elastomeric fluoropolymer, an alternating co-polymer of tetrafluoroethylene and propylene (TFE/P) is especially preferred. Commercially available examples thereof include, but are not limited to fluoroelastomers selected from the Aflas ^® 100/150 ranges available from AGC Chemicals Europe and the TBR range by DuPont Performance Elastomers.

[0020] The content of elastomeric fluoropolymer is preferably between 10 and 95 wt.-%, more preferably between 15 and 90 wt.-%, and further preferably between 20 and 80 wt.-% based on the total weight of the composition.

[0021] In the cross-linkable composition according to the present invention, the semi crystalline fluoroplastic is preferably a co-polymer, further preferably a co-polymer comprising fluoroalkylene and a perfluoroether as main chain monomers. The fluoroalkylene is preferably a perfluoroalkylene, such as hexafluoropropylene (HFP) or tetrafluoroethylene (TFE), for example, of which tetrafluoroethylene (TFE) is particularly preferred. The perfluoroether is not particularly limited and may include perfluoroalkoxy alkanes derived from (per)fluoroalkylvinylethers (PAVE) CF2-CFOR ^f , wherein R ^f is a perfluorinated group with 1 to 6 carbon atoms; or from perfluorooxyalkylvinylethers CF2- CFOX, wherein X is a Ci-Ci2-perfluorooxyalkyl having one or more ether groups. The co monomeric unit -CF2-CF(OR ^f )-, wherein R ^f is a perfluorinated group with 1 to 6 carbon atoms, is particularly preferred. Preferred co-monomers include perfluoro(ethyl vinyl ether) (PEVE), perfluoro(propyl vinyl ether) (PPVE) and perfluoro(methyl vinyl ether) (PMVE). Especially preferred melt-fabricable fluoropolymers include co-polymers such as PFA (TF E/PAVE copolymer), TFE/HF P/PAVE copolymer and/or PPVE and MFA (TFE/PMVE/PAVE copolymer wherein the alkyl group of PAVE has at least two carbon atoms). Among semi-crystalline fluoroplastics, thermoplastic fluoropolymers comprising acid anhydride functional groups have been shown to exhibit particularly favourable compatibility with elastic fluoropolymers.

[0022] The expression “acid anhydride functional group”, as used herein, denotes a residual group having two carboxyl groups in one molecule condensed by dehydration. [0023] Suitable acid anhydride functional groups are pendant groups which may be grafted onto one or more of the aforementioned co-monomers (e.g. by replacing a fluorine substituent) or provided independently as pendant group of a co-monomer, i.e. through co polymerization. Among compounds for grafting onto and thereby becoming part of the semi crystalline fluoroplastic, maleic acid and maleic anhydride (MAnh) are preferred. Maleic anhydride can be halogen-substituted, e.g., dichloromaleic anhydride and difluoromaleic anhydride. Grafting may be brought about by using a grafting compound comprising a linking group (including, but not limited to an unsaturated or saturated hydrocarbon group which is involved in addition or association of radicals (particularly an organic group having an a,b-unsaturated double bond at its terminal), an amino group or a phenol group which is involved in nucleophilic reaction, a peroxy group or an azo group. Preferred linking groups include a group having a carbon-carbon unsaturated bond. The amount of the grafting compound to be used for grafting is usually from 0.01 to 100 parts by weight, preferably from 0.1 to 20 parts by weight, per 100 parts by weight of the fluorine-containing polymer. In the case of a grafting compound of a polymer type, it may be used in a larger amount (up to about 50 parts by weight). Exemplary grafting methods and optional radical-forming agents used in the grafting process will be known to the skilled artisan and are disclosed in US 5,736,610 A, for example. Commercially available examples of a suitable semi crystalline fluoroplastics functionalized with acid anhydride functional groups include Fluon ^® PFA resins available from AGC Chemicals Europe.

[0024] In a preferred embodiment from the viewpoint of processability, the melting point of the semi-crystalline fluoroplastic comprising anhydride functional groups is in the range of from 240°C to 340°C, further preferably from 290°C to 320°C.

[0025] In addition, it may be preferred that the density of the semi-crystalline fluoroplastic is between 1.5 to 3 g/ml, preferably between 1.9 and 2.4 g/ml.

[0026] The cross-linkable composition according to the present invention preferably contains semi-crystalline fluoroplastic in a content of between 5 and 90 wt.-% based on the total weight of the composition, preferably between 10 and 80 wt.-%, and further preferably between 20 and 70 wt.-%.

[0027] While not being limited thereto, particularly favourable tensile strength and flexibility characteristics may be achieved by adjusting the weight ratio of elastic fluoropolymer to semi-crystalline fluoroplastic in the blend to the range of from 10 : 1 to 1 : 10, more preferably from 4 : 1 to 1 : 4, further preferably from 3 : 1 to 1 : 3, and especially preferably from 2.5 : 1 to 1 : 2.

[0028] The compositions according to the first embodiment of the present invention may contain additives commonly used in polymer formulations, such as radiation crosslinking promoters (or so-called prorads); antioxidants; UV-stabilizers; conductive fillers (such as carbon black for imparting electrical conductivity); acid acceptors or scavengers (e.g. zinc oxide); plasticizers, lubricants, and processing aids typically utilized in perfluoroelastomer compounding; and pigments (e.g. titanium dioxide or carbon black). Such additives are typically used in total contents of less than 15 wt.-%, preferably less than 10 wt.-%, based on the total weight of the cross-linkable composition. [0029] As examples of radiation crosslinking promoters, compound having at least two ethylenic double bonds, present as allyl, methallyl, propargyl, acrylyl, or vinyl groups may be mentioned, such as triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimellitate, triallyl trimesate, tetraallyl pyromellitate, diallyl isophthalate, diallyl terephthalate, 1,4-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate (TMPTM), diallyl esters of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)indane, diallyl adipate, diallyl phthalate (DAP), pentaerythritol tri methacrylate, glycerol propoxy trimethacrylate, liquid poly(1, 2-butadiene), tri-(2-acryloxyethyl)isocyanurate, tri-(2- methacryloxyethyl)isocyanurate, and combinations thereof. Mixtures of crosslinking promoters can be used. Preferably, radiation crosslinking promoters are used in a total amount of up to 8 wt.-%, more preferably in a total amount of up to 5 wt.-% based on the total weight of the cross-linkable composition, such as from 0.05 to 5 wt.-% or from 0.1 to 3 wt.-%.

[0030] As exemplary antioxidants, alkylated phenols, organic phosphite or phosphates, alkylidene polyphenols, thio-bis-alkylated phenols and polymerized derivatives thereof; dilauryl thio-dipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate (DSTDP), and combinations thereof may be mentioned. Preferably, the antioxidant(s) is (are) used in a total amount of up to 4 wt.-%, more preferably in a total amount of up to 2 wt.-% based on the total weight of the cross-linkable composition.

[0031] Advantageously, adjusting the type and quantity of components of the cross-linkable composition according to the first embodiment allows for a fine-tuning of toughness and flexibility of the blend, which is then ready for further processing (including moulding and/or extrusion, for example). Upon cross-linking, these properties are then stabilized to be maintained even at extreme temperatures.

Cross-Linked Products, Articles Comprising the Same and Methods of Manufacture [0032] In this regard, a second embodiment according to the present invention relates to a cross-linked product obtained by subjecting the composition according to the first embodiment to ionizing radiation. As has been set out above, the cross-linked products exhibit excellent tensile strength and flexibility over a wide range of temperatures, both when subjected to sudden temperature changes (e.g. a heat or cold shock) and to prolonged exposure to extreme temperatures.

[0033] In general, the radiation used for cross-linking should exhibit a sufficiently high energy to penetrate the thickness of the fluoropolymer being treated and to produce ionization therein. The energy level used is any energy level which penetrates the thickness of the sample being irradiated under the atmospheric conditions employed, typically at least 0.5 MeV, and preferably from 1 to 10 MeV. Suitable radiation sources include, but are not limited to gamma rays, X-rays, alpha particles, electron beams, photon beams, deuteron beams, and the like, of which electron beam irradiation is usually preferred. Irradiation may be carried out at room temperature or at elevated temperatures.

[0034] The irradiation process is desirably performed so that the composition is exposed to radiation for a sufficient time and at sufficient dose to cause an improvement in tensile properties without degradation effects. In this regard, it is preferred that the composition is subjected to ionizing radiation at a dose level of up to 150 kGy, preferably at a dose level of from 5 to 100 kGy, further preferably at a dose level of from 10 to 80 kGy.

[0035] The thus obtained cross-linked products are useful in many applications, such as seals, gaskets, tubes, wire or cable jackets and insulation, and rollers which will be exposed to environments involving extreme temperatures, harsh chemicals and/or high pressure situations.

[0036] In a third embodiment, the present invention relates to a heat-shrinkable article comprising the cross-linked product according to the second embodiment. The heat- shrinkable article may comprise additional components used in the preparation of heat- shrink materials. In preferred embodiments, the heat-shrinkable article is a tubular article prepared by forming a tubing by extruding the cross-linkable composition according to the first embodiment, cross-linking the same by ionizing irradiation, radially expanding the cross-linked tubular article under a heated condition and then rapidly cooling the same in order for it to maintain its expanded shape.

[0037] In a fourth embodiment, the present invention relates to cable jackets or sealing elements comprising the cross-linked product according to the second embodiment. The shape of the sealing element is not particularly limited and may include O-ring, V-ring, and X-ring designs, for example. In addition, the seal element may comprise a multilayer composition, wherein the cross-linked product according to the second embodiment forms at least one layer of the multilayer configuration. While not being limited thereto, cable jackets according to the present invention may also comprise the cross-linked product in a multilayer configuration and/or in a composite (e.g., in composites comprising reinforcing fibers known in the art).

[0038] As indicated above, heat-shrinkable articles, cable jackets and sealing elements according to the present invention are particularly useful in equipment exposed to high temperatures and/or temperature changes, such as in aerospace engineering, for example. [0039] In a fifth embodiment, the present invention relates to a process of manufacturing a cross-linked product, comprising the steps of: (i) mixing an elastomeric fluoropolymer and a semi-crystalline fluoroplastic to prepare a crosslinkable composition; (ii) optionally subjecting the crosslinkable composition to a forming step; and (iii) subjecting the crosslinkable composition to ionizing radiation to obtain the cross-linked product.

[0040] Preferred embodiments of the mixture of an elastomeric fluoropolymer and a semi crystalline fluoroplastic are explained in the context of the first embodiment above. The methods of preparing the blend of the elastomeric fluoropolymer and the semi-crystalline groups in step (i) are not particularly limited and may be suitably chosen by the skilled artisan depending on the compatibility of the polymers. For example, these may include dry blending, extrusion mixing and/or melt processing.

[0041] In the optional step (ii), the cross-linkable composition is subjected to a shaping process. Suitable methods include moulding methods (incl. injection moulding, transfer molding, rotational moulding, thermoforming and compression moulding, for example), extrusion moulding, casting, machining, and the like.

[0042] Step (iii) comprises subjecting the crosslinkable composition to ionizing radiation to obtain the cross-linked product, as described above in conjunction with the second embodiment.

[0043] It will be understood that the preferred features of the first to fifth embodiments may be freely combined in any combination, except for combinations where at least some of the features are mutually exclusive.

EXAMPLES

[0044] In Examples 1 to 4, blends comprising different contents of the fluoroelastomer Aflas ^® 150FC (commercially obtained from AGC Chemicals) and the semicrystalline fluoroplastic Fluon ^® PFA EA-2000 (anhydride-functionalized semicrystalline thermoplastic copolymer commercially obtained from AGC Chemicals) have been prepared by twin screw extrusion mixing, using a LabTech co-rotating modular twin screw extruder with a a 5 kW drive motor (£ 1200 rpm) and a screw diameter of 20 mm in a standard screw configuration. The heating zones of the twin screw extruder were set up according to Table 1. [0045] TABLE 1

[0046] Upon mixing, the blends were subjected to tape extrusion, using a 32 m Baughan Extruder equipped with an Inconel mixing screw (30 to 50 rpm) and the following heating zone setup:

[0047] TABLE 2

[0048] Subsequently, the thus produced tapes were electron beam irradiated at 20 kGy (2 Mrad) and 40 kGy (4 MRad) dosage levels, respectively. [0049] The irradiated tapes and non-irradiated control samples were subjected to tensile strength (i.e. tensile strength at break) and ultimate elongation (i.e. elongation at break) tests according to ISO 37 (type 2 dumb bell test) at 23 ± 2°C, with an initial jaw separation of 50 mm and a jaw separation rate of 100 ± 10 mm per minute.

[0050] Where applicable, measurements have been repeated upon subjecting the samples to a heatshock at 315°C for 4 hours, and upon thermal aging for one week at 270°C prior. In addition, the low temperature flexibility of the irradiated samples has been tested by inspecting the samples for cracks upon exposure to a temperature of -75°C for 4 hours and subsequent bending. The sample compositions of Examples 1 to 4 and their evaluation are summarized in Table 3. [0051] TABLE 3

[0052] As is shown in Table 3, the tensile strength and ultimate elongation of the unirradiated samples may be suitably adjusted by varying the contents of fluoroelastomer and the semi-crystalline fluoroplastic. While the non-crosslinked samples melt upon exposure to a temperature of 315°C, the irradiated samples maintain their tensile strength and ultimate elongation performance at excellent levels and withstand both heatshocks at 315°C and long-term heat exposure at 270°C. In addition, the irradiated samples are resistant to cracking at low temperatures (i.e. 75°C) and maintain their flexibility.

[0053] Accordingly, the above results show that the cross-linkable compositions of the present invention enable manufacturing of toughened articles, which maintain favorable mechanical properties when exposed to extreme temperatures.

[0054] Once given the above disclosure, many other features, modifications, and improvements will become apparent to the skilled artisan.