Method for processing fluorinated thermoplastic elastomers

Abstract

An injection molding process for molding fluorinated thermoplastic elastomeric polymer compositions is disclosed, and articles made using this process exhibit little shrinkage.

Description

[Technical Field]

[0001] The present invention relates to a process for processing thermoplastic elastomer compositions based on fluoropolymers, preferably copolymers containing units derived from vinylidene fluoride (VDF) and hexafluoropropene (HFP). Processing of these fluorothermoplastic elastomers (F-TPE) allows for the production of wearable or consumer electronics products or article parts using conventional thermoplastic processing equipment. [Background technology]

[0002] Thermoplastic elastomers are a class of polymeric materials that exhibit elastomeric behavior at service temperatures, but can be processed and recycled at elevated temperatures like thermoplastics. To achieve these hybrid properties, at least one phase of the polymer system typically has low hardness, low TG, and / or low crystallinity. Therefore, injection molding these materials presents challenges: maintaining part dimensions without specialized cooling systems.

[0003] Document WO2018046355 discloses compositions of dynamically cured thermoplastic vulcanizates (TPVs), a class of thermoplastic elastomers, but does not provide solutions for injection molding said TPVs. Similarly, documents WO2018050688, US20160177079, and US20160194512 disclose fluorinated thermoplastic elastomer compositions, but do not discuss solutions for injection molding parts from these compositions. Therefore, there is a need for a process that reproducibly produces high-quality parts with low shrinkage and variable surface structure. Summary of the Invention [Problem to be solved by the invention]

[0004] To extrude complex or useful parts from TPE resins, researchers must understand the underlying mechanisms and be able to control the dimensional changes that occur under processing conditions. Residual stresses in the amorphous regions of TPEs are the primary driver of final part shrinkage. Similarly, the kinetics of crystallization in the semi-crystalline phase must be controlled so that crystallization occurs within a reasonable time frame in the mold.

[0005] This is perhaps counterintuitive to what is commonly thought to be the cause of shrinkage in semi-crystalline polymers (i.e., crystallization itself). While density change due to crystallization certainly contributes to the volume change of a molded part, this is more closely dependent on the overall crystallinity and / or volume percent crystalline phase. In less crystalline materials, this is less of a dominant factor. [Means for solving the problem]

[0006] A process is disclosed for injection molding thermoplastic elastomeric materials, preferably fluorinated thermoplastic elastomeric polymer compositions, using conventional injection molding equipment, whereby parts made by this process exhibit very little dimensional change upon removal from the mold itself and favorably maintain their integrity after exposure to high temperatures.

[0007] In the disclosed process, the mold temperature is set to the highest melt transition (T m ), preferably lower than T c and T m Between, preferably T m 10 to 70°C lower than T m and more preferably, the T m Generally, the cooling time for this process is greater than 60 seconds, preferably greater than 70 seconds, and may range from 70 to 1000 seconds, preferably from 80 to 900 seconds, and even more preferably from 100 to 800 seconds. Generally, the barrel temperature is T m 30 to 220°C higher than T m50 to 200°C higher than T m 600 to 180°C higher.

[0008] The gate size of the mold should be maximized to reduce shear, which will result in less shrinkage.

[0009] The length of the runner path feeding the mold should be minimized, while the cross-sectional area should be maximized to minimize shear stresses.

[0010] The filling speed of this process ranges from 1 to 100 cm 3 / sec, preferably 5-50cm 3 / second range.

[0011] Fluorinated thermoplastic elastomer compositions that can be processed under these conditions include, but are not limited to, fluoropolymer thermoplastic elastomer polymers, fluoropolymer thermoplastic elastomer polymer blends, and fluorothermoplastic vulcanizates and F-TPEs produced by segmented block copolymerization. Examples of F-TPEs produced by segmented block copolymerization are described in US4158678, US4243770, US5198502, WO2018149757, WO2018050688, or US6107363. Examples of fluorothermoplastic vulcanizates are described in US20160177079, WO2015014699, US20160194512, and US2008032080.

[0012] Using the method of the present invention, the fluorinated thermoplastic elastomer compositions can be readily injection molded to produce parts with shrinkage less than 4.3%, preferably less than 4%, more preferably less than 3%, and even more preferably less than 2%.

[0013] In some embodiments, the thermoplastic elastomer compositions used in the present invention comprise a blend of a non-crosslinked, sufficiently high viscosity (or molecular weight) fluoropolymer "S" and a non-crosslinked, sufficiently high viscosity (or molecular weight) fluoropolymer "H." The fluoropolymer blend comprises 20-80 wt. % S and 80-20 wt. % H. Both polymer S and polymer H are produced without a crosslinking agent.

[0014] In one embodiment, the polymer H of the first aspect is a homopolymer or copolymer having at least 70% by weight of vinylidene fluoride monomer units. S is a fluoropolymer copolymer having at least 35% by weight, preferably at least 40% by weight, of HFP.

[0015] Aspect 1 of the present invention is a process for molding a fluorinated thermoplastic elastomeric polymer composition, said process comprising the steps of: (I) To provide a semi-crystalline fluorinated thermoplastic elastomer polymer composition having a formation ΔH of 1 to 30 J / g, preferably 1 to 20 J / g, more preferably 1 to 10 J / g. (II) injection molding the fluorinated thermoplastic elastomeric polymer composition. Including, (a) The barrel temperature is T m 30 to 220°C higher than T m 50 to 200°C higher than T m 60 to 180 degrees Celsius higher, (b) The mold temperature is the maximum melt transition temperature (T m ), preferably less than T c and T m and preferably between T m 10 to 70°C lower than T m 10 to 60°C lower than T m 10 to 40 degrees Celsius lower than (c) The cooling time of the mold is longer than 60 seconds, preferably 70 to 1000 seconds, preferably 80 to 900 seconds, and even more preferably 100 to 800 seconds.

[0016] Aspect 2: The process of aspect 1, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a fluoropolymer blend, the blend comprising an elastomeric fluoropolymer and a thermoplastic fluoropolymer.

[0017] Aspect 3: T of the fluorinated thermoplastic elastomer polymer composition m 3. The process of aspect 1 or 2, wherein the heating temperature is greater than 40°C, preferably greater than 60°C, and more preferably greater than 80°C.

[0018] Aspect 4: T of the fluorinated thermoplastic elastomer polymer composition m The process according to any one of aspects 1 to 3, wherein the heating temperature is 40°C to 230°C, preferably 60°C to 200°C, and more preferably 80°C to 175°C.

[0019] Aspect 5: For a given composition, T c T m T c The process according to any one of aspects 1 to 4, wherein the temperature is at least 0°C, preferably above 10°C, and more preferably above 15°C.

[0020] Aspect 6: For a given composition, T c T m T c The process according to any one of aspects 1 to 5, wherein the heating temperature can be in the range of 0°C to 215°C, preferably 10°C to 215°C.

[0021] Aspect 7: For a given composition, T c T m T of the composition, provided that it is at least 15°C lower than m is less than 120°C, preferably less than 100°C, and T c The process according to any one of aspects 1 to 6, wherein the temperature is at least 0°C, preferably above 10°C, and more preferably above 15°C.

[0022] Aspect 8: the fluoropolymer thermoplastic elastomer polymer composition comprises a fluoropolymer blend comprising Fluoropolymer S and Fluoropolymer H; H is a fluoropolymer comprising 0 to 30 wt %, preferably 15 to 30 wt %, more preferably 20 to 30 wt %, of a monomer selected from the group consisting of HFP, fluorinated or perfluorinated vinyl ether, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or a combination thereof; Aspect 8. The process of any one of aspects 1 to 7, wherein S preferably comprises at least 35 wt%, preferably at least 40 wt%, and most preferably at least 43 wt%, of a monomer selected from the group consisting of hexafluoropropene (HFP), fluorinated or perfluorinated vinyl ether, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or a combination thereof; the amount of H is 20 to 80 wt% of the composition; and the amount of S is 20 to 80 wt% of the composition.

[0023] Side 9: 230℃, 100s -1 The melt viscosity of H measured at 230°C for 100 seconds is 1 to 30 kP. -1 The process according to aspect 8, wherein the melt viscosity of S measured by is 10 to 55 kP.

[0024] Aspect 10: The process of aspect 8 or 9, wherein H comprises at least one monomer selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, and 1,1,1 trifluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluorobutyl vinyl ether (PBVE), fluorinated or perfluorinated vinyl ethers including long chain perfluorinated vinyl ethers, fluorinated dioxoles, C4 or higher partially or perfluorinated alpha olefins, C3 or higher partially or perfluorinated cyclic alkenes, fluorinated or partially fluorinated acrylates and methacrylates, and combinations thereof.

[0025] Aspect 11: The process of any one of aspects 8-10, wherein S includes at least one monomer selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, and 1 , 1,1-trifluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluorobutyl vinyl ether (PBVE), fluorinated or perfluorinated vinyl ethers including long chain perfluorinated vinyl ethers, fluorinated dioxoles, C4 or higher partially or perfluorinated alpha olefins, C3 or higher partially or perfluorinated cyclic alkenes, fluorinated or partially fluorinated acrylates and methacrylates, and combinations thereof.

[0026] Aspect 12: The process of any one of aspects 8 to 11, wherein fluoropolymer H is a copolymer of VDF and HFP, wherein VDF constitutes at least 70 wt% of H, and fluoropolymer S is a copolymer of VDF and HFP, wherein HFP constitutes at least 30 wt% of S, preferably at least 40 wt% of S, and more preferably at least 45 wt% of S.

[0027] Aspect 13: The process of any one of Aspects 8 to 12, wherein the amount of H is 40 to 60 wt % of the composition and the amount of S is 60 to 40 wt % of the composition.

[0028] Aspect 14: The process of any one of Aspects 8 to 13, wherein the total proportion of fluoropolymers H and S in the composition is at least 85 wt%, preferably at least 90 wt%, and more preferably at least 95 wt%.

[0029] Aspect 15: The melt viscosity of the fluoropolymer blend of S and H is 100 s at a temperature of 230 °C. -1 15. The process according to any one of aspects 8 to 14, wherein the shear rate is 1000 to 4400 Pa·s, preferably 1000 to 3000 Pa·s, and more preferably 800 to 2200 Pa·s.

[0030] Aspect 16: The process of any one of Aspects 1 to 7, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a fluorinated thermoplastic vulcanizate (TPV).

[0031] Aspect 17: The process of aspect 16, wherein the TPV comprises a crosslinker selected from the group consisting of melamine resins, epoxy resins, di- or higher polyisocyanates, polyaziridines, polycarbodiimides, polyoxazolines, dialdehydes (such as glyoxal), di- and trifunctional acetoacetates, malonates, acetals, thiols and acrylates, cycloaliphatic epoxy molecules, organosilanes (such as epoxy silanes, amino silanes), carbamates, diamines, and triamines, inorganic chelating agents (certain zinc and zirconium salts, titanates, glycourils and other aminoplasts, etc.), triallyl cyanurate; triallyl isocyanurate (TAIC); tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl-acrylamide; fluorinated bisolefins as defined below, N,N'-bisallylcyclo-oct-7-ene-disuccinimide (BOSA); N,N,N'-tetraallyl-malonamide; trivinyl-isocyanurate; 2,4,6-trivinyl-methyltrisiloxane.

[0032] Aspect 18: The process of aspect 1, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a VDF and HFP-based copolymer.

[0033] Aspect 19: An article produced from the process of any one of aspects 1 to 18, having an out-of-mold shrinkage of less than 4.3%, preferably 3%, and more preferably less than 1%, according to the test method.

[0034] Aspect 20: An article produced from the process of any one of aspects 1 to 19, wherein the article exhibits shrinkage of less than 5%, preferably 3%, and more preferably less than 1%, after annealing the part at 65°C for 72 hours, according to the test method.

[0035] Aspect 21: The article of any one of aspects 1 to 19, which exhibits shrinkage of less than 5%, preferably 3%, and more preferably less than 1% after annealing the part at 80°C for 72 hours according to the test method.

[0036] Aspect 22: A process for molding a fluorinated thermoplastic elastomer, said process comprising the steps of: (I) To provide a semi-crystalline polymer composition having a formation ΔH of 1 to 10 J / g. (II) the polymer, (a)T m Barrel temperature is 50 to 200°C higher than (b) Melting transition (T m ), preferably less than T c and T m and more preferably between T m Mold temperature 10~60℃ lower than (c) A mold cooling time of 70 to 800 seconds. injection molding, The process, wherein the fluorinated thermoplastic elastomer composition comprises a blend of H polymer and S polymer with an H ratio of 20% to 80%.

[0037] Aspect 23: The process of aspect 22, wherein H comprises a copolymer comprising vinylidene fluoride and HFP, and S comprises a copolymer comprising vinylidene fluoride and HFP. DETAILED DESCRIPTION OF THE INVENTION

[0038] All references cited in this application are incorporated herein by reference. Unless otherwise specified, all percentages in compositions are percent by weight.

[0039] The term "polymer" is used to refer to both homopolymers, copolymers, and terpolymers (three or more monomer units), unless otherwise specified. Any copolymer or terpolymer can be random, block, or gradient, and the polymer can be linear, branched, star, comb, or any other morphology.

[0040] In the context of this application, unless otherwise stated, all viscosities are measured at a temperature of 230°C and 100 s -1 The melt viscosity is measured at a shear rate of 10 to 3000 s. More specifically, the melt viscosity can be measured using a DYNISCO LCR 7000 capillary rheometer. Measurements are performed at 230°C and 10 to 3000 s. -1 The viscosity was measured at shear rates in the range of 100S. -1 It is recorded as.

[0041] T c and T m The formation ΔH was identified by differential scanning calorimetry (DSC) at a heating / cooling rate of 10 °C / min during the first cooling and second heating, respectively. The formation ΔH was determined by the endothermic region (T m ) or the heat generation area during the first cooling (T c ) and dividing by the rate of temperature rise and the sample mass. T m All references to T refer to the highest melt transition temperature of the fluorinated thermoplastic elastomeric polymer composition unless otherwise specified. c All references to the minimum crystallization temperature of the fluorinated thermoplastic elastomeric polymer composition unless otherwise specified.

[0042] By semi-crystalline it is meant that the thermoplastic elastomeric polymer composition has a ΔH of formation between 1 and 60 J / g.

[0043] Shrinkage Test: Shrinkage is defined as the percent change in length in one dimension of a Type I ASTM tensile bar from a 165 mm mold size and is simply measured with a caliper with a sensitivity of at least 0.1 mm. Post-demold shrinkage is measured 24 hours after demolding, during which time the tensile bar is at ambient temperature (20-25°C). Unless otherwise noted, shrinkage refers to shrinkage outside the mold (the article is not annealed).

[0044] Annealing Procedure. After removal from the mold, the article is heated to the indicated temperature for the indicated time, and then measured 24 hours after removal from the annealing heat according to the shrinkage test described above. "Annealing Shrinkage."

[0045] "Elastomer" herein means a material that has an elastic recovery of at least 80%, preferably at least 90%, when subjected to a stress / relaxation protocol according to ASTM Standard, Special Publication No. 184. This protocol applies to a tensile bar as defined in ASTM D638. The sample is subjected to 100% tensile deformation at 25°C. 100% deformation is maintained for 5 minutes, after which the sample is released. After 5 minutes of relaxation, the residual deformation is measured. Elastic recovery is defined as the initial sample length minus the residual deformation. The tensile protocol is performed on an Instron Model 4201, 4202, or the like, equipped with a 100 or 200 lb load cell.

[0046] Fluorinated thermoplastic elastomer means a polymeric material that exhibits elasticity at ambient temperatures and can be processed as a plastic by melt processing techniques. Examples of fluorinated thermoplastic elastomer (TPE) materials include blends (usually thermoplastic elastomers and elastomers), TPVs, and block copolymers (containing one or more blocks of thermoplastic and one or more blocks of elastomer).

[0047] The present invention provides a process for injection molding a fluorinated thermoplastic elastomeric polymer composition, said process comprising the following steps: (I) To provide a semi-crystalline fluorinated thermoplastic elastomer polymer composition having a formation ΔH of 1 to 30 J / g, preferably 1 to 20 J / g, more preferably 1 to 10 J / g. (II) injection molding the fluorinated thermoplastic elastomeric polymer composition. Including, (a) The barrel temperature is T m 30 to 200°C higher than T m and more preferably, the T m 60 to 180 degrees Celsius higher, (b) The mold temperature is the maximum melt transition temperature (T m ), preferably less than T c and T m and preferably between T m 10 to 70°C lower than T m 10 to 60°C lower than T m 10 to 40 degrees Celsius lower than (c) The cooling time of the mold is longer than 60 seconds, 70 seconds or more, 70 to 1000 seconds, preferably 80 to 900 seconds, and even more preferably 80 to 800 or 100 to 800 seconds.

[0048] The present invention provides articles made by the disclosed processes.

[0049] The process of the present invention results in articles with low out-of-mold shrinkage. Preferably, the out-of-mold shrinkage is 4.3% or less, less than 4%, less than 3%, and more preferably less than 1%, as measured by shrinkage testing.

[0050] The barrel temperature is higher than the melting point of the thermoplastic elastomer composition. Preferably, the barrel temperature is less than T to ensure that the fluorinated thermoplastic elastomer polymer composition flows into the mold with low residual flow-induced stress.m It is at least 30°C higher, preferably at least 50°C higher.

[0051] Two types of relevant residual stress in molding are flow-induced stress and thermally induced stress. Flow-induced residual stress occurs when a polymer is subjected to shear during processing. When in the molten state, polymer molecules are unstressed and tend to assume a random coil state. During processing, polymers may undergo shear and elongation, causing the molecules to become oriented in the direction of flow. If solidification occurs before the polymer molecules have fully relaxed to the random coil state, the molecular orientation becomes fixed in the molded part.

[0052] Polymers can also experience thermally induced residual stresses during processing. This occurs during cooling. Polymers shrink as they cool. During cooling, the polymer cools at different rates from the mold walls to the center. As the polymer begins to cool, the outer surface begins to shrink, while the majority of the polymer in the core is still hot and unshrunk. As the inner core cools, its shrinkage is restrained by the outer layers, which are already rigid.

[0053] The mold temperature reaches the highest melting transition (T m ) and preferably the mold temperature is lower than the T c and T m and more preferably between T m It is important that the temperature is 10 to 70°C lower than the melting point of the fluorinated thermoplastic elastomer polymer composition, as this ensures that the fluorinated thermoplastic elastomer polymer composition solidifies before it is removed from the mold.

[0054] The mold cooling time is greater than 60 seconds, preferably greater than 70 seconds, more preferably greater than 80 seconds, and preferably less than 1000 seconds. The cooling time can be 70 to 1000 seconds, 80 to 900 seconds, or 100 to 800 seconds. If the cooling time is too short, the part will not solidify significantly. If the cooling time is too short, shrinkage will be significant.

[0055] The combination of mold temperature and cooling time allows for proper crystallization of the fluorinated thermoplastic elastomeric polymer composition, thereby providing a molded part that retains its shape and size after demolding.

[0056] The thermoplastic elastomeric polymer composition that can be molded according to the present invention can be a blend of at least two fluoropolymer polymers, one fluoropolymer being elastomeric and the other being thermoplastic. The blend may or may not contain a crosslinking agent. If the blend contains a crosslinking agent, it is typically referred to as a TPV. Such crosslinking agents are known in the art.

[0057] T of fluorinated thermoplastic elastomer polymer composition m is higher than 40°C, preferably higher than 60°C, more preferably higher than 80°C. m The heating temperature may be in the range of 40°C to 230°C, preferably 60°C to 200°C, and more preferably 80°C to 170°C.

[0058] Fluorinated thermoplastic elastomer polymer composition T c The crystallization temperature of T is at least 0°C, preferably above 10°C, and more preferably above 15°C. For a given fluorinated thermoplastic elastomeric polymer composition, T c T m T c The temperature can be in the range of 0°C to 170°C, preferably 10°C to 170°C.

[0059] In one embodiment, for a given fluorinated thermoplastic elastomeric polymer composition, T c T m the T of the fluorinated thermoplastic elastomer polymer composition, provided that the T m is less than 120°C, preferably less than 100°C, and the crystallization temperature T c is at least 0°C, preferably above 10°C, more preferably above 15°C.

[0060] Examples of thermoplastic elastomeric polymer compositions can be found in WO201804635, WO2018050688, US20160177079, US20160194512. Such compositions can be processed according to the present invention.

[0061] One thermoplastic elastomeric polymer composition used in the present invention comprises a blend of a non-crosslinked, sufficiently high melt viscosity fluoropolymer "S" and a non-crosslinked, sufficiently high melt viscosity fluoropolymer "H." The fluoropolymer blend comprises 20-80 wt. % S and 80-20 wt. % H. Both polymer S and polymer H are produced without a crosslinking agent.

[0062] Fluoropolymer H: Polymer H can be a homopolymer or a copolymer containing more than 50% by weight of fluoromonomer.

[0063] Polymer H is a fluoropolymer comprising 0 to 30 wt %, preferably 15 to 30 wt %, more preferably 20 to 30 wt % of a monomer selected from the group consisting of HFP, fluorinated or perfluorinated vinyl ethers including perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluorobutyl vinyl ether (PBVE), trifluoropropene, 1-chloro-3,3,3-trifluoropropene, long-chain perfluorinated vinyl ethers and 2,3,3,3-tetrafluoropropene, or combinations thereof.

[0064] In one embodiment, H is preferably a homopolymer or a copolymer having 70 to 100 wt. % of a fluoromonomer containing 0 to 30 wt. % of HFP, and is heated at 230° C. for 100 s -1 The melt viscosity measured by the method is 1 to 30 kP, preferably 4 to 20 kP.

[0065] Fluoropolymers H of the present invention include, but are not limited to, polymers containing at least 50% by weight of one or more fluoromonomers. The term "fluoromonomer" as used in accordance with the present invention means a fluorinated and olefinically unsaturated monomer capable of undergoing a free radical polymerization reaction. Exemplary fluoromonomers suitable for use in accordance with the present invention include, but are not limited to, vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoropropene, 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, fluorinated dioxoles, C4 or higher partially or perfluorinated alpha olefins, C3 or higher partially or perfluorinated cyclic alkenes, fluorinated or partially fluorinated acrylates and methacrylates, and combinations thereof. Fluoropolymers used in the practice of the present invention include the polymerization products of the above-mentioned fluoromonomers, such as homopolymers made by polymerizing vinylidene fluoride (VDF) with itself, or copolymers made by polymerizing vinylidene fluoride (VDF) with hexafluoropropene (HFP).

[0066] Fluoroterpolymers are also contemplated, including terpolymers such as those having tetrafluoroethylene, hexafluoropropene, and vinylidene fluoride monomer units. Most preferably, the fluoropolymer is a polyvinylidene fluoride (PVDF) polymer homopolymer or copolymer. Although the present invention is exemplified with respect to PVDF, those skilled in the art will recognize that the term PVDF can refer to other fluoropolymers when exemplified.

[0067] Polymer H is preferably a polyvinylidene fluoride (PVDF) polymer. PVDF can be a homopolymer, copolymer, or polymer alloy. Polyvinylidene fluoride polymer H of the present invention includes homopolymers made by polymerizing vinylidene fluoride (VDF), as well as copolymers, terpolymers, and higher polymers of vinylidene fluoride, where vinylidene fluoride units constitute more than 51% by weight of the total weight of all monomer units in the polymer, preferably 70%, and more preferably more than 75% of the total weight of the monomer units. Copolymers, terpolymers and higher polymers (generically referred to herein as "copolymers") of vinylidene fluoride can be made by reacting vinylidene fluoride with one or more monomers from the group consisting of vinyl fluoride, trifluoroethene, tetrafluoroethene, one or more of partially or fully fluorinated alpha olefins (3,3,3-trifluoro-1-propene, 1,2,3,3,3-pentafluoropropene, 3,3,3,4,4-pentafluoro-1-butene, hexafluoropropene, partially fluorinated olefins such as hexafluoroisobutylene, perfluoroolefins, and the like. Fluorinated vinyl ethers (such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro-N-propyl vinyl ether, and perfluoro-2-propoxypropyl vinyl ether), fluorinated dioxoles (such as perfluoro(1,3-dioxole) and perfluoro(2,2-dimethyl-1,3-dioxole)), allyl, partially fluorinated allyl, or fluorinated allyl monomers (such as 2-hydroxyethyl allyl ether or 3-allyloxypropanediol), and ethene or propene, as well as fluorinated or partially fluorinated acrylates or methacrylates. Preferred copolymers or terpolymers are formed with vinyl fluoride, 2,3,3,3-tetrafluoropropene, trifluoroethene, tetrafluoroethene (TFE), and hexafluoropropene (HFP).

[0068] Preferred copolymers of polymer H include those containing about 70 to about 99 wt. % VDF and correspondingly about 1 to about 30 wt. % HFP, preferably 15 to 30 wt. % HFP; terpolymers of VDF / HFP / TFE; and copolymers of VDF and TFE.

[0069] In the case of polymer H, it is preferred that all monomer units are fluoromonomers, although copolymers of fluoromonomers and non-fluoromonomers are also contemplated by the present invention. In the case of copolymers containing non-fluoromonomers, at least 60% by weight of the monomer units are fluoromonomers, preferably at least 70% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight. Useful comonomers include, but are not limited to, ethylene, propylene, styrenics, acrylates, methacrylates, vinyl esters, vinyl ethers, non-fluorine-containing halogenated ethylenes, vinylpyridines, N-vinyl linear and cyclic amides.

[0070] Fluoropolymer S:The fluoropolymer S of the present invention preferably contains at least 35 wt%, preferably at least 40 wt%, and most preferably at least 43 wt% of a monomer selected from the group consisting of fluorinated or perfluorinated vinyl ethers, including hexafluoropropene (HFP), perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), and perfluorobutyl vinyl ether (PBVE), long-chain perfluorinated vinyl ethers, and 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or combinations thereof. Preferably, the monomer selected from this group is 35 wt% to 70 wt%, preferably 40 to 70 wt%, more preferably 43 to 70 wt%. The remaining weight percent is preferably made up of other fluoromonomers. The term "fluoromonomer" as used in accordance with the present invention means a fluorinated and olefinically unsaturated monomer capable of undergoing a free-radical polymerization reaction.Exemplary fluoromonomers suitable for use in accordance with the present invention include, but are not limited to, vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoropropene, 1,2-dichloro-1,2-difluoropropene, ... Fluoropolymers S used in the practice of the present invention include the polymerization products of the above fluoromonomers, for example, copolymers prepared by polymerizing vinylidene fluoride (VDF) with hexafluoropropene (HFP).

[0071] Fluoroterpolymers are also contemplated, including terpolymers such as those having tetrafluoroethylene, hexafluoropropene, and vinylidene fluoride monomer units.

[0072] The polymer S is preferably a vinylidene fluoride (VDF) hexafluoropropene (HFP) copolymer. S can be a copolymer or a polymer alloy. The polyvinylidene fluoride polymer S of the present invention includes copolymers, terpolymers, and higher polymers of hexafluoropropene (HFP), in which hexafluoropropene (HFP) units constitute more than 35% by weight, preferably 40% by weight, and more preferably 43% by weight, of the total weight of all monomer units in the polymer. HFP monomer units can constitute as much as 70% by weight of the total weight of all monomer units in the polymer S. Copolymers, terpolymers and higher polymers (generically referred to herein as "copolymers") of vinylidene fluoride can be made by reacting vinylidene fluoride with one or more monomers from the group consisting of vinyl fluoride, trifluoroethene, tetrafluoroethene, partially or fully fluorinated alpha olefins (3,3,3-trifluoro-1-propene, 1,2,3,3,3-pentafluoropropene, 3,3,3,4,4-pentafluoro-1-butene, hexafluoropropene, partially fluorinated olefins, hexafluoroisopropyl ... perfluorobutylene, perfluorinated vinyl ethers (such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro-N-propyl vinyl ether, and perfluoro-2-propoxypropyl vinyl ether), fluorinated dioxoles (such as perfluoro(1,3-dioxole) and perfluoro(2,2-dimethyl-1,3-dioxole)), allyl, partially fluorinated allyl, or fluorinated allyl monomers (such as 2-hydroxyethyl allyl ether or 3-allyloxypropanediol), and ethene or propene. Preferred copolymers or terpolymers are formed with vinyl fluoride, trifluoroethene, tetrafluoroethene (TFE), and hexafluoropropene (HFP).

[0073] Preferred copolymers of Polymer S include those containing levels of HFP of about 35 to about 70 wt. % and correspondingly about 65 to about 30 wt. % VDF, preferably 40 to 55 wt. % and about 60 to about 45 wt. %; and terpolymers of VDF / HFP / TFE.

[0074] In one embodiment of the present invention, for polymer S, it is preferred that all monomer units are fluoromonomers, although copolymers of fluoromonomers and non-fluoromonomers are also contemplated by the present invention. For copolymers containing non-fluoromonomers, at least 60% by weight of the monomer units are fluoromonomers, preferably at least 70% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight. Useful comonomers include, but are not limited to, ethylene, propylene, styrenic, acrylate, methacrylate, vinyl ester, vinyl ether, non-fluorine-containing halogenated ethylene, vinylpyridine, N-vinyl linear and cyclic amides.

[0075] Polymer S has a melt viscosity of 10 to 55 kP, preferably 15 to 55 kP, more preferably 20 to 50 kP, even more preferably 25 to 50 kP, and most preferably 30 to 50 kP.

[0076] In a preferred embodiment, the polymer S comprises more than 30% and up to 70% by weight of HFP, more preferably more than 40% and up to 70% by weight of HFP.

[0077] In one embodiment, S is a copolymer of 30-65 wt. % VDF (vinylidene fluoride) and 35-70 wt. % HFP, having a viscosity of 10-55 kP, preferably 15-55 kP, more preferably 20-50 kP, even more preferably 25-50 kP, and most preferably 30-50 kP.

[0078] At least one fluoropolymer S (i.e., either a single fluoropolymer S or a mixture of fluoropolymers S) preferably has low or no crystallinity. This is characterized by a heat of fusion of less than 20 J / g, preferably less than 15 J / g, and even more preferably less than 10 J / g, calculated from the first endotherm detected in a differential scanning calorimeter (DSC) scan. DSC scans are performed according to ASTM D451-97 using a DSC apparatus. The instrument is equipped with a dry box through which a nitrogen purge is performed. 9-10 mg specimens are used and crimped onto aluminum pans. The DSC run begins at -50°C, followed by a 10°C / min temperature ramp to 210°C.

[0079] The fluorinated thermoplastic elastomeric polymer composition is prepared by combining polymer S and polymer H in a ratio of 20-80% by weight of S to 80-20% by weight of polymer H; preferably 25-75% by weight of S to 75-25% by weight of polymer H; more preferably 60-40% by weight of S to 40-60% by weight of polymer H, based on the total weight of H and S. In one embodiment, the blend is prepared by combining or mixing a latex of S with a latex of H in the desired ratio. Fluoropolymers S and H, when combined together, can also be in the form of a powder.

[0080] In one embodiment, the thermoplastic elastomeric fluoropolymer composition comprises a fluoropolymer blend comprising fluoropolymer S and fluoropolymer H, wherein H is a fluoropolymer comprising 0 to 30 wt%, preferably 15 to 30 wt%, more preferably 20 to 30 wt% of a monomer selected from the group consisting of HFP, fluorinated or perfluorinated vinyl ethers, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or combinations thereof, S preferably comprises at least 35 wt%, preferably at least 40 wt%, most preferably at least 43 wt% of a monomer selected from the group consisting of hexafluoropropene (HFP), fluorinated or perfluorinated vinyl ethers, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or combinations thereof, and wherein the amount of H is 20 to 80 wt% of the composition and the amount of S is 20 to 80 wt% of the composition.

[0081] One fluorinated thermoplastic elastomeric polymer composition that can be processed according to the present invention is a composition comprising a fluoropolymer blend comprising fluoropolymer S and fluoropolymer H, where H is a fluoropolymer containing vinylidene fluoride and less than 30 weight percent HFP; and S is a vinylidene fluoropolymer containing more than 35 weight percent HFP, the amount of H being 20-80 weight percent of the composition, and the amount of S being 20-80 weight percent of the composition.

[0082] At least one fluoropolymer S (ie either a single fluoropolymer S or a mixture of fluoropolymers S) is preferably an elastomer.

[0083] When two or more fluoropolymers S are present in the fluorinated thermoplastic elastomeric polymer composition, the viscosity values ​​given herein are those of the corresponding mixtures of fluoropolymers S in the same relative proportions as they are in the composition.

[0084] When two or more fluoropolymers H are present in the fluorinated thermoplastic elastomeric polymer composition, the viscosity values ​​given herein are those of the corresponding mixtures of fluoropolymers H in the same relative proportions as they are in the composition.

[0085] The production of fluoropolymers is well known to those skilled in the art. Fluoropolymers can be produced via suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, or solution-assisted suspension or emulsion polymerization. Reactions for producing latexes for polymer H and polymer S are known to those skilled in the art and are disclosed, for example, in U.S. Pat. Nos. 4,360,652, 6,869,997, 8,080,621, 8,158,734, 8,697,822, 8,765,890, and many other patents, the contents of which are incorporated herein by reference. Preferably, no fluorosurfactants are used in the polymerization process.

[0086] Other additives The fluorinated thermoplastic elastomer polymer composition used in the present invention may also contain typical additives, including but not limited to: dyes, pigments, colorants, impact modifiers, antioxidants, flame retardants, UV stabilizers, flow aids, conductive additives such as metals, carbon black, and carbon nanotubes, antifoaming agents, waxes, solvents, rheology modifiers such as plasticizers, surfactants, fillers (including nanofillers), and antistatic agents. Other additives that provide whitening may be added to the fluorinated thermoplastic elastomer polymer composition, including but not limited to: metal oxide fillers such as zinc oxide; phosphate or phosphite stabilizers; and phenolic stabilizers. Any residual additives used to synthesize at least one fluoropolymer H or S or other polymer may be present.

[0087] Plasticizers are defined in the Encyclopedia of Polymer Science and Engineering (WILEY & SONS, 1989), pp. 568-569 and 588-593. They can be monomeric or polymeric. Dibutyl sebacate, dioctyl phthalate, Nn-butylsulfonamide, polymeric polyesters, and combinations thereof are examples of suitable plasticizers. Suitable polymeric polyesters can be derived, for example, from adipic acid, azelaic acid, or sebacic acid and diols, and combinations thereof. Their molecular weight is preferably at least 1500 g / mol, more preferably at least 1800 g / mol.

[0088] When additives are present, they are preferably present in the fluorinated thermoplastic elastomeric polymer composition in an amount of 0.1 to 10 wt %, more preferably 0.2 to 5 wt %, and most preferably 0.5 to 3 wt % for each additive.

[0089] Crosslinking agent In TPVs, a crosslinker is used in the elastomer portion of the TPV. When a radical mechanism is used, a crosslinker is used in addition to a radical generator. Crosslinkers that can be used include, but are not limited to: melamine resins, epoxy resins, di- or higher polyisocyanates, polyaziridines, polycarbodiimides, polyoxazolines, dialdehydes (such as glyoxal), di- and trifunctional acetoacetates, malonates, acetals, thiols and acrylates, cycloaliphatic epoxy molecules, organosilanes (such as epoxy silanes, amino silanes), carbamates, diamines, and triamines, inorganic chelating agents (certain zinc and zirconium salts), and the like. , titanates, glycourils and other aminoplasts, etc.), triallyl cyanurate; triallyl isocyanurate (TAIC); tris(diallylamine)-S-triazine; triallyl phosphite; N,N-diallyl-acrylamide; fluorinated bisolefins as defined below, N,N'-bisallylcyclo-oct-7-ene-disuccinimide (BOSA); N,N,N'-tetraallyl-malonamide; trivinyl-isocyanurate; 2,4,6-trivinyl-methyltrisiloxane, etc. Mixtures of the above crosslinkers or crosslinkers can be utilized.

[0090] Goods The process of the present invention can be used to overmold a variety of other objects or parts.

[0091] The process of the present invention can be used to make articles, such as strip-shaped or plate-shaped articles. The articles of the present invention can be selected in particular from wearable articles and household appliances. In particular, in embodiments, the articles are intended to come into contact with the human body, more particularly with human skin.

[0092] Other articles that can be made include sensor supports, electronic device supports, casings, belts, gloves, pads, strips and bands.

[0093] Flexible components for equipment such as diaphragms, O-rings, and seals can be made using the process of the present invention.

[0094] Parts used for overmolding. [Example]

[0095] Table 1 shows the T values ​​at 83°C injected under different conditions. m , 20°C T c , and T m The results show that the fluorinated TPE blend has a ΔH of 7 J / g for 1000 sq ft and the resulting part shrinkage. All samples were injected at a 5 cm injection speed using an ASTM Type I drawbar mold. 3 It was made using a / s injection molding machine.

[0096] [Table 1]

[0097] The data show that, by following the present invention, thermoplastic elastomer compositions can be molded with shrinkage from the mold of less than 4.3%, or even less than 3%, or even less than 2%. After annealing at 65°C and 90% relative humidity for 72 hours, shrinkage of the parts remains less than 5%. Examples 1, 3, and 12 show that barrel temperature increases outside mold shrinkage and decreases annealing shrinkage. Looking at Examples 6 to 9, there is a tendency for shrinkage to decrease as the holding time increases.

Claims

1. 1. A process for molding a fluorinated thermoplastic elastomeric polymer composition, said process comprising the steps of: a. Providing a semi-crystalline fluorinated thermoplastic elastomeric polymer composition having a formed ΔH of 1 to 30 J / g, preferably 1 to 20 J / g, more preferably 1 to 10 J / g. b. Injection molding the fluorinated thermoplastic elastomeric polymer composition. Including, i. The barrel temperature is T m 30 to 200°C higher than T m 50 to 200°C higher than T m 60 to 180 degrees higher, ii. The mold temperature is the melt transition temperature (T m ), preferably less than T c and T m and preferably between T m 10 to 70°C lower than T m 10 to 60°C lower than T m 10 to 40 degrees Celsius lower than iii. The cooling time of the mold is greater than 60 seconds, preferably greater than 70 seconds, preferably between 70 and 1000 seconds, preferably between 80 and 900 seconds, and even more preferably between 100 and 800 seconds; process.

2. 10. The process of claim 1, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a fluoropolymer blend, the blend comprising an elastomeric fluoropolymer and a thermoplastic fluoropolymer.

3. T of the fluorinated thermoplastic elastomer polymer composition m 2. The process of claim 1, wherein the temperature is higher than 40°C, preferably higher than 60°C, more preferably higher than 80°C.

4. T of the fluorinated thermoplastic elastomer polymer composition m 2. The process of claim 1, wherein the heating temperature is between 40°C and 230°C, preferably between 60°C and 200°C, more preferably between 80°C and 175°C.

5. For a given composition, T c T m T c 2. The process of claim 1, wherein the temperature is at least 0°C, preferably above 10°C, more preferably above 15°C.

6. For a given composition, T c T m T c The process of claim 1, wherein the temperature can range from 0°C to 215°C, preferably from 10°C to 215°C.

7. For a given composition, T c T m the T of the composition, provided that the T m is less than 120°C, preferably less than 100°C, and T c 2. The process of claim 1, wherein the temperature is at least 0°C, preferably above 10°C, more preferably above 15°C.

8. The fluoropolymer thermoplastic elastomer polymer composition comprises a fluoropolymer blend comprising Fluoropolymer S and Fluoropolymer H; H is a fluoropolymer comprising 0 to 30 wt %, preferably 15 to 30 wt %, more preferably 20 to 30 wt % of a monomer selected from the group consisting of HFP, fluorinated or perfluorinated vinyl ether, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or a combination thereof; S preferably comprises at least 35 wt. %, preferably at least 40 wt. %, and most preferably at least 43 wt. % of monomers selected from the group consisting of hexafluoropropene (HFP), fluorinated or perfluorinated vinyl ethers, 2,3,3,3-tetrafluoropropene, trifluoropropene, 1-chloro-3,3,3-trifluoropropene, or combinations thereof; 4. The process of claim 3, wherein the amount of H is 20-80% by weight of the composition and the amount of S is 20-80% by weight of the composition.

9. 230°C, 100s -1 The melt viscosity of H measured at 230°C for 100 seconds is 1 to 30 kPoise. -1 9. The process of claim 8, wherein the melt viscosity of S measured by is 10 to 55 kPoise.

10. The process of claim 8 or 9, wherein H comprises at least one monomer selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,2-di ...fluoromethyl-3,3,3-trifluoropropene, 1,2-difluoromethyl-3,3,3-trifluoropropene, 1,2-difluoromethyl-3,3,3-trifluoropropene, 1,2 trifluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluorobutyl vinyl ether (PBVE), fluorinated or perfluorinated vinyl ethers including long chain perfluorinated vinyl ethers, fluorinated dioxoles, C4 or higher partially or perfluorinated alpha olefins, C3 or higher partially or perfluorinated cyclic alkenes, fluorinated or partially fluorinated acrylates and methacrylates, and combinations thereof.

11. The process of claim 8 or 9, wherein S comprises at least one monomer selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene (HFIB), perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-trifluoro-1-propene, 2-trifluoromethyl-3,3,3-trifluoropropene, 1,1-dichloro-1,1-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,1,1-trifluoromethyl-3,3,3-trifluoropropene, 1,2-dichloro-1,2-difluoroethylene, 1,2-di ...fluoromethyl-3,3,3-trifluoropropene, 1,2-difluoromethyl-3,3,3-trifluoropropene, 1,2-difluoromethyl-3,3,3-trifluoropropene, 1,2 trifluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, perfluoromethyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluorobutyl vinyl ether (PBVE), fluorinated or perfluorinated vinyl ethers including long chain perfluorinated vinyl ethers, fluorinated dioxoles, C4 or higher partially or perfluorinated alpha olefins, C3 or higher partially or perfluorinated cyclic alkenes, fluorinated or partially fluorinated acrylates and methacrylates, and combinations thereof.

12. 10. The process of claim 8 or 9, wherein fluoropolymer H is a copolymer of VDF and HFP, VDF constituting at least 70% by weight of H, and fluoropolymer S is a copolymer of VDF and HFP, HFP constituting at least 30% by weight of S, preferably at least 40% by weight of S, more preferably at least 45% by weight of S.

13. 10. The process of claim 8 or 9, wherein the amount of H is 40-60% by weight of the composition and the amount of S is 60-40% by weight of the composition.

14. 10. A process according to claim 8 or 9, wherein the total proportion of fluoropolymers H and S in the composition is at least 85% by weight, preferably at least 90% by weight, more preferably at least 95% by weight.

15. The melt viscosity of the fluoropolymer blend of S and H is 100 s at 230°C. -1 10. The process according to claim 8 or 9, wherein the viscosity is from 1000 to 4400 Pa s, preferably from 1000 to 3000 Pa s, more preferably from 800 to 2200 Pa s, at a shear rate of

16. The process of any one of claims 1 to 7, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a fluorinated thermoplastic vulcanizate (TPV).

17. 17. The process of claim 16, wherein the TPV comprises a crosslinker selected from the group consisting of melamine resins, epoxy resins, di- or higher polyisocyanates, polyaziridines, polycarbodiimides, polyoxazolines, dialdehydes (such as glyoxal), di- and trifunctional acetoacetates, malonates, acetals, thiols and acrylates, cycloaliphatic epoxy molecules, organosilanes (such as epoxy silanes, amino silanes), carbamates, diamines, and triamines, inorganic chelating agents (certain zinc and diols), and the like. tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl-acrylamide; fluorinated bisolefins as defined below, N,N'-bisallylcyclo-oct-7-ene-disuccinimide (BOSA); N,N,N'-tetraallyl-malonamide; trivinyl-isocyanurate; 2,4,6-trivinyl-methyltrisiloxane.

18. 10. The process of claim 1, wherein the fluorinated thermoplastic elastomeric polymer composition comprises a VDF and HFP based copolymer.

19. A process described in any one of claims 1 to 9, wherein the article produced from the process has an out-of-mold shrinkage of less than 4.3%, preferably 3%, and more preferably less than 1% according to a test method.

20. A process described in any one of claims 1 to 9, wherein the article produced from the process exhibits shrinkage of less than 5%, preferably 3%, and more preferably less than 1% after annealing the part at 65°C for 72 hours according to the test method.

21. A process described in any one of claims 1 to 9, wherein the article produced from the process exhibits shrinkage of less than 5%, preferably 3%, and more preferably less than 1% after annealing the part at 80°C for 72 hours according to the test method.

22. 1. A process for molding a fluorinated thermoplastic elastomer composition, said process comprising the steps of: a. Providing a semi-crystalline polymer composition having a formation ΔH of 1 to 10 J / g. b. The polymer i.T m Barrel temperature is 50 to 200°C higher than ii. Melting transition (T m ), preferably less than T c and T m and more preferably between T m Mold temperature 10 to 60°C lower than iii. A mold cooling time of 80 to 800 seconds; injection molding, The process wherein said fluorinated thermoplastic elastomer composition comprises a blend of H polymer and S polymer with an H ratio of 20% to 80%.

23. 23. The process of claim 22, wherein H comprises a copolymer comprising vinylidene fluoride and HFP and S comprises a copolymer comprising vinylidene fluoride and HFP.

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