Expandable tfe copolymers, method of making, and porous, expanded articles thereof

The present invention relates to fluoropolymers, which are tetrafluoroethylene monomer units and at least one other comonomer unit * (eg, Fluoroplastics) of at least 1.0% by weight or greater than 1.0% by weight as defined herein. -Vol 1: Non-Melt Processible Fluoroplastics; see Williams Andrew, Inc., Norwich, NY, at p.25 19 (2000); see ISO 12086), any fluoropolymer. Means that these comonomer units are polymerized to produce a fine powder type stretchable tetrafluoroethylene copolymer. Not only the porous products produced by stretching the above-mentioned copolymers (stretching under controlled conditions), but also the polymerization methods of these monomers are described.

Dispersion polymerization techniques for tetrafluoroethylene (TFE) monomers are known. Dispersion polymerization of TFE produces a resin known as "fine powder". See, for example, US Pat. No. 4,016,345 (Holmes, 1977). In such methods, generally, when adding tetrafluoroethylene monomers in the presence of a suitable polymerization initiator, when stirring, and 10-40 kg / cm.²A fully dispersible reagent is a water carrier such that in the presence of self-pressure of tetrafluoroethylene, the polymerization proceeds until it reaches the level of colloidally dispersed polymer particles and then stops the reaction. Introduced in.

On the other hand, the particulate tetrafluoroethylene resin is also produced by the suspension polymerization method, and the tetrafluoroethylene monomer is polymerized in a water-soluble suspension that has been stirred at high speed, and the dispersant is used in the suspension. Is used little or no. The type of particles produced by suspension polymerization is referred to by the technical term "granular" resin or "granular powder". See, for example, US Pat. No. 3,655,611 (Mueller, 1972).

Regarding these two polymerization methods, it is stated that various fluorinated alkylethylene comonomer and tetrafluoroethylene are copolymerized. See, for example, US Pat. No. 4,792,594 (Gangal et al., 1988). However, the present invention particularly relates to a water-soluble dispersion polymerization technique, and the product of the polymerization reaction is a copolymer of the present invention dispersed in the category of water-soluble colloidal dispersion using the technique. In this method, the tetrafluoroethylene monomer is pressurized in a pressure sterilizer containing water and a polymerization initiator, along with paraffin wax and emulsifier that suppress coagulation formation. The reaction mixture is agitated and the polymerization is carried out at the appropriate temperature and pressure. The polymerization results in the formation of water-soluble dispersed polymer particles, after which the dispersed polymer particles are coagulated by techniques known in the art to obtain what has become known as a fine powder polymer. ..

Various prior patents disclose techniques for homopolymerization of tetrafluoroethylene and polymerization of small amounts (<1.0% by weight) of other monomers with TFE. For example, US Pat. No. 4,576,869 (Malhotra, 1986). US Pat. No. 6,177,533 B1 (Jones, 2001), etc. can be mentioned.

Fine powder resins are known to be useful for paste extrusion methods and stretching (stretching) methods. Then, in those methods, the extrusions of the paste extrusion method are stretched after removing the extrusion auxiliary lubricant, and have various cross-sectional shapes such as rods, filaments, sheets, tubes, etc., and are porous. And yet produce a strong product. Such an extension method is disclosed in the pioneering patent US Pat. No. 3,953,566 (Gore, 1976), which is also commonly introduced in the present invention.

The stretching method was fully disclosed in the aforementioned '566 patent as applied to fluorocarbon polymers, and the method would identify what is now called a "stretched" form of TFE fluoropolymer, and further. , As a stretched or stretchable TFE polymer or copolymer, helps define what is meant herein.

The term "copolymer" is applied inconsistently as it is used in connection with fluoropolymers in the prior art. All objectives set forth herein follow the usual conventions of polymer science, as set forth in the Fluoroplastics text cited above and the ISO 12086 classification cited above. The term "copolymer" applies to any fluoropolymer containing at least one comonomer in excess of 1.0% by weight added to TFE. Fluoropolymers containing less than 1.0% comonomer are properly classified as "improved" homopolymers (Id.), But may actually need to be referred to as "improved" homopolymers. However, the term "polymer" is sometimes misused in the literature. Examining each particular example of such use, in fact, determining whether the referenced composition is an "improved" homopolymer or a genuine copolymer, i.e., the polymer product is actually 1.0 mass. The actual concentration of copolymers used to determine if they contain more than a percentage of the copolymer units must be determined.

As defined herein, the present invention is capable of providing genuine TFE copolymers of the fine powder type, which are useful because they are stretchable, as defined above. And produce a stretched TFE copolymer product.

U.S. Pat. No. 4,837,267 (Malhotra, 1989) discloses a composition of three components called "core-shell TFE copolymers", which are described as non-molten and processable, the composition of which is chlorotrifluoroethylene (CTFE) present in the core. ) Monomer-containing, perfluoro (n-alkyl vinyl) ether copolymer re-curing unit of 3-7 carbon atoms (column 1, rows 45-55). The total conomer content in the particles is said to be 0.001 to 2 mass percent. All of the examples presented relate to terpolymers, which have a much lower comonomer concentration than stated, i.e., in Example 1, CTFE is 0.23% and PPVE is 0.0145. % (The total is 0.2445% by mass), in Example 2, HFP is 0.13%, and PPVE is an extremely small amount that cannot be determined. Therefore, the stated 2% cap is not supported by the specification and examples presented. Moreover, the '267 patent makes no explicit or suggestive description or suggestion of stretchable or stretchable TFE copolymer compositions.

Japanese Patent Application (Published) 2005-306033A, published on November 4, 2005, discloses a thin PTFE film, which is non-porous and non-gas permeable (" It is stated on p.5) and contains "trace monomer units" in the range of 0.001-2 mol% described as "improved" PTFE (p.7). It is stated that the object of the present invention is obtained by "heat treatment" of a "porous PTFE resin film" and that the film is "substantially non-porous". In this document, there is no explicit description or suggestion of a TFE copolymer composition that is both porous and stretchable.

U.S. Pat. No. 4,391,940 (Hoechst, 1983) discloses and describes a partially modified tetrafluoroethylene polymer with a "three-shell" particle structure. It states that the resin is suitable for paste extrusion, produces cable insulation, and highly stretchable, non-sinterable tapes ('940 patent, abstract). This patent describes a fluorine-based modified monomer, which can be copolymerized with tetrafluoroethylenes such as, for example, perfluoropropenes, perfluoroalkyl vinyl ethers, halogen-substituted or hydrogen-substituted fluoroolefins. The specification states that the total amount of comonomer improver is very low, so that the particular performance of pure polytetrafluoroethylene is maintained, i.e., due to the extremely high melt viscosity of the improved polymer, it can be treated by melting. Note that it remains non-sexual ('940 patent, column 1, rows 62 and below). The disclosed product comprises improved polymer particles, which have a polymer core of at least one modified fluoroolefin comonomer of "0.05-6% by weight" and are in direct proximity to the core. A second outer shell of a polymer containing at least one modified fluoroolefin unit of "0.1-15% by weight" that has the first inner shell of the TFE unit and is in direct proximity to the inner shell. (Columns 3, 5 rows or less). Does the "three-shell" product example provided with respect to an example of the principles disclosed in that document cause defects at a relatively modest elongation ratio after stretching and removing the lubricant? Or completely torn. For example, the detailed method described in Example 31 (column 14, columns 60-16, line 6) causes defects at an elongation ratio of 4: 1 and completely at an elongation ratio of 8: 1. A tearing product was produced ('940 patent, Table 3).

Recently issued US Pat. No. 6,841,594 (Jones,) for the purpose of comparison and, in context, to disclose various prior arts. 2005) teaches that polytetrafluoroethylene (PTFE) means tetrafluoroethylene polymerized on its own in the absence of any significant comonomer, and "modified" PTFE has a concentration of It means that it is a TFE polymer with a low monomer, and because of such a low concentration, it teaches that the melting point of the obtained polymer is not lower than the melting point of PTFE. As confirmed in the preceding references above, the concentration of such comonomer is preferably less than 1% by weight, more preferably less than 0.5% by weight. The modified comonomer cited is, for example, hexafluoropropylene (HFP), perfluoro (methyl vinyl ether) (PMVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (ethyl vinyl ether). Examples include (PEVE), chlorotrifluoroethylene (CTFE), perfluoro-butylethylene (PFBE), and other monomers having side groups introduced into their molecules. These teachings are consistent with those disclosed above and are consistent with the definitions set forth herein. That is, in contrast to the term "modified homopolymer", the term "copolymer" means any fluoropolymer containing at least one comonomer in excess of 1.0% by weight added to TFE.

U.S. Pat. No. 6,127,486 (Burger et al., 2000) discloses a blended polymer of fluoropolymers and "thermoplastic" ones, stating that the "thermoplastic" ones include "PTFE copolymers" (column 4). , 46 lines). The amount of comonomer is such that, for the disclosed resins, the [modified] PTFE is "incapable of processing during melting" (specially highlighted herein). It teaches that it is restricted. The PTFE is expressed as modified PTFE, "in modified PTFE, the comonomer is contained in an amount of 2% by weight or less, preferably 1% by weight or less, based on the amount of PTFE." (Column 4). , 50 lines). No examples of copolymers with more than 1.0% by weight of comonomer added are provided, the patent relating to blended polymers, which have completely different physical properties from the genuine copolymers that form the subject of the present invention. It has.

As another recent document, Japanese Patent Application No. 10-243976 (Asahi Glass Co., Ltd., claiming priority on December 26, 1997) still states that the copolymer of TFE and the modified homopolymer. It further teaches the level of the technical field. The patent application, entitled "Tetrafluoroethylene Copolymers and Their Applications," includes, among other things, claims relating to polymers with added comonomer with a content of 0.005 to 0.05 mol% (about 0.012 to 0.123% by weight). The patent discusses known copolymerization techniques, and a further related Japanese application, JP (Kokoku) 3-66926, is R._fCH = CH₂(In the formula, R_fIs_C1-10It is a perfluoroalkyl group. ) Is proposed to modify PTFE. In the proposed method, comonomer is added continuously during the polymerization reaction in order to increase the modification level from the initial period. The modification is stated to be performed primarily to improve the extrudability of the fine paste, for example to reduce the extrusion pressure, and the content of polymerization units based on comonomer is 0.5. It is less than% by weight, but "in substantive terms, it is still relatively high" (more than 0.1% by weight). As a result, the product is substantially non-melt moldable and has a significantly lower crystallinity. And the literature mentions "another drawback", which is that such modified PTFE is not heat tolerant due to the structure of the comonomer incorporated. Finally, the Asahi patent application concludes with the following citation:

In addition, the structure of the comonomer exacerbates the molecular orientation and causes breakage during elongation, creating a product that is substantially unusable for the production of elongated porous articles. An object of the present invention is to provide a PTFE product that has excellent extrudability, is uniformly elongated, and produces a high-strength porous article.

It is then stated that this goal is achieved by limiting the introduction of comonomer-based polymerization units, which can be copolymerized with TFE, to an amount that does not affect the effect of processability.

Specifically, the Asahi application provides a product of TFE and a fluorinated comonomer, which fluorinated comonomer is of the general formula CH.₂= CH-R_f(In the formula, R_fIs C₁_-₁₀Represented by a perfluoroalkyl group), this polymer contains a polymerization unit based on a fluorinated comonomer in a proportion of 0.005 to 0.05 mol%. Further, a porous polymer article is provided, which is obtained by a method in which the modified PTFE described above is paste extruded and then stretched at a temperature of 25 O ° C or higher. However, it should be noted in this reference that the amount of monomer copolymerized exceeds a certain limit. The application states:

The content of the fluorinated comonomer-based polymerization unit of this application needs to be precisely controlled for study of extensibility. The content of the unit in PTFE should be reduced to the range of 0.005 to 0.05 mol%. A content of more than 0.05 mol% results in a slight decrease in polymer crystallinity and a decrease in paste extrusion pressure, with a significantly opposite effect on extensibility. If the content is less than 0.005 mol%, it will be substantially difficult to improve the physical characteristics of the stretched article, and another correction effect will be obtained. The range of 0.01 to 0.04 mol% is particularly preferable.

This is also consistent with the other teachings of the prior art document discussed above. In the examples of this Asahi reference, a "high" content (as defined by the applicant) of 0.42% by weight of perfluorobutylethylene comonomer is used, a low paste extrusion pressure is desirable, and "excellent". Extrusion characteristics were obtained. However, when stretched, the test sample broke. The specification states that at a "high" level of 0.42% by weight comonomer concentration, "... breakage occurred during elongation and it was not possible to obtain a porous article" (p.12, It is disclosed as paragraph 0050). In spite of these careful teachings, in contrast to those teachings, the present invention relates to genuine TFE copolymers, all of which genuine TFE copolymers contain more than 1.0 mass percent of comonomer units and all of them. Authentic TFE copolymers are stretchable, form porous stretched articles, and relate to the method of their production and further to the stretched articles produced thereby. Prior public literature does not disclose or suggest such a porous stretched copolymer article or resin produced from it.

<p num="0021"> In contrast to the teachings of the prior art, TFE copolymers with a wide range of comonomer unit concentrations as claimed herein are up to 25: 1 elongation ratio and 25: 1 elongation ratio, as described below. It forms a molded article that can be stretched beyond and is uniform and feasible. This synergistic result is truly amazing to those skilled in the art.</p>

<p num="0022"> A method of copolymerizing a fine powder type stretchable tetrafluoroethylene (TFE) copolymer is provided, in which the copolymer is composed of a tetrafluoroethylene (TFE) monomer unit of 99.0% by mass or less and at least 1.0% by mass or at least 1.0% by mass or more. It contains one other copolymer, i.e. a unit of copolymer other than tetrafluoroethylene. The other comonomer is an ethylenically unsaturated comonomer having sufficiently high reactivity with TFE, so that it can be polymerized with TFE. The method is to supply a tetrafluoroethylene (TFE) monomer unit of 99.0% by mass or less and at least 1.0% by mass or more than 1.0% by mass of other comomers to the pressurizing reactor in the pressurizing reactor. Including the step of copolymerizing the TFE monomer with at least one other comonomer, the proportions are based on the total mass of the supplied monomer, initiating the monomer polymerization with a free radical initiator, and , The supply of other monomers is stopped at the time of the polymerization reaction before the completion of the reaction. In one embodiment, optionally, excess comonomer is removed from the reactor as needed before the reaction is complete. (Discharge). The at least one other comonomer may be, for example, an olefin such as ethylene, propylene, isobutylene, and also chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), vinylidene fluoride (CFH = CH).₂), Vinylidene difluoride (CF)₂= CH₂), Hexafluoroisobutylene (HFIB). Trifluoro-ethylene (CF)₂= CFH)₁, And a fluorine-based monomer selected from the compounds represented by the following three general formulas. The general formula of fluorodioxol is as follows.</p><p num="0023"><chemistry num="1"><img id="000002" he="62" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0024"> In the formula, R₁And R₂ Is F or is a 1-3 carbon alkyl group containing at least one fluorine, and X, Y may be F10 and / or H.</p><p num="0025"> The general formula of fluorodioxol is as follows.</p><p num="0026"><chemistry num="2"><img id="000003" he="69" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0027"> In the formula, R_f Is a perfluoroalkyl carbon with 1-5 carbon atoms, and R₁And R₂Is F and / or CF₃Is.</p><p num="0028"> The general formula of fluorodioxalane is as follows. </p><p num="0029"><chemistry num="3"><img id="000004" he="78" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0030"> In the formula, R₁And R₂May be a perfluoroalkyl carbon with F and / or 1-5 carbon atoms. The at least one other comonomer may be a perfluoroalkylethylene monomer, eg, a monomer selected from the group consisting of perfluorobutylethylene (PFBE), perfluorohexylethylene (PFHE) and perfluorooctylethylene (PFOE). .. Alternatively, at least one other comonomer may be a perfluoroalkyl vinyl ether monomer, for example consisting of perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE). It may be a monomer selected from the group. Two or more other comonomer may be fed to the pressurized reactor to produce a multi-component copolymer, i.e., a terpolymer or the like.</p><p num="0031"> The monomer feed may be introduced as a preload for polymerization, or at least one other comonomer may be introduced during the reaction either incrementally or intermittently.</p><p num="0032"> The method of one embodiment preferably comprises stopping the supply of at least one other comonomer in less than 90% of the reaction completion.</p><p num="0033"> High concentrations of comonomer in the copolymer produced are, for example, at least 1.5% by weight of at least one other comonomer, at least 2.0% by weight of at least one other comonomer, and at least 5.0% by weight of at least one other comonomer. This is achieved by feeding the reactor with at least one other copolymer at high concentration levels.</p><p num="0034"> The aforementioned method is supplied with a polymerizable tetrafluoroethylene (TFE) monomer unit of 99.0% by mass or less and a reaction of at least 1.0% by mass or more than 1.0% by mass based on the total mass of the polymer produced. Produces a fine powder type stretchable tetrafluoroethylene (TFE) copolymer containing a polymerizable comonomer unit of one other comonomer. Since this genuine copolymer is stretchable, it is a porous stretched copolymer material with a microstructure characterized by nodes 1 interconnected by fibril 2, as shown in FIG. 1, well described below. It becomes. In addition, good alternative nodes 1, fibrils 2 and microstructures are illustrated in Figures 2 and 3.</p><p num="0035"> The stretchable copolymer produced contains at least one other polymerizable comonomer within the following group, which is an olefin such as ethylene, propylene, isobutylene, eg, chlorotrifluoroethylene (CTFE), Hexafluoropropylene (HFP), vinylidene fluoride (CFH = CH)₂), Vinylidene difluoride (CF)₂= CH₂), Hexafluoroisobutylene (HFIB) and trifluoro-ethylene (CF)₂= CFH)₁, Fluorodioxol and fluorodioxalane, and perfluoroalkylethylene monomers, such as perfluorobutylethylene (PFBE), perfluorohexylethylene (PFHE), perfluorooctylethylene ( PFOE), and there are perfluoroalkyl vinyl ether monomers, such as perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE). .. The copolymer produced may contain more than one polymerizable comonomer, the comonomer content in the copolymer is consistently greater than 1.0% by weight, and may be other comonomeres in the polymerizable unit greater than 1.5% by weight. Indeed, other comonomers of polymerizable units greater than 5.0% by weight may be used.</p><p num="0036"> In a further embodiment of the invention, a copolymer material is produced that exhibits excellent adhesive properties that cannot be achieved with PTFE homopolymers. That is, after placing the copolymer under conditions of lower temperature and / or shorter time and / or lower pressure than required to adhere the PTFE homopolymer to itself, the copolymer is itself or others. Can be adhered to the material of. For example, as described later herein with respect to room temperature adhesion tests, this adhesion or bond can be achieved with these excellent copolymers at temperatures below about 29 O ° C (where relative to PTFE homopolymers). It is cooler than the required temperature.)</p><p num="0037"> The copolymer of the present invention is produced in the form of fine particles dispersed in an aqueous medium, and the fine particles are solidified using known techniques to produce a fine powder resin. Further provided in accordance with the present invention is a porous stretched TFE copolymer material having a node microstructure interconnected by fibril. These porous stretched copolymer materials can be produced in the form of molded articles such as sheets, films, tubes, rods, continuous filaments, for example. And these articles are generally robust, i.e., the matrix tensile strength in at least one direction exceeds 5,000 psi. For a product, at least one matrix tensile strength can exceed 30,000 psi. As such, it provides an ultimately robust, porous and genuine copolymer stretched TFE article that is useful in a variety of applications.</p><p num="0038"> The copolymer of the present invention is produced in the form of fine particles dispersed in an aqueous medium, and the fine particles are solidified using known techniques to produce a fine powder resin. Further provided in accordance with the present invention is a porous stretched TFE copolymer material having a node microstructure interconnected by fibril. These porous stretched copolymer materials can be produced in the form of molded articles such as sheets, films, tubes, rods, continuous filaments, for example. And these articles are generally robust, i.e., the matrix tensile strength in at least one direction exceeds 5,000 psi. For a product, at least one matrix tensile strength can exceed 30,000 psi. As such, it provides an ultimately robust, porous and genuine copolymer stretched TFE article that is useful in a variety of applications. In a further embodiment, such stretched TFE material may be compressed or otherwise processed to achieve reduced porosity utilizing known processing techniques.</p><p num="0039"> The copolymers of the present invention can be used in a wide variety of medical and commercial devices. Medical devices include incorporating the copolymers of the invention into long-term and short-term implantable devices, as well as disposable or single-use consumables and devices. These devices are, but are not limited to, vascular grafts (for treating, replacing, attaching or augmenting blood vessels, or other vascular grafts), other shunting conduits, etc. For surgical and laparoscopic sheets and patches, intracavitary prosthesis (eg, stent grafts), components of cell suppression devices, substrates for drug delivery, catheters, space replenishment or augmentation devices, junction spacers, devices Surface coatings, lenses, laboratory or clean room surface surface coatings, seals, gaskets, vascular contact surfaces, bags, containers, fabric liners.</p>

The attached drawings are as follows.<figref num="1">FIG. 1 is a photomicrograph of an SEM of a stretched sheet of copolymer resin prepared according to the present invention described herein, taken at 200X magnification, with fine details of node 1 and fibril 2 of this material. It shows the structure and shows that the intersections of each node are interconnected by a variety of fibril 2.</figref><figref num="2">FIG. 2 is a SEM micrograph of a stretched bead sample of the copolymer resin prepared in Example 6, taken at 200X magnification, showing the microstructures of node 1 and fibril 2 of this material, respectively. It is shown that the intersections of the nodes of are interconnected by the diverse fibrils 2.</figref><figref num="3">FIG. 3 is a micrograph of another SEM of a sample of a stretched sheet of copolymer resin prepared in Example 6, taken at a magnification of 20,00 OX, showing the node 1 and fibril 2 microstructures.</figref><figref num="4">FIG. 4 shows the differential scanning calorimetry (DSC) results, which show the peak temperature of the melt transition of the materials of Examples 10, 12 and 13, and the temperature of the melt transition of the PTFE homopolymer material of Comparative Example. Shows the peak of.</figref>

A method of polymerizing a fine-powder type genuine tetrafluoroethylene (TFE) copolymer is provided in which the copolymer contains a polymerized comonomer unit of at least one non-TFE at a concentration of at least 1.0 mass percent or more than 1.0 mass percent. Containing in concentration, it can also be contained in concentrations above 5.0 mass percent, the copolymer is stretchable, i.e. the copolymer is stretchable and the microstructure of the nodes interconnected by fibrils. Produces a TFE copolymer article that is robust, useful, and stretchable.

The copolymers of the present invention are made by a polymerization method, the copolymerization reaction is initiated with a suitable initiator, then the initiator addition is stopped and the progress is 15% to 90% with respect to the completion of the reaction. Slow down the reaction at the point and proceed towards completion. Preferably, the initiator addition is stopped at the midpoint of the reaction, i.e. 20-60% of completion.

Dispersants that are substantially non-telogenic are used. Ammonium perfluorooctanoic acid (APFO or "C-8") is one acceptable dispersant. Programmed addition methods (pre-loading and pumping) are known and preferred. As described herein, attention is paid to the purification of the material in order to achieve the preferred properties of the polymerization. There is a need to minimize ionic impurities that can increase ionic strength, as well as soluble organic impurities that can cause chain transfer or chain termination. It is particularly important to use ultrapure water in all such polymerization reactions.

The fracture strength associated with TFE polymer beads produced from a particular resin, extruded and stretched (stretched) is directly related to the resin's general suitability for stretching. Come on. And various methods are used to measure the breaking strength. The following means were used to prepare and test stretched bead samples made from the copolymers of the present invention. Data for the study are reported below.

For the given resin, 113.4 g of fine powder resin to 130 cc / lb (24.5 g) Isopar^TM Mix with K. The mixture is aged in a constant temperature water bath at 22 ° C for about 2 hours. A 1-inch diameter cylindrical preform is made by applying preliminary pressure of about 270 psig for about 20 seconds. The preform is inspected to ensure that it is crack free. Extruded beads were made by extruding a pre-lubricated resin through a 0.100 inch diameter die with an inlet angle of 30 degrees. The extruded barrel is 1 inch in diameter and the ram is operating at 20 inches / minute. The extrusion barrel and die are left at room temperature to maintain 23 ° C plus or minus 1.5 ° C. Dry the beads at 225-230 ° C for about 25 minutes and Isopar Get rid of K. Discard the first and last approximately 8 feet of extruded beads to eliminate end effects. The 2.0 inch portion of the extruded beads is stretched at 290 ° C and at an initial rate of elongation of 100% per second by stretching to a final length of 50 inches (25: 1 stretch ratio), which is per second. It has a constant speed of 2 inches. The maximum breaking load of the removed sample, which was removed approximately 1 foot long from near the center of the stretched beads and held at room temperature (23 ° C plus or minus 1.5 ° C), was 2 inches initial sample length and 12 inches / minute. Instron with crosshead speed^TMMeasure using a tensile test device. Make two measurements and record the average of the two samples. This means is similar to that described in US Pat. No. 6,177,533B1. Stretching here is performed at 290 ° C instead of 300 ° C.

A core-shell resin structure containing a polymerization monomer added to TFE, which is structurally identical to that produced by the techniques described herein and is disclosed earlier than the present application, has long been known. See, for example, US Pat. Nos. 4,576,869 (Malhotra), 6,541.589B1 (Baillie) and 6,841,594B2 (Jones). As described in the following examples, for the compositions described in the claims, the resins made according to the present invention are genuine copolymers, i.e., the content of comonomer is greater than 1.0% by mass. This is verified using solid NMR spectroscopy, mass balancing, and methods of detecting residual monomers in the polymerized batch gas phase through gas chromatography. All of the compositions can be stretched to an elongation ratio of at least 25: 1 and can be demonstrated by SEM testing as shown below, but with excellent node 1 and fibril 2 as shown in FIG. The figure is shown in FIGS. 2 and 3 which forms a stretched copolymer article with the microstructure of, and further in another microstructure of the superior node 1 and fibril 2.

The properties of the copolymer material are examined by standard analytical techniques available in the art, the standard analytical techniques of which are not particularly limited, but are limited to DCS, NMR (including fluorine, protons, carbon). And other known NMR techniques), TGA, IR, FTIR, Raman spectroscopy, and other suitable techniques.

<u style="single">test</u><u style="single">Differential scanning calorimetry (DSC)</u> This test was performed using a TA Instruments Q2000DSC and a standard TA Instruments aluminum pan and lid for differential scanning calorimetry (DSC). Mass measurements were performed on a microbalance of Sartorius MC 210P.

The Q2000 was calibrated by using the Calibration Wizard, which is available via the Thermal Advantage supplied to this device. All calibrations and scans were performed under a constant nitrogen flow of 50 ml / min.

The sample was placed on a dish and the mass was recorded with an accuracy of 0.01 mg and the sample was in the range of 5.00 mg to lO.OO mg. These values were entered into the Q2000 Thermal Advantage control software. The lid was placed on a dish and crimped using standard pressure. As a reference, a dish excluding the sample article was prepared and its mass was also entered into the software. A dish containing the sample article was filled into the Q2000 sample sensor, while an empty dish was filled into the reference sensor. The sample was equilibrated at -5 O ° C and then raised to 400 ° C at a rate of 20 ° C / min. Data were analyzed using Universal Analysis 2000 V.3.9A from TA Instruments.

<u style="single">Adhesion test</u> Cut the extruded PTFE tape into a rectangle 20 mm wide x 75 mm long and Fred S. A carver press model # 3895 manufactured by Carver Inc. (Wabash Indiana) was heat-bonded to an aluminum foil substrate to prepare a 90-degree peeled sample. The tape was combined with 23 micron thick Heavy Strength aluminum foil from Reynolds Consumer P Rod ucts Co. (Richmond, VA 23230). UBE Industries, A polyimide release film commercially available from LTD., (Tokyo, Japan) with a thickness of 25 microns of Upilex grade 25 SDADB is used to prevent adhesion to the press plate and to be pre-cracked at 90 degrees. The peeling test was started. The melt press time and normal force were 30 minutes and 450 kg, respectively. Samples were prepared at melt press temperatures of 195 ° C, 29 O ° C and 350 ° C. Once bound, the sample was cooled, while still applying pressure for about 20 minutes to about 21 ° C. Foil PTFE tape stripped samples at each binding temperature were prepared simultaneously to maintain a common thermal history. The 90 degree peel test is performed at a test speed of 1 mm / sec using an Imass SP-2000 Slip-Peel test device commercially available from lnstrumentors Inc. (Strongsville, OH). The result is J / m²Recorded in. The material showed adhesion and showed any measurable value. If the sample broke before the test, it was recorded as "no adhesion".

NMR analysis A 10-25 mg sample was filled into a 2.5 mm ZrO spinner using standard Bruker 2.5 mm packaging parts (Bruker BioSpin Inc., Boston, MA). Bruker-BioSpin's 2.5mm Proton-enhanced Magic Angle Spinning (CPMAS) probe placed on a Bruker ultra-shielding and superconducting magnet with a standard inner diameter of 7.05T¹⁹F spectra were collected at approximately 296 Kelvin. The sample was placed at a magic angle and rotated at 32.5 kHz. At 282.4 MHz using the Bruker BioSpin Avance Il 300 MHz system¹⁹F NMR data was collected. The software and data processing used for data collection was Topspin 1.3. Data were collected using the conditions shown in Table B. The spectrum reference was externally -123 ppm PTFE. at.

<tables num="1"><img id="000005" he="53" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<tables num="2"><img id="000006" he="74" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

The following examples are intended to illustrate the invention, but are by no means configured to limit the scope of the invention.

<p num="0056"> Example 1 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0057"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then 0.8 MPa of VDF was added and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min and approximately 2 kg of TFE was added. After adding the 2 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO for 3Kg TFE₄Was added at 20 mL / min and the addition of KMnO4 was further reduced to 10 mL / min for the 4 kg TFE. Then 4 kg of TFE was added and no more KMnO4 was added.</p><p num="0058"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0059"> Then, the polymerization reaction was continued, 14.3 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 44.73 kg, containing 32.6% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C. The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.296 microns and the standard specific density was 2.156. The measurement result of the VDF concentration of the copolymer was 3.48 mol% (2.26 mass%). The breaking strength of the beads was 6.6 lbs.</p><p num="0060"> The measurement result of the matrix tensile strength of the sample was 37,299 psi.</p><p num="0061"> Example 2 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0062"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then, 0.8 MPa of trifluoroethylene (here, designated TrFE) was added, and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.1 g / L) was infused at 80 ml / min and consumed approximately 0.5 kg of TFE. By the time the 2 kg TFE was consumed, the speed was reduced to 40 ml / min. The pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO for the next 0.5 kg TFE₄Was added again at 40 mL / min and continued until 4 kg of TFE was consumed. After consuming 4kg of TFE, KMnO₄I didn't add any more.</p><p num="0063"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0064"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 45.74 kg containing 35.8% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C. The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.283 microns and the standard specific density was 2.213. The measurement result of the trifluoroethylene concentration of the copolymer was 3.2 mol% (2.6 mass%). The fracture strength of the bead sample was 7.24 lbs.</p><p num="0065"> The measurement result of the matrix tensile strength of the sample was 28,602 psi.</p><p num="0066"> Example 3 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0067"> 8 ml of PFBE was added to the discharged reactor, the reactor was heated to 83 ° C. and stirred at 60 rpm. Then 0.8 MPa of VDF was added and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.1 g / L) was injected at 80 ml / min to complete the addition of approximately 2 kg of TFE. After adding the 2 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO at 40 mL / min until 4 kg of TFE is consumed₄Was added. After adding the 4 kg TFE, no more KMnO4 was added.</p><p num="0068"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0069"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 42.76 kg with a 29.0% solid content. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0070"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.263 microns and the standard specific density was 2.157. The measurement result of the VDF concentration of the copolymer was 4.30 mol% (2.80% by mass). The measurement result of the PFBE concentration of the copolymer was 0.03 mol% (0.07% by mass), and the total copolymer concentration in the composition was 2.87% by mass. The fracture strength of the bead sample was 13.6 lbs.</p><p num="0071"> The measurement result of the matrix tensile strength of the sample was 44,878 psi.</p><p num="0072"> Example 4 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0073"> 19.94 g of PFOE was added to the discharged reactor, the reactor was heated to 83 ° C and stirred at 60 rpm. Then 0.8 MPa of VDF was added and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.1 g / L) was injected at 80 ml / min to complete the addition of approximately 2 kg of TFE. After adding the 2 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO at 40 mL / min until consuming an additional 0.5 kg of TFE₄Was added again. Decelerate to 20 mL / min until consuming 4 kg of TFE and KMnO₄Was added. After adding the 4 kg TFE, no more KMnO4 was added.</p><p num="0074"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0075"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 42.82 kg containing 28.4% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0076"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.240 microns and the standard specific density was 2.159. The measurement result of the VDF concentration of the copolymer was 3.50 mol% (2.20 mass%). The measurement result of the PFOE concentration of the copolymer was 0.03 mol% (0.16 mass%), and the total copolymer concentration in the composition was 2.36 mass%. The fracture strength of the bead sample was 14.1 lbs.</p><p num="0077"> The measurement result of the matrix tensile strength of the sample was 48,236 psi.</p><p num="0078"> Example 5 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0079"> 8 ml of PFBE was added to the discharged reactor, the reactor was heated to 83 ° C. and stirred at 60 rpm. Then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 1 kg of TFE. At this point, the pressure in the reactor was reduced to 50 Kpa using a vacuum device, pressurized with a VDF of 0.8 MPa until the pressure reached 2.8 MPa, followed by the addition of TFE. KMnO at 80 mL / min until an additional 1.0 kg of TFE is consumed₄Was added again. KMnO decelerates to 40 mL / min until 4 kg of TFE is consumed at the time of consumption₄Was added. After consuming the 4 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO until the 5kg TFE is consumed₄An additional amount of was added at 10 mL / min. After consuming the 5 kg TFE, no more KMnO4 was added.</p><p num="0080"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0081"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 48.8 kg, containing 34.5% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0082"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.234 microns and the standard specific density was 2.151. The measurement result of the VDF concentration of the copolymer was 3.15 mol% (2.04% by mass). The measurement result of the PFBE concentration of the copolymer was 0.03 mol% (0.07% by mass), and the total copolymer concentration in the composition was 2.11% by mass. The fracture strength of the bead sample was 8.6 lbs.</p><p num="0083"> The measurement result of the matrix tensile strength of the sample was 31,342 psi.</p><p num="0084"> Example 6 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0085"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 1 kg of TFE. At this point, the pressure in the reactor was reduced to 50 Kpa using a vacuum device, pressurized with a VDF of 0.8 MPa until the pressure reached 2.8 MPa, followed by the addition of TFE. KMnO at 80 mL / min until consumed additional 2 kg of TFE₄Was added again. KMnO decelerates to 40 mL / min until 4 kg of TFE is consumed at the time of consumption₄Was added. After consuming the 4 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO until the 5kg TFE is consumed₄An additional amount of was added at 40 mL / min. After consuming the 5 kg TFE, no more KMnO4 was added.</p><p num="0086"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0087"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 46.86 kg, containing 35.0% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0088"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.265 microns and the standard specific density was 2.158. The measurement result of the VDF concentration of the copolymer was 3.35 mol% (2.17% by mass). The fracture strength of the bead sample was 6.6 lbs. The SEM of the microstructure of the bead sample is shown in Figure 2.</p><p num="0089"> The measurement result of the matrix tensile strength of the sample was 26,053 psi.</p><p num="0090"> The copolymer material formed in this example was then lsopar K (Exxon mobil Corp., Fairfax, It was blended with VA) in a fine powder state at a ratio of 0.196 g / g. The lubricant was compressed in a cylinder to form pellets and placed in an oven set at 49 ° C for approximately 12 hours. The compressed and heated pellets were ram extruded to produce a tape approximately 16.0 cm wide and 0.73 mm thick. The extruded tape was then scrolled between compression rolls to a thickness of 0.256 mm. The tape was then stretched laterally to a width of approximately 56 cm (ie, a 3.5: 1 ratio) and dried at a temperature of 25 O ° C. The dry tape was stretched between bank rolls on a heating plate set to a temperature of 345 ° C. The speed ratio between the 2nd bankroll and the 1st bankroll was 10: 1. The width of the stretched tape was 12.1 cm. The tape stretched in the longitudinal direction is then stretched laterally to a ratio of approximately 25: 1 at a temperature of approximately 360 ° C, then suppressed from shrinking to 380 ° C for approximately 24 seconds. It was heated in the set oven. The SEM of the obtained sheet is shown in Fig. 3. Figure 3 was taken at a magnification of 20,00 OX and shows the microstructure of Node 1 and Fibril 2.</p><p num="0091"> Example 7 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0092"> 8 ml of PFBE was added to the discharged reactor, the reactor was heated to 83 ° C. and stirred at 60 rpm. Then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 1 kg of TFE. At this point, the pressure in the reactor was reduced to 50 Kpa using a vacuum device, pressurized with 0.8 MPa TrFE until the pressure reached 2.8 MPa, followed by the addition of TFE. KMnO at 80 mL / min until consumption of additional 3 kg of TFE₄Was added again. After consuming the 4 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO until the 5kg TFE is consumed₄An additional amount of was added at 40 mL / min. After consuming the 5 kg TFE, no more KMnO4 was added.</p><p num="0093"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0094"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 46.9 kg, containing 33.1% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0095"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.227 microns and the standard specific density was 2.217. The measurement result of the TrFE concentration of the copolymer was 4.2 mol% (3.5 mass%). The measurement result of the PFBE concentration of the copolymer was 0.03 mol% (0.07% by mass), and the total copolymer concentration in the composition was 3.57% by mass. The fracture strength of the bead sample was 3.48 lbs.</p><p num="0096"> The measurement result of the matrix tensile strength of the sample was 13,382 psi.</p><p num="0097"> Example 8 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0098"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 1 kg of TFE. At this point, the pressure in the reactor was reduced to 50 Kpa using a vacuum device, pressurized with 0.8 MPa TrFE until the pressure reached 2.8 MPa, followed by the addition of TFE. KMnO at 80 mL / min until consumption of additional 3 kg of TFE₄Was added again. After consuming the 4 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO until the 5kg TFE is consumed₄An additional amount of was added at 40 mL / min. After consuming the 5 kg TFE, no more KMnO4 was added.</p><p num="0099"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0100"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 47.22 kg, containing 34.8% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0101"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.276 microns and the standard specific density was 2.219. The measurement result of the TrFE concentration of the copolymer was 4.17 mol% (3.5 mass%). The fracture strength of the bead sample was 3.95 lbs.</p><p num="0102"> The measurement result of the matrix tensile strength of the sample was 15,329 psi.</p><p num="0103"> Example 9 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0104"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 1 kg of TFE. At this point, the pressure in the reactor was reduced to 50 Kpa using a vacuum device, pressurized with 1.2 kg HFP until the pressure reached 1.9 MPa, followed by the addition of TFE. KMnO at 80 mL / min until consumption of additional 3 kg of TFE₄Was added again. After consuming the 4 kg TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. KMnO until the 5kg TFE is consumed₄An additional amount of was added at 80 mL / min. After consuming the 5 kg TFE, no more KMnO4 was added.</p><p num="0105"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0106"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 48.54 kg containing 30.4% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0107"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.302 microns and the standard specific density was 2.157. The measurement result of the HFP concentration of the copolymer was 0.77 mol% (1.25 mass%). The fracture strength of the bead sample was 7.60 lbs.</p><p num="0108"> The measurement result of the matrix tensile strength of the sample was 34,178 psi.</p><p num="0109"> Example 10 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0110"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then, 0.81 MPa of CTFE was added, and then TFE was added to bring the pressure to 2.8 MPa. At this point, a solution containing 3 g ammonium persulfate and 3 g sodium hydrosulfite in 2000 ml of DI aqueous solution was injected at 40 ml / min until 2 kg of TFE was consumed. After adding 2 kg of TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. Additional initiator solution was added again at 20 mL / min until all 2.5 kg of TFE was consumed. At this point the speed was reduced to 10 mL / min. After consuming all 3 kg of TFE, no more initiator was added.</p><p num="0111"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0112"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 48.54 kg containing 30.4% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0113"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.245 microns and the standard specific density was 2.228. The measurement result of the CTFE concentration of the copolymer was 3.9 mol% (4.5% by mass). The fracture strength of the bead sample was 7.6 lbs.</p><p num="0114"> The measurement result of the matrix tensile strength of the sample was 23,991 psi.</p><p num="0115"> Adhesion tests will be conducted and the results will be reported in Table 2. A DSC scan for this material is shown in FIG. 4, showing that the material undergoes a first melt transition at about 247 ° C.</p><p num="0116"> Example 11 In a 50 liter horizontal polymerization reactor with a 3-blade stirrer, 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), 0.2 g of FeSO₄, And 5 g of succinic acid dissolved in about 5 Og of DI water was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0117"> 8 ml of PFBE was added to the discharged reactor, the reactor was heated to 83 ° C. and stirred at 60 rpm. Then, 0.81 MPa of CTFE was added, and then TFE was added to bring the pressure to 2.8 MPa. A solution containing 3 g of ammonium persulfate and 3 g of sodium hydrosulfite in 2000 ml of DI aqueous solution was injected at 40 ml / min until 2 kg of TFE was consumed. After adding 2 kg of TFE, the pressure in the reactor was reduced to 50 Kpa using a vacuum device and pressurized to 2.8 MPa with fresh TFE. Additional initiator solution was added again at 20 mL / min until all 3.0 kg of TFE was consumed. At this point the speed was reduced to 10 mL / min. After consuming 3 kg of TFE, no more initiator was added.</p><p num="0118"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0119"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 47.19 kg, containing 36.6% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0120"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.178 microns and the standard specific density was 2.247. The measurement result of the CTFE concentration of the copolymer was 3.1 mol% (3.7 mass%). The measurement result of the PFBE concentration of the copolymer was 0.03 mol% (0.07% by mass), and the total copolymer concentration in the composition was 3.77% by mass. The fracture strength of the bead sample was 3.48 lbs.</p><p num="0121"> Example 12 Dissolve in 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), and approximately 5 Og of DI water in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer. 5 g of succinic acid was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0122"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then 2.0 MPa of VDF was added and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.063 g / L) was infused at 80 ml / min to complete the addition of approximately 4 kg of TFE. KMnO while adding the next 2 kg of TFE₄Was added at 40 mL / min. After consuming 6 kg of TFE, no more KMnO4 was added.</p><p num="0123"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0124"> Then, the polymerization reaction was continued, 16 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 48.64 kg containing 31.2% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C.</p><p num="0125"> The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.321 microns and the standard specific density was 2.137. The measurement result of the VDF concentration of the copolymer was 11.8 mol% (7.90% by mass). The fracture strength of the bead sample was 10.53 lbs. The measurement result of the matrix tensile strength of the sample was 37,000 psi.</p><p num="0126"> Adhesion tests will be conducted and the results will be reported in Table 2. A DSC scan for this material is shown in Figure 4, showing that the material undergoes a first melt transition at about 185 ° C.</p><p num="0127"> Example 13 1.5 kg of wax, 28 kg of deionized water (DI), 18 g of ammonium perfluorooctanoate (APFO), 1.5 g of ZnCl in a 50 liter horizontal polymerization reactor equipped with a 3-blade stirrer.₂And 5 g of succinic acid dissolved in about 5 Og of DI water was added. The reactor and its additions were heated to a temperature above the melting point of the wax. The reactor was repeatedly drained and pressurized with TFE (up to about 1 Atm or less) until the oxygen level was reduced to 20 ppm or less. The addition was briefly agitated at about 60 rpm during the drain and purge cycles to ensure that the water was deoxidized.</p><p num="0128"> The reactor was heated to 83 ° C and stirred at 60 rpm. Then 2.0 MPa of VDF was added and then TFE was added to bring the pressure to 2.8 MPa. At this point, KMNO of DI aqueous solution₄(0.1 g / L) was injected at 80 ml / min to complete the addition of approximately 4 kg of TFE. KMnO while adding the next 2 kg of TFE₄Was added at 40 mL / min. After consuming 5 kg of TFE, an additional 200 g of initiator solution was added. Added KMnO₄The total amount of solution was 3.375 kg.</p><p num="0129"> Approximately 320 g of 20% APFO solution was added in 4 OmL increments, the first increase was added after about 1 kg of TFE was added, followed by each 4 OmL increase after each 1 kg of TFE was added. Minutes were added and, as a result, the final increase was added after 8 kg of TFE had reacted.</p><p num="0130"> Then, the polymerization reaction was continued, 9 kg of TFE was added to the reactor, and then the reaction was stopped. The mass of the dispersion produced was 40.18 kg, containing 19.6% solids. The dispersion was coagulated with nitric acid and dried at 170 ° C. The size (RDPS) of the dispersion liquid particles of the polymer particles themselves was 0.339 microns, and the measurement result of the VDF concentration of the copolymer was 23.8 mol% (16.7% by mass). The fracture strength of the bead sample was 8.62 lbs. The measurement result of the matrix tensile strength of the sample was 23,511 psi.</p><p num="0131"> Adhesion tests will be conducted and the results will be reported in Table 2. A DSC scan for this material is shown in Figure 4, showing that the material undergoes a first melt transition at about 193 ° C.</p><p num="0132"> A summary of the results shown in the above examples is shown in Table 1. Adhesion results are reported in Table 2. The aforementioned examples are provided to illustrate certain preferred embodiments of copolymers made according to the principles set forth herein, without limitation. Further copolymers, terpolymers, etc. that incorporate comonomer known to react with TFE can also be used. It is possible to add these additional comonomer at a given concentration and react the comonomer based on the reactivity ratio of the monomer to TFE, whether discharged or not, and all of the above will be issued. As shown in the published literature (see, eg, Well-Architectured Fluoropolymers: Synthesis, Properties, and Applications; Elsevier; Amsterdam 2004, pp.209), those skilled in the art know. That is.</p><p num="0133"> Although the present invention is disclosed herein in connection with an embodiment and a detailed description, it is not possible for a person skilled in the art to make improvements and modifications from such detailed contents. , It is possible without departing from the gist of the present invention, and such improved inventions and modified inventions are considered to be within the scope of the claims shown below.</p><p num="0134"><tables num="3"><img id="000007" he="102" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0135"><tables num="4"><img id="000008" he="54" wi="158" file="JP5756079B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p>