TW575626B - Compositions of low melt viscosity polytetrafluoroethylene and non-fluorinated polymer - Google Patents

Description

575626 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of invention (2) Compared with the amount (Μη), it has at least 2,000,000. Similar to high melt viscosity PTFE, low MV PTFE has thermal stability, chemically inert lubricity and high melting temperature. The very low MV of this PTFE causes the PTFE to melt and flow, as shown by its melt viscosity, but the very low molecular weight loss and strength of this PTFE, therefore, is extruded from this low MV PTFE through melt extrusion. Plastic objects can crack during handling. For example, when the MV is measured, it is extruded with very slight burnt cracks, and the tensile test sample formed by injection molding breaks when it is only sandwiched in a tensile testing machine. Therefore, the resin There is no measurable tensile strength. Therefore, although the solution is flowable, low-MV V PTFE is not melt-manufacturable. This attribution utilizes low MV PTFE to such applications as liquid lubricants and additives in support coatings. This low MV PTFE is often referred to as the PTFE micropowder and is different from the PTFE region described above as the high MV PTFE. There is a need to seek greater availability of low MV PTFE. Summary of the Invention The present invention satisfies this need by combining low MV PTFE with an unfluorinated polymer (which is thermally stable at a temperature of at least 140 ° C) in an amount of 5 to 95% by weight per resin Based on the combined weight of low MV PTFE and unfluorinated polymer, based on 100% by weight in total. The resulting composition comprising a low MV PTFE and a non-fluorinated polymer is melted to produce a product that exhibits improved properties. For example, these compositions, which mainly contain low MV PTFE, show unexpectedly high strength and greater dimensional stability under load. Compositions containing primarily unfluorinated polymers also show unexpectedly high strength. -5- This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) i .---: --------- installation (please read the precautions on the back to write this page) «I» I 1 · IP «I · 1 > ρ Order · ----- ♦ Ββ 1 I BBS I:

-UB · OH ΜΗΚ I 575626 A7 V. Description of the invention (3 t The present invention <In a specific embodiment, the fibrous filler is present in the combination Μ 埴 ^ The amount is: low MVPTFE, unfluorinated polymer and fiber, The combined weight of quasi-like authentic materials is 10 to 35% by weight. The small proportion of the soil, FE, and the presence of FE in the two-component composition surprisingly improves the composition and early edge of the two-component composition. Low Mv PTFE with high load also shows unexpectedly high tensile strength when used in the composition. Detailed description of the low MV PTFE used in the present invention, whether obtained by degrading high MV PTFE by irradiation or by direct polymerization, It is preferred to have a melt viscosity of ㈧ 工 X 10 Poise &lt; fe. Unless otherwise indicated, the melt viscosity disclosed herein is in accordance with ASTM (American Society for Testing and Materials) D 丨 23 9_52 D procedures Measured at 372 ° C, modified as shown in US Patent No. 4,38,618. These resins are also called pTFE fine powders and are in phase with the usual PTFE (it is south) viV PTFE. Difference. PTFE micropowder (low MV PTFE) is a tetragas acetamidine homopolymer or Modified homopolymer (containing a small amount, such as less than 0.5 mole% comonomer to improve the ability to form a film), which has a molecular weight of 50, 000 to 70,000 Μη). PTFE micropowder is further recorded in the Encyclopedia of Chemical Technology published by John Wiley &amp; Sons, Fourth Edition, Volume 11, (1994), ρ · 637-639 and HJ Hendriock's "Text" PTFE Micropowder "Powder", published by Kunstoffe German Plastics, 76, p 920-126 (1986), etc. Although PTFE fine powder is meltable and flowable, as mentioned above, it is not itself meltable and can be manufactured. Thermal stability without fluorination Examples of polymer include poly (arylene ether ketone), poly (1,4 (2,6-dimethylphenyl) oxide is commonly called polyphenylene ether, polyphenylene sulfide-6- this paper rule 7 rabbit China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first

• Line. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575626 'A7 B7 V. Description of the invention (4) Ether, polyimide, imine and polyether. These polymers are also fluorine-free and thermoplastic. All these resins are thermally stable at temperatures of at least 140 ° C. By thermal stabilization is meant that the resin can be used continuously or independently exposed to such a high temperature for a long period of time, such as ten days without degradation of the resin ^ 3 is shown without any visible change in chemical or physical properties. The present invention is applicable to all such thermally stable polymers. The unfluorinated polymer is preferably thermally stable at a temperature of at least 170 ° C, and more preferably at least 200 ° C. The polymer preferably has a melting temperature of at least 220 / C and more preferably at least 275 ° C. In the case of amorphous polymers, the glass transition temperature should preferably be at least 220 ° C. Polyether fluorene is an amorphous polymer with a long-term use temperature (thermal stability) of up to 190 ° C and a glass transition temperature of 220 ° C. Polyammonium imine is thermally stable at a temperature of at least 250 ° C and melts at a temperature of at least 290 ° C. Polyphenylene sulfide melts at 285 ° C. Because providing the highest thermal stability, aromatic unfluorinated thermal stabilization polymers are preferred. For example, polyarylene ether ketones are thermally stable at least 250 ° C and melt at temperatures of at least 300 ° C. Especially preferred is polyarylene ether ketone. Poly (arylene ether ketone) is a well-known family of resins. It includes polyether ketones with the following repeating units: -JI —: --------- Packing-(Please read the precautions on the back first ΐ ^ ιιιι (Write this page) Order · • Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Polyether ether brewing with repeating unit I: This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 575626 A7 V. Description of the invention (, 〇 II 〇

〇-, 〇- and polyethers with repeating units_

-〇

• I ^ 1 pack --- (Please read the note on the back to write this page first) Among them, the aryl group between the ketone groups of polyetherketone ketone is typically a p- and m- aryl group &lt; mixture, for example and In other words, the derivatives derived from m-xylylene terephthalate and terephthalate exist as repeating units constituting the resin. These resins, commonly referred to as PEK, PEEK and PEKK, are disclosed in one or more of the following U.S. patents: 3,065,205; 3,441,538; 3,442,857; 5,357,040; 5 Hills 1,827; 4,578,427; 3,516,966; 4,704,448, and 4,816,556. In addition to high melting temperatures, polyaryletherketones typically have high molecular weights: high strength and engineering plastics, and high modulus characteristics. The intrinsic viscosity of the resin, for example, may be at least 0.4, which is about 30. Below 0, it is measured for a 0.5 wt% solution of concentrated H2sO4. Polyetheretherketone (PEEK) is good because of its high melting temperature of ° 34 ° C. Polyetherketone ketone (ρΕΚΚ), which has a melting temperature of at least 34 ° C is better because it can have low melt viscosity and slow crystallization, which facilitates the mixing of resin with low MV PTFE and provides melt flow order. , Line · Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Co-operative Printer Standard (CNS) A4 Specification 8- (210 x 297 mm) 575626 A7 B7 V. Description of Invention (6) to the resulting composition. PEKK typically contains units derived from both terephthalylene (T) and isophthalene si (I) halides. The ratio of the two halides is 90:10 to 30: 70 ° and more typically 80:20 To 60: 40 ° When the ratio of T units decreases and I units increase, the crystallinity of PEKK decreases until 60:40. PEKK crystallizes so slowly that it shows similar melting point except that it shows a melting point. The present invention can be applied to all polyarylene ether ketone trees, that is, they can be beneficially combined with MV PTFE and to all kinds of non-fluorinated thermally stable polymers. The ratio of low MV PTFE to non-fluorinated thermally stable polymer can be widely changed based on the special MV of PTFE, the specific thermally stable polymer used, and the required result. A preferred composition includes 10 to 90 wt% of each of these components to a total of 100 wt% of the combination. Another preferred composition includes 15 to 30 wt% low MV PTFE or 30 to 85 wt% low MV PTFE, more preferably 40 to 85 wt% low MV PTFE, and most preferably 50 to 85 wt% For low-MV V PTFE, the remaining 100% by weight of each composition to the two components are unfluorinated polymers. Although low MV PTFE and unfluorinated polymers are the main components of the composition of the present invention, these compositions may also contain other ingredients. In a preferred embodiment of the present invention, a fibrous filler is also present in the composition. The fibrous filler is thermally stable and formally stable at a temperature at which the thermally stable polymer is stable. The composition is stable at the temperature at which the composition is manufactured, such as at least 330 ° C and more preferably at least 350 ° C. Examples of the fibrous filler include glass fibers, ink fibers and titanate fibers. The combination of fibrous filler and non-fluorinated polymer increases the tensile strength beyond that of non-fluorinated -9- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) I ^ ---; --------- Equipment --- (Please read the note on the back to write this page first) · --- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575626 V. Description of the polymer () Intrinsic strength. Low MV PTFE offers many improvements to this combination such as improved toughness and even further improved tensile strength, which is unexpected given that low MV PTFE itself does not have actual strength as a molded article. When When fibrous filler is present, the preferred ratio is 10 to 30% by weight, together with

30 to 80 wt% of a thermally stable polymer and 10 to 50 wt% of a low MV PTFE 'achieve a total of 100 wt% of these three component combinations. An even better composition is 20 to 30 wt% fibrous filler, 30 to 60 wt% heat-settling polymer and 15 to 40 wt% low mv PTFE, reaching a total of 100 as described above. wt%. It can melt the components of the composition of the present invention into a part of the extrusion process or can be pre-mixed, and then melt the moon hill at a temperature at which both resins are melted. The solution mixing temperature will be It is at least 3 3 0 ° C so as to be higher than the melting temperature of low MV PTFE. It is usually melted at a temperature of 32 ×: s 327t and preferably at 24 C to 327 ° C. Under these conditions, depending on the situation, low MV PTFE or unfluorinated polymers become homogeneous and dispersed into fine particles (regions). In the Wang Yao component, it becomes a matrix. The produced extrudate can be used in the case of injection molding of articles or by: It is a piece or a polymer that can be cut into molded particles for chemical conversion, which itself (with no fibrous filler ) Compared with the K article, the composition of the present invention has practicality for improving the article. Reconstruction Example This paper ruler 10- 575626 V. Description of the invention (8) Bottom] In the example only, 'Unless otherwise indicated, it will be low] VIV PTFE and heat-settling polymer and fibrous filler (if present) The blend is dry-mixed, and then melted by injection molding. The degrees in the screw / plunger chamber are as follows: rear = 37 (rc, center = 38 (rc and front = 38 (rc. Screw cup rate) 120 rpm and back pressure is 035 Mpa. Molding temperature is about 100 ° C and mold cycle is 2G seconds / 2G seconds. The tensile modulus test rod molded in this way has a "shape", 21.6 cm long, 127 Centimeter width (in the test area) and 0.J2 cm thickness. The tensile modulus is determined by the test procedure of ASTM (American Society for Testing and Materials) D638. The PEKK resin used in each example is in accordance with US Patent No. 4,816,556 ( (} Acridine, etc.). Example 1 In this experiment, the thermally stable polymer is a butyl unit: 1 unit ratio of 60:40. The test rod of the polymer itself has a tensile die of 3416 Mpa Kg / cm2. Low MV PTFE is a ZONYL® fluorine additive, MP1600 grade, with (in 3 At 72 C, MFR of 17 g / 10 parts, from which the melt viscosity is measured at 3x103 poise.) PEKK contains a small amount of Ti02 pigment (10% by weight). Low MV V PTFE does not have a tensile mold The quantity is because: the test rod formed from it breaks when it is sandwiched in a tensile testing machine. The Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a test rod of 80: 20 weight ratio of MP1600 and PEKK blends. It shows a tensile modulus of 2001 MPa. Although the blend is mainly composed of, low strength, and low MV V PTFE, the blend shows very high strength. In addition, PEKK itself has a tensile strain vs. The fracture (elongation) (5%) is reduced to L3% by the blend, that is, the low MV PTFE increases the shape stability of ρΕκκ under increased load ° -11-This paper applies to a 0 standard (CNS) ) A4 size (210 X 297 mm) 575626 A7 B7 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Example 2 Except that no Ti02 exists in PEKK, the same low MV PTFE and PEKK are used here In experiments. 50:50 weight ratio blends of these polymers (experiments The tensile modulus is 360 ksi (2484 MPa), which is an unexpected decrease in the tensile modulus of PEKK itself, without the presence of Ti02 (3105 MPa). Example 3 In this experiment, the low MV PTFE used and the example 1 is the same and the thermally stable polymer is PEKK, where the weight ratio of TVS I units is 80:20. When compared with PEKK itself at 3664 MPa, the tensile modulus of a test bar containing 30% by weight of MP 1600 and 70% by weight of PEKK was 3195 MPa. When the PEKK content of the blend is reduced to 50:50 weight ratio, the tensile modulus of the blend test rod is still extremely high, namely: 3 188 MPa. Example 4 In this experiment, the thermally stable polymer was polyphenylene sulfide (PPS). This resin with 20% by weight and 40% by weight, the low MV PTFE blend of Example 1 can be easily extruded into a molded tablet. The resulting molded tablets can be used for injection molding to form strong objects that exhibit low surface friction and high chemical inertness of the fluoropolymer. Similar results were obtained when P P S was replaced by other thermostable polymers. Example 5 This experiment shows the surprising effect of a low MV PTFE on a combination of a thermally stable polymer and a fibrous filler. The polymer and low MV PTFE are the same as those used in Example 2 and the fibrous filler is glass fiber (cut glass fiber with a length of 0.64 cm, general practicality). As mentioned above, PEKK / Ti〇2 mixed -12- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back first-write this page) · Line 575626 A7

V. Description of the invention (10) The printed product of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs itself shows a tensile modulus of 3,416 MPa. Glass fibers are present in the composition at 80:20 and 70:30 weight ratios (PEKK composition: glass fibers) in the composition, each producing a tensile modulus of 6279 Mpa and 7866 MPa. The composition of 60: 20: 20 (PEKK composition: MP1600: glass fiber) was produced by a considerable amount of the low MV PTFE of Example 1 instead of 20% by weight of the PEKK / Ti02 composition, resulting in a tensile modulus of 6969 MPa. Numbers close to the above 80 ·· 20 blends are unexpected because MP1600 has no tensile strength. Even more unexpected is an increase in toughness, bringing MP1600 to the composition. When compared to the PEKK / Ti02 composition itself, 4.10 Joules / cm, the 80:20 composition showed a notched Izod's impact strength of 4.27 Joules / cm (ASTM 256). The 60:20:20 composition showed an impact strength of 5.06 Joules / cm, which is about 20% larger than the 80:20 composition. When the MP 1600 content is reduced to 15% by weight and the PEKK composition is increased to 65% by weight, and the remainder is glass fiber, it is notched compared to the PEKK / Ti02-glass fiber composition (80 ·· 20) itself. Dagger one is still larger (4.72 Joules / cm). The MP 1600 content was further reduced to 5 wt% to produce a 75: 5 (MP1600): 20 (glass fiber) composition still producing a higher impact strength of 4.79 Joules / cm. When the proportion of MP1600 is increased to form a 30 (pEKK) · 40 (mP1600): 20 (glass fiber) composition, the tensile modulus is increased to 8211 Mpa, and when the glass fiber content is increased to 30 weight % While the "sacrifice" ρΕΚΚ composition increases its' tensile modulus to 10971 MPa, which is much larger than this amount might be expected with respect to increasing the glass fiber content. ; --- · --------- install --- (please read the note on the back to write this page) order --- line- -13- ^ 12 rate know application date 3 cavities ~ Case No. 088114182 Category C cS L The above columns are filled out by the Bureau) 92 · 4 · 10 Η Amendment added A4 C4 fI Patent Specification Chinese 575626 Chinese Specification Replacement Page (April 1992), IS name low melting Composition of viscosity polytetrafluoroethylene and unfluorinated polymer

COMPOSITIONS OF LOW MELT VISCOSITY POLYTETRAFLUOROETHYLENE AND NON-FLUORINATED POLYMER Name Nationality Jacques Rejigny American Inventor Residence, Domicile Installed No. 708 Kilburn Road, Wilmington, Delaware, USA Name (Name) Nationality American DuPont Co., Ltd. U.S. Line III. Applicant No. 1-7, Makati Street, Wilmington, Delaware, USA 2 Μ Marian Dee. McNair's paper scale is applicable to China National Standard (CNS) A4 (210X 297 mm) ) 575626 No. 088114182 Chinese Patent Specification Replacement Page (April 1992) A7 B7 April · 1st 0 Correction _ Add Axe. Five Descriptions of the Invention (1) Scope of the Invention The present invention relates to low-melt viscosity polytetrafluoro The use of acetylene. BACKGROUND OF THE INVENTION Polytetrafluoroethylene (PTFE), such as Teflon (TEFLON'TEF fluoropolymer resin (DuPont)) is usually available, although because of its thermal stability, high melting temperature, chemical inertness and lubricity (low friction Coefficient and non-viscosity characteristics) are known, but they are also known for their non-melt manufacturability, that is, it cannot be manufactured by these common melt manufacturing techniques such as melt extrusion including injection molding. Conversely This resin is manufactured through these non-melt flow technologies. For example, paste extrusion (fine powder PTFE) and compression molding (granular PTFE) become strong objects, and their strength can be increased by sintering. Large. The non-melt manufacturability of PTFE stems from the fact that it cannot flow in a molten state, so it has a melt viscosity of at least 1 X 109 poise at 380 ° C. The term "polysilicon" used in the literature "Fluorofluorene" or "PTFE" refers to this non-melt flowable, non-melt-producible PTFE. However, in the following discussion, for clarity, this PTFE will be referred to as high MV (melt viscosity) PTFE. Low MV PTF E is also commercially available and used in small amounts (relative to high MV PTFE consumption). Low MV PTFE with MV of 50 to 1 X 105 poise at 372 ° C, for example, with ZONYL® fluorine additive ( DuPont) is available. Low MV PTFE can be obtained by irradiating the high MV PTFE to reduce molecular weight or directly via polymerization techniques, as disclosed in US Patent No. 5,223,343 (Example 1). In either case, the average molecular weight (Μη) of the number of low MV PTFE is from 50,000 to 700,000, when compared with the molecule of high MV PTFE -4- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

Patent Application Patent Scope Replacement (April 1992) 6. Scope of Patent Application • A composition comprising: 10 to 90% by weight of a thermoplastic non-gasified polymer, which is at least 14% t at a temperature of t), and 90 to 10% by weight of low-melt viscosity polytetrafluoroacetam, to achieve the combined weight of thermoplastic unfluorinated polymer and low-melt viscosity polytetrafluoroacetam Based on a total weight of 1,000 weight. The melt viscosity of the low-melt viscosity polytetrafluoroethylene is from 50 to 1 x 105 poise. 2. The composition according to item 1 of the patent application scope, wherein the non-gasified polymer is selected from one of the following compounds: polyarylene ether, polyphenylene sulfide, polyphenylene sulfide, polyamine醯 imine and polyether 飒. 3. The group of predecessors according to item 1 of the scope of patent application, wherein the composition contains 10 to 35% by weight of fibrous filler to achieve the low melting viscosity of polytetrafluoroethylene and polymer The weight of the fibrous filler is 100% by weight based on the total weight. 4. The composition according to item 3 of the scope of patent application, wherein the amount of the non-fluorinated polymer is 30 to 80% by weight, and the amount of the low-melt viscosity polytetrafluoroacetam is 10 to 50% by weight. %, And the amount of the fibrous filler is from 0 to 30% by weight to reach 100% by weight.乂: A composition comprising: 30 to 85% by weight of a low-melt viscosity polytetrazolene, and the remainder of the composition comprises a thermoplastic unfluorinated foot permanent compound, which is at least 14 (rc Thermal stability at the temperature), to reach a total weight of 100% by weight based on the combined weight of the thermoplastic unfluorinated polymer and low-melt viscosity polytetraethylene, low-melt viscosity polytetrafluoroethylene The melt viscosity is from 50 to 1 x 105 poise. 6. The composition according to item 5 of the scope of patent application, wherein the composition contains the paper ruler standard (_μ7 见 格 (Gong Gongdong) ---- -575626 A8 B8 C8 —---— —_D8 ___ 6. Apply for patents ranging from 40 to 85% by weight of low melt viscosity polytetrafluoroethylene. 7. Composition according to item 5 of the scope of patent application, where the combination The composition contains 50 to 85% by weight of low-melt viscosity polytetrafluoroethylene. 8. The composition according to item 2 of the patent application scope, including 80% by weight of low-melt viscosity polytetrafluoroethylene and 20% by weight / 〇Polyarylene ether ketone. 9. Composition according to item 2 of the scope of patent application Includes 50% by weight of low-melt viscosity polytetrafluoroacetam and 50% by weight of polyarylene ether ketone. 10. Composition according to item 2 of the scope of patent application, including 30% by weight of low melt viscosity Polytetrafluoroethylene and 70% by weight of poly (arylene ether ketone). 11. Composition according to item 2 of the scope of patent application, including low weight melt polytetrafluoroethylene of 40% ❶ / 〇, and the rest is polytetrafluoroethylene. Phenyl sulfide. 12. A composition according to item 4 of the scope of patent application, comprising 60% by weight of polyarylene ether ketone, 20% by weight of low melt viscosity polytetrafluoroethylene and 20% by weight of fibrous fibers. 13. The composition according to item 4 of the scope of patent application, which includes 30% by weight of polyarylene ketone '40% by weight of low-melt viscosity polytetrafluoroethylene and 30% by weight of fibrous fibers. · 2, this paper size applies to towel g S & F (CNS) A4 size _ χ 裂 公 ^