High melt flow PEAK compositions

Abstract

A composition [composition (C)] comprising at least one poly(aryl ether ketone) polymer having a melt flow rate (MFR) equal to or higher than 8 g/10 min at 400.degree. C. and under a load of 2.16 kg, [(PAEK.sub.HMF) polymer], from 0.1 to 50 wt. % of at least one poly(tetrafluoroethylene) polymer having a D50 particle size equal to or below 10.mu.m, and having a melt viscosity equal to or lower than 1.times.10.sup.5 Pas at 372.degree. C., from 0 to 50% wt. % of at least one poly(aryl ether sulfone) polymer having a melt flow of at least 15 g/10 min at 365 degree C. and under a load of 5.0 kg, [(PAES) polymer], from 0 to 50% wt. % of at least one reinforcing filler, with the proviso thatshould the composition (C) comprise a (PAES) polymer having MFR of more than 22 g/10 min, then the (PTFE) polymer is present in an amount of less than 40 wt. %, andshould the composition (C) comprise a (PAES) polymer having MFR of 22 g/10 min or less, then the (PTFE) polymer is present in an amount of less than 30 wt. %, and wherein all % are based on the total weight of the composition (C).

Claims

1. A composition (C) comprising: from 0.1 to 99.9 % by weight (wt. %) of at least one poly(aryl ether ketone) polymer, (PAEK.sub.HMF) polymer, having a melt flow rate (MFR) equal to or higher than 8 g/10 min at 400 C. and under a load of 2.16 kg, as measured in accordance with ASTM method D1238; from 0.1 to 50 wt. % of at least one poly(tetrafluoroethylene) polymer, (PTFE) polymer, having a D50 particle size equal to or below 10 m measured by laser scattering technique, and having a melt viscosity equal to or lower than 110.sup.5 Pa.Math.s at 372 C. measured according to a modified ASTM D-1238-52T method; from 0 to 50% wt. % of at least one poly(aryl ether sulfone) polymer, (PAES) polymer, having a melt flow of at least 15 g/10 min at 365 C. and under a load of 5.0 kg, as measured in accordance with ASTM method D1238; and from 0 to 50 % wt. % of at least one reinforcing filler, with the proviso that: should the composition (C) comprise a (PAES) polymer having a melt flow of more than 22 g/10 min, when measured in accordance with ASTM method D1238 at 365 C. and under a load of 5.0 kg, then the (PTFE) polymer is present in an amount of less than 40 wt. %, and should the composition (C) comprise a (PAES) polymer having a melt flow of 22 g/10 min or less, when measured in accordance with ASTM method D1238 at 365 C. and under a load of 5.0 kg, then the (PTFE) polymer is present in an amount of less than 30 wt. %, wherein all % are based on the total weight of the composition (C).

2. The composition (C) according to claim 1, wherein more than 50% moles of recurring units of the (PAEK.sub.HMF) polymer are recurring units (R.sub.PAEK.sub._.sub.HMF) selected from the group consisting of formulae (J-A) to (J-O): ##STR00016## ##STR00017## wherein: each of R, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and j is zero or is an integer from 0 to 4.

3. The composition (C) according to claim 1 comprising from 40 to 90 wt. % of the (PAEK.sub.HMF) polymer, based on a total weight of the composition (C), with the proviso that (PAES) polymer is absent.

4. The composition (C) according to claim 1 comprising from 40 to 70 wt. % of the (PAEK.sub.HMF) polymer, based on a total weight of the composition (C), with the proviso that (PAES) polymer is present.

5. The composition (C) according to claim 1, wherein the melt flow rate (MFR) of the (PAEK.sub.HMF) polymer is from 30 g/10 min to 55 g/10 min at 400 C. and under a load of 2.16 kg, as measured in accordance with ASTM method D1238.

6. The composition (C) according to claim 1, wherein the (PTFE) polymer has a D50 particle size from 2 m to 8 m measured by laser scattering technique.

7. The composition (C) according to claim 1 comprising from 15 to 35 wt. % of the (PAES) polymer, based on the total weight of the composition (C).

8. The composition (C) according to claim 1, wherein more than 50% moles of recurring units of the (PAES) polymer are recurring units (R) of formula (A) as shown below:
Ar.sup.1-(T-Ar.sup.2).sub.nOAr.sup.3SO.sub.2[Ar.sup.4-(T-Ar.sup.2).sub.nSO.sub.2].sub.mAr.sup.5O(formula A) wherein: Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, and Ar.sup.5, equal to or different from each occurrence, are independently an aromatic mono- or polynuclear group; T and T, equal to or different from each other and at each occurrence, is independently a bond or a divalent group optionally comprising one or more than one heteroatom; and n and m, equal to or different from each other, are independently zero or an integer of 1 to 5.

9. The composition (C) according to claim 1, wherein the (PAES) polymer is a poly(biphenyl ether sulfone) comprising more than 50 wt. % of recurring units (Ra) selected from the group consisting of those of formulae (F), (H) and (J) ##STR00018## and mixtures thereof.

10. The composition (C) according to claim 1, wherein the composition further comprises a reinforcing filler in an amount of at most 50 wt. % and other ingredients in an amount below 50 wt. %, and wherein all % are based on the total weight of the composition (C).

11. A method for manufacturing a film (F) comprising the composition (C) of claim 1, wherein the composition (C) is processed under the form of a film by cast extrusion or hot blown extrusion techniques.

12. The method of claim 11, wherein the film (F) has a mono- or bi-axial orientation.

13. The method of claim 11 comprising extruding the composition (C) in molten form through a die having an elongated shape to obtain an extruded tape, and casting and/or calendering the extruded tape to form the film (F).

14. A film (F) comprising the composition (C) of claim 1, wherein the film (F) has a thickness equal to or below 200 m, and a total rugosity of equal to or below 80 inch.

15. A method for manufacturing a wire coating (W) comprising the composition (C) of claim 1, wherein the amount of the (PTFE) polymer is less than 40 wt. %, and the method is an extrusion wire coating process.

16. A wire coating (W) or coated wire comprising the composition (C) of claim 1, wherein the amount of the (PTFE) polymer is less than 40% wt.

17. The wire coating (W) or coated wire according to claim 16, wherein the wire coating (W) has a thickness equal to or below to or below 200 m.

Description

EXAMPLES

(1) The invention will be now described in more details with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

(2) Raw Materials

(3) KETASPIRE KT-880 [MFR (400 C./2.16 kg) is 39.5 g/10 min; MV (400 C., 1000 s.sup.1) is 0.15 kPa.Math.s; IV is 0.75 dl/g-0.77 dl/g] and KETASPIRE KT-820 [MFR (400 C./2.16 kg) is 6 g/10 min; MV (400 C., 1000 s.sup.1) is 0.41 kPa.Math.s;] are aromatic polyetheretherketone (PEEK) polymers commercially available from Solvay Specialty Polymers USA, LLC.

(4) RADEL R 5100 PPSU [MFR (400 C./2.16 kg) is 17.2 g/10 min] and DURADEX D-3000 [MFR (400 C./2.16 kg) is 30.2 g/10 min] are polyphenylsulfone (PPSU) homopolymers from Solvay Specialty Polymers USA, L.L.C. PTFE: Polymist XPP-511 is a polytetrafluoroethylene powdered resin, obtained from SOLVAY SPECIALTY POLYMERS ITALY S.p.A. having a D50 particle size of 20 m, a melting point T.sub.m(II) of 329 C. The melt viscosity (MV) is equal to or lower than 110.sup.5 Pa.Math.s at 372 C. measured according to a modified ASTM D1238-52T method PTFE: Polymist F5-A is a polytetrafluoroethylene powdered resin, obtained from SOLVAY SPECIALTY POLYMERS ITALY S.p.A. having a D50 particle size of 4 m, a melting point T.sub.m(II) of 326 C. The melt viscosity (MV) is equal to or lower than 110.sup.5 Pa.Math.s at 372 C. measured according to a modified ASTM D1238-52T method
The Following Characterizations Carried out on the Materials of the Examples are Indicated Hereinafter:
Melt Flow Rate (MFR)

(5) The melt flow rate (MFR) of the (PTFE) polymer was measured at 372 C. and under a load of 10 kg and the MFR of the PEEK polymer at 400 C. and under a load of 2.16 kg, both in accordance with ASTM method D1238.

(6) The melt flow rate (MFR) of the PPSU polymers was measured at 365 C. and under a load of 5 kg, in accordance with ASTM method D1238.

(7) The melt flow rate (MFR) of the polymer compositions was measured at 400 C. and under a load of 2.16 kg, both in accordance with ASTM method D1238.

(8) Viscosity Measurements

(9) The melt viscosity (MV) of the (PTFE) polymer is measured at 372 C. in accordance with the procedure ASTM D-1238-52T modified as notably described in U.S. Pat. No. 4,380,618. The cylinder, orifice and piston tip are made of a corrosion-resistant alloy, Haynes Stellite 19, made by Haynes Stellite Co. The 5.0 g sample is charged to the 9.53 mm (0.375 inch) inside diameter cylinder, which is maintained at 372 C. Five minutes after the sample is charged to the cylinder, it is extruded through a 2.10 mm (0.0825 inch) diameter, 8.00 mm (0.315 inch) long square-edge orifice under a load (piston plus weight) of 5000 grams. This corresponds to a shear stress of 44.8 KPa (6.5 pounds per square inch). The melt viscosity in poises is calculated as 53170 divided by the observed extrusion rate in grams per minute.

(10) Melt viscosity (MV) measurements of PEEK polymers were made with a capillary rheometer according to ASTM D3835. Readings were taken at 400 C. using a die with the following characteristics: diameter: 1.016 mm, length: 20.32 mm, cone angle 120 and a shear rate of 1000 s.sup.1.

(11) The viscosity of a melt of KETASPIRE KT-880 PEEK polymers was also measured as a function of shear rate at several temperatures using an LCR-7000 Capillary Rheometer and using a die with the following characteristics: diameter: 1.016 mm, length: 20.32 mm, cone angle 120, as shown in Table 1 below:

(12) TABLE-US-00001 TABLE 1 Shear Rate (1/s) Visc. (kPa .Math. s) at 400 C. 100.2 0.225 400.9 0.187 1002.3 0.154 2505.7 0.121 5011.5 0.960 7015.9 0.850 10022.8 0.710

(13) Reduced viscosity (RV) of the PEEK polymers were measured in 95-98% sulfuric acid (d=1.84 g/ml) at a polymer concentration of 1 g/100 ml at 25 C. using a Cannon-Fenske viscometer tube (No. 50) according to ASTM D2857.

(14) Intrinsic viscosity (IV) of the PEEK polymers were measured in 95-98% sulfuric acid (d=1.84 g/ml) at a polymer concentration of 0.1 g/100 ml at 25 C. using a Cannon-Fenske viscometer tube (No. 50) according to ASTM D2857.

(15) The Second Melting Temperature (T.sub.m(II) Melting Point)

(16) The second melting temperature was measured according to the ASTM D3418 method which has been modified in such a way that the heating and cooling steps are carried out as shown in Table 2 below:

(17) TABLE-US-00002 TABLE 2 Step # 1 Heat to 250 C. at 50 C./minute 2 Heat from 250 C. to 380 C. at 10 C./minute 3 Hold for 2 minutes 4 Cool from 380 C. to 250 C. at 10 C./minute 5 Hold for 2 minutes 6 Heat from 250 C. to 380 C. at 10 C./minute 7 Hold for 2 minutes 8 Cool down

(18) The melting point observed at the second heating period was recorded and is hereby referred to as the melting point of the (PTFE) polymer (T.sub.m(II)).

(19) General Description of the Compounding Process of the Polymer Compositions

(20) All polymer compositions (PEEK/PTFE polymer compositions shown in Tables 4 and PEEK/PPSU/PTFE polymer compositions shown in Table 5) were produced by melt compounding on a Berstorff A, 25-mm twin screw co-rotating intermeshing extruder having an L/D ratio of 40 using compounding conditions as shown in Table 3.

(21) TABLE-US-00003 TABLE 3 Set Point ( C.) Barrel 2 330 Barrel 3 330 Barrel 4 330 Barrel 5 340 Barrel 6 340 Barrel 7 340 Barrel 8 340 Adapter 340 Die 340 Screw Speed (RPM) 210 Torque (Amps) 7 Feed Rate (lb/hr) 20

(22) The mechanical properties of the polymer compositions prepared were tested according to ASTM standards. For the preparation of the test specimen, in particular tensile and flex bars, and 44 inch plaques, the polymer compositions were molded on the Toshiba-150 injection molder according to the conditions as shown in Table 4.

(23) TABLE-US-00004 TABLE 4 Tensile and flex bars, and 4 4 inch plaques were made with the following conditions: ISO bars 4 4 plaques Temp C. Temp C. Zone 1 380 Zone 1 375 Zone 2 390 Zone 2 375 Zone 3 Zone 3 365 Zone 4 385 Nozzle temp. 365 Zone 5 380 Mold temp. 195 Mold temp. 195 Cycle time 44 sec Cycle time 46 sec Fill time 1.5 sec Fill time 8 sec Plast. time 16 sec Charge time 12 sec Hold time 1 6 sec Hold time 1 6 sec Hold time 2 15 sec Cooling time 12 sec Cooling time 16 sec Back pressure 4% Hold pressure 1 10% Inj. pressure 400 psi Hold pressure 2 12%

(24) The various ASTM employed were the following: Flexural Strength and Modulus, Tensile Strength and Modulus: D638 Notched Izod Impact: D256.

(25) The mechanical properties are summarized in Tables 5, 6 and 7.

(26) TABLE-US-00005 TABLE 5 KETASPIRE KT-880 PEEK polymer.sup.a KETASPIRE KT-820 PEEK polymer.sup.a Examples N.sup.o 1 2 3 4 5 C6 C7 C8 C9 CIO Polymist F5-A PTFE (wt. %).sup.a 10 20 30 40 50 10 20 30 40 50 Polymer composition (C) properties MFR [400 C./2.16 kg] (g/10 min) 43.8 44.25 49 Flexural Strength (psi) 21010 19291 17470 16362 14970 16789 Flexural Modulus (psi) 546746 518637 482441 461356 430059 480290 Tensile Strength (psi) 13500 12000 10400 9310 8360 10600 Tensile Modulus (psi) 529000 497000 475000 437000 414000 472000 Notched Izod Impact (ft-lb/in) 1.81 1.53 1.5 1.34 Film properties Film Quality.sup.b/ Good/ Good/ Good/ Good/ Good/ Poor/ Poor/ Poor/ Poor/ Poor/ Wire Coating Quality.sup.c Good Good Good Poor Poor Poor Poor Poor Poor Poor Examples N.sup.o C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 Polymist XPP-511 PTFE 10 20 30 40 50 10 20 30 40 50 (wt. %).sup.a Polymer composition (C) properties Flexural Strength (psi) 18062 15559 13377 14102 12070 1000 Flexural Modulus (psi) 487000 435000 39200 384000 350000 323000 Tensile Strength (psi) 11500 9940 8450 9320 7800 6370 Tensile Modulus (psi) 472000 424000 378000 388000 340000 319000 Film properties Film Quality.sup.a/ Poor/ Poor/ Poor/ Poor/ Poor/ Poor/ Poor/ Poor/ Poor/ Poor/ Wire Coating Quality.sup.b Poor Poor Poor Poor Poor Poor Poor Poor Poor Poor .sup.aThe wt % of the PEEK polymer is the residual weight for giving a total weight of 100% .sup.bExtruded 50 m thick film having a poor quality refers to films having a lot of tears and voids; a excellent quality refers to film having no tears and looking visually homogeneous .sup.c50 m thick wire coatings having a poor quality refers to wire coatings having a lot of tears and voids; an excellent quality refers to wire coatings having no tears and looking visually homogeneous

(27) TABLE-US-00006 TABLE 6 KETASPIRE KT-880 PEEK polymer.sup.a KETASPIRE KT-880 PEEK polymer.sup.a Examples N.sup.o 22 23 24 C25 C26 Examples No 27 28 C29 Polymist F5-A PTFE (wt. %) 10 20 30 40 50 Polymist F5-A PTFE 10 20 30 (wt. %) DURADEX FD-3000 PPSU 22.5 20 17.5 15 12.5 RADEL R 5100 PPSU 33.5 29.5 26 Polymer composition (C) Polymer composition (C) properties properties Flexural Strength (psi) 16800 15400 Flexural Strength (psi) 14690 12558 Flexural Modulus (psi) 455000 429000 Flexural Modulus (psi) 384459 344422 Tensile Strength (psi) 11000 9650 Tensile Strength (psi) 10100 8140 Tensile Modulus (psi) 446000 419000 Tensile Modulus (psi) 372000 297000 Notched Izod Impact (ft-lb/in) 1.59 1.36 Notched Izod Impact (ft-lb/in) Film properties Film properties Film Quality.sup.a/ Good/ Good/ Good/ Poor/ Poor/ Film Quality.sup.a/ Good/ Good/ Poor/ Wire Coating Quality.sup.b Good Good Good Poor Poor Wire Coating Quality.sup.b Good Good Poor Examples N.sup.o C30 C40 C50 Examples N.sup.o C51 C52 C53 Polymist XPP-511 PTFE 10 20 30 Polymist XPP-511 PTFE 10 20 30 (wt. %) (wt. %) DURADEX D-3000 PPSU 22.5 20 17.5 RADEL R 5100 PPSU 33.5 29.5 26 Polymer composition (C) Polymer composition (C) properties properties Flexural Strength (psi) 12994 Flexural Strength (psi) 14690 12558 Flexural Modulus (psi) 359182 Flexural Modulus (psi) 384459 344422 Tensile Strength (psi) 8370 Tensile Strength (psi) 10100 8140 Tensile Modulus (psi) 328000 Tensile Modulus (psi) 372000 297000 Film properties Film properties Film Quality.sup.b/ Poor/ Poor/ Poor/ Film Quality.sup.b/ Poor/ Poor/ Poor/ Wire Coating Quality.sup.c Poor Poor Poor Wire Coating Quality.sup.c Poor Poor Poor .sup.aThe wt % of the PEEK polymer is the residual weight for giving a total weight of 100% .sup.bExtruded 50 m thick film having a poor quality refers to films having a lot of tears and voids; a excellent quality refers to film having no tears and looking visually homogeneous .sup.c50 m thick wire coatings having a poor quality refers to wire coatings having a lot of tears and voids; an excellent quality refers to wire coatings having no tears and looking visually homogeneous

(28) TABLE-US-00007 TABLE 7 KETASPIRE KT-820 PEEK polymer.sup.a Examples No C54 C55 C56 Polymist F5-A PTFE 10 20 30 (wt. %) RADEL R 5100 PPSU 33.5 29.5 26 Polymer composition (C) properties Flexural Strength (psi) 17038 Flexural Modulus (psi) 446138 Tensile Strength (psi) 11000 Tensile Modulus (psi) 427000 Notched Izod Impact (ft-lb/in) 2.13 Film properties Film Quality.sup.a/ Poor/ Poor/ Poor/ Wire Coating Quality.sup.b Poor Poor Poor Examples No C57 C58 C59 Polymist XPP-511 PTFE 10 20 30 (wt. %) RADEL R 5100 PPSU 33.5 29.5 26 Polymer composition (C) properties Flexural Strength (psi) 16248 Flexural Modulus (psi) 437616 Tensile Strength (psi) 11000 Tensile Modulus (psi) 425000 Film properties Film Quality.sup.b/ Poor/ Poor/ Poor/ Wire Coating Quality.sup.c Poor Poor Poor .sup.aThe wt % of the PEEK polymer is the residual weight for giving a total weight of 100% .sup.bExtruded 50 m thick film having a poor quality refers to films having a lot of tears and voids; a excellent quality refers to film having no tears and looking visually homogeneous .sup.c50 m thick wire coatings having a poor quality refers to wire coatings having a lot of tears and voids; an excellent quality refers to wire coatings having no tears and looking visually homogeneous
Manufacturing of Films

(29) Films were prepared from all the polymer compositions (Tables 5, 6 and 7). All film extrusions were carried out on a 0.75 inch Brabender lab scale film line including a single screw extruder with a 0.75 inch general purpose (GP) screw having an L/D of 25. No mixing section and no screen pack were used. Details of the extrusion conditions can be found in Table 8:

(30) TABLE-US-00008 TABLE 8 Set Point Zone #1 Temp = 330 C. Zone #2 Temp = 340 C. Zone #3 Temp = 350 C. Film Die Temp = 360 C. Screw RPM 60 to 80 rpm Line Speed Set Point 4 (no units on the line) Finished thickness 0.050 mm target Roll Temperature 90 C. (set point)

(31) The film die used was a 125 mm wide, non-coated, flex lip film die and the material channel inside the die was an industry standard coathanger design. Die gap was set to approximately 0.015 inch and the distance from the die face to roll stack was approximately 12 to 19 mm. The roll stack was a 3 roll, up stack configuration. Nip gap between the bottom and middle roll was controlled by spring tensioners. The roll stack temperature was set to 90 C. The heating unit had difficulty in maintaining this temperature so the actual roll temp varied between 80 C. and 95 C.

(32) The film was thus run in an up-stack configuration while utilizing a 3 roll cooling stack. Slight variations were done on screw speed and zone and die temperature setting to optimize the process for some of the different materials, however these adjustments were within 5% of the above set-points.

(33) The film obtained had a thickness of approximately 50 m and a film width of 115 mm. The surface roughness (rugosity) and mechanical properties of the films made from example 3 and comparative examples C8 and C13 (see table 5) were measured and the results are summarized in Table 9.

(34) The rugosity was determined using a Profilometer. The films were tightened to a flat surface and a thickness probe was placed on different points of the film to measure thickness using the respective equipment, MarSurf GD25 from the company Mahr. The average of these points were calculated and reported as Rugosity.

(35) TABLE-US-00009 TABLE 9 Film made Film made Film made Film made from sample from sample from sample No 3 No C8 No C13 Examples No 57 C58 C59 Rugosity (inch) 5.6 87 181.4 Tensile Strength at Break 10123 7656 (psi) Tensile Strength at Yield (psi) 7356 5436 548 Tensile Modulus (psi) 212 174 59 Elongation at Break (%) 197 163 9 Elongation at Yield (%) 7.4 5.6 6.3
Manufacturing of Wire Coatings

(36) Wire coatings were prepared from all the polymer compositions (Tables 5, 6 and 7). All wire coatings were carried out on a 1.5 inch Entwhistle with a general purpose (GP) screw having an L/D of 24, using a 80:100:80 mesh screen pack to improve back-pressure in the screw. There were no mixing sections on the screw. The conductor diameter was 0.080 inch, the conductor material was Copper. The Die was 0.268 inch and the tip was 0.225 (flush). The wire line was set up with a standard payout reel, resistive pre-heating station, tubing type cross head connected to the single screw extruder. Down stream equipment included a cooling trough, in-line wire diameter gage, and a take-up reel.

(37) Details of the wire coating conditions can be found in Table 10:

(38) TABLE-US-00010 TABLE 10 Set Point (Temp. C.) Zone #1 327 Zone #2 338 Zone #3 349 Zone #4 360 Flange #1 355 Flange #2 355 Neck 371 Head 371 Die #1 371 Die #2 371 Melt Temp 360 Screw RPM 15 rpm Line Speed 36.5 m/min (120 ft/min) Finished Diameter 0.855 inch Pre-Heat Utilized torch

(39) To allow for the crystallization of the polymers, the trial was conducted without cooling water in the down line cooling troughs. A small amount of air was blown onto the wire at the end of the cooling troughs at approximately 0.6 meters from the cross head. The wire conductor (copper wire) was preheated utilizing a propane torch since the on-line resistance heater was not functional. The conductor temperature was around 95 C. The wire was manufactured on a tubing-type cross head. A slight, in measurable, amount of vacuum was applied to ensure optimum draw down of the polymer on to the wire. The coated wire was pulled through rollers and collected on a wire-wheel at a rate of 36.5 m/min with the extruder running at 15 rpm. The thickness of the total coating and wire was measured through an imbedded laser measuring device. The thickness of the naked wire was then subtracted from the total thickness to determine coating thickness. A coated wire with a 50 m thickness was obtained.