PAEK/PAES compositions

Abstract

A composition [composition (C)] comprising from 1 to 90% by weight (wt. %) of at least one poly(aryl ether ketone) [(PAEK) polymer, herein after], from to 25 wt. % of at least one polyphenylsulfone polymer [(PPSU) polymer, herein after], from 1 to 90% wt. % of at least one poly(aryl ether sulfone) polymer [(P1) polymer, herein after], selected from a group consisting of at least one high temperature poly(aryl ether sulfone) polymer [(PAES.sub.HT) polymer, herein after] and at least one polyethersulfone polymer [(PESU) polymer, herein after]; from 0 to 50% wt. % of at least one reinforcing filler, and wherein all % are based on the total weight of the composition (C).

Claims

1. A composition (C) comprising: from 1 to 90% by weight (wt. %) of at least one poly(aryl ether ketone), (PAEK) polymer, wherein more than 50% by moles of recurring units of the (PAEK) polymer are recurring units (R.sub.PAEK) comprising a Ar—C(O)—Ar′ group, with Ar and Ar′, equal to or different from each other, being aromatic groups; from 1 to 25 wt. % of at least one polyphenylsulfone polymer, (PPSU) polymer, wherein more than 50% by moles of recurring units of the (PPSU) polymer are recurring units (R.sub.ppsu) of formula (A): ##STR00023## and from 30 to 85 wt. % of at least one poly(aryl ether sulfone) polymer, (P1) polymer, selected from at least one high temperature poly(aryl ether sulfone) polymer, (PAES.sub.HT) polymer, wherein more than 50% by moles of recurring units of the (PAES.sub.HT) polymer are recurring units (R.sub.PAES), the recurring units (R.sub.PAES), equal to or different from each other at each occurrence, are complying with formula (G): ##STR00024## 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; each of j′, equal to or different from each other and at each occurrence, is independently an integer from 0 to 4; Ar.sup.1 and Ar.sup.2 are equal or different from each other and at each occurrence, are independently aromatic moieties selected from the group consisting of those complying with following formulae: ##STR00025## wherein each of R is selected from the group consisting of:hydrogen, 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, k and I, equal or different from each other, are independently 0, 1, 2, 3 or 4; each of T, equal to or different from each other, is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—;—C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCI.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—;—N═N—; —R.sup.aC═CR.sup.b—; where each R.sup.a and R.sup.b; independently of one another, is a hydrogen or a C.sub.1-C.sub.12-alkyl, C.sub.1-C.sub.12-alkoxy, or C.sub.6-C.sub.18-aryl group ; —(CH.sub.2).sub.q- and -(CF.sub.2).sub.q— with q =integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms ; and mixtures thereof ; and n is 0, 1, 2, 3 or 4; and from 0 to 50 wt. % of at least one reinforcing filler, and wherein all % are based on a total weight of the composition (C).

2. The composition (C) according to claim 1, wherein the recurring units (R.sub.PAEK) are selected from the group consisting of formulae (J-A) to (J-O): ##STR00026## ##STR00027## 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 an integer from 0 to 4.

3. The composition (C) according to claim 1, wherein more than 50% moles of recurring units of the (PAEK) polymer are recurring units (R.sub.PAEK) selected from the group consisting of formulae (J′-A) to (J′-O): ##STR00028## ##STR00029##

4. The composition (C) according to claim 1, comprising 35-75 wt. % of the (PAEK) polymer, based on the total weight of the composition (C), with the proviso that the reinforcing filler is absent.

5. The composition (C) according to claim 1, comprising 5-30 wt. % of the (PAEK) polymer, based on the total weight of the composition (C), with the proviso that the reinforcing filler is present.

6. The composition (C) according to claim 1, comprising from 4 to 10 wt. % of the (PPSU) polymer, based on the total weight of the polymer composition (C).

7. The composition (C) according to claim 1, wherein the recurring units (R.sub.PAES) are those selected from the group consisting of formulae (H) to (K), as shown below, and mixtures thereof: ##STR00030##

8. The composition (C) according to claim 1, wherein more than 75% by moles of the recurring units of the (PAES.sub.HT) polymer are a mix of recurring units (R.sub.PAES-1) and (R.sub.PAES-2) wherein the recurring units (R.sub.PAES-1) comply with formula (O): ##STR00031## and the recurring units (R.sub.PAES-2) comply with formula (P): ##STR00032## and the mole amount of the recurring units (R.sub.PAES-1) in the (PAES.sub.HT) polymer is from 50-98%, based on the total amount of recurring units (R.sub.PAES-1) and (R.sub.PAES-2) comprised in the (PAES.sub.HT) polymer.

9. The composition (C) according to claim 1, comprising 30-70 wt. % of the (P1) polymer, based on the total weight of the composition (C), with the proviso that the reinforcing filler is absent.

10. The composition (C) according to claim 1, comprising 30-65 wt. % of the (P1) polymer, based on the total weight of the composition (C), with the proviso that the reinforcing filler is present.

11. The composition (C) according to claim 1, wherein the reinforcing filler is a glass fiber present in an amount equal to or at most 40 wt. %, based on the total weight of the polymer composition (C).

12. A process for manufacturing the polymer composition (C) according to claim 1, which comprises mixing: a. the at least one (PAEK) polymer; b. the at least one (PPSU) polymer; c. the at least one (P1) polymer; and d. optionally, the at least one the reinforcing filler, and optionally, other ingredients (I).

13. An article comprising the polymer composition (C) according to claim 1.

14. The composition (C) according to claim 1 comprising 5 to 45 wt. % of the at least one reinforcing filler.

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 [MV (400° C., 1000 s.sup.−1) ranges from 0.12-0.18 kPa.Math.s; IV is 0.75 dl/g-0.77 dl/g] is an aromatic polyetheretherketone (PEEK) polymers commercially available from Solvay Specialty Polymers USA, LLC. KETASPIRE® KT-820 [MV (400° C., 1000 s.sup.−1) ranges from 0.38-0.50 kPa.Math.s;] is an aromatic polyetheretherketone (PEEK) polymers commercially available from Solvay Specialty Polymers USA, LLC. RADEL® R 5100 PPSU [MFR (365° C./5 kg) is in the range from 14-20 g/10 min] is a polyphenylsulfone (PPSU) homopolymer from Solvay Specialty Polymers USA, L.L.C. Veradel® A-201 NT PESU [MFR (380° C./2.16 kg) is in the range from 15-25 g/10 min] is a polyethersulfone (PESU) homopolymer from Solvay Specialty Polymers USA, L.L.C. Veradel® A-301 NT PESU [MFR (380° C./2.16 kg) is in the range from 25-35 g/10 min] is a polyethersulfone (PESU) homopolymer from Solvay Specialty Polymers USA, L.L.C. EpiSpire® EP-340P high temperature sulfone polymer [MFR (400° C./5.0 kg) is in the range from 8-15 g/10 min] is (PAES.sub.HT) polymer comprising recurring units (R.sub.PAES-1) complying with formula (I) and recurring units (R.sub.PAES-2) complying with formula (H). It has a glass transition temperature, Tg, of 268° C. and is commercially available from Solvay Specialty Polymers USA, LLC OCV 910A chopped fiberglass from Owens-Corning Vetrotex Hostanox PEPQ, an aromatic organic phosphonite melt thermal stabilizer available from Clariant Sachtolith-L, a zinc sulfide grade available from Sachtleben Chemie GmbH Zinc oxide, grade Aktiv® available from Lanxess Corp.
The following characterizations carried out on the materials of the Examples are indicated hereinafter:
Melt Flow Rate (MFR)

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

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

(6) The melt flow rate (MFR) of the PESU polymer was measured at 380° C. and under a load of 2.16 kg, in accordance with ASTM method D1238.

(7) The melt flow rate (MFR) of the (PAES.sub.HT) polymer was measured at 400° C. and under a load of 5 kg, both in accordance with ASTM method D1238.

(8) Viscosity Measurements

(9) 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.

(10) The viscosity of a melt of KETASPIRE® KT-880 PEEK polymers was also measured as a function of shear rate at 400° C. 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:

(11) 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

(12) 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.

(13) General Description of the Compounding Process of the PEEK/PPSU/PESU and PEEK/PPSU/PAES.sub.HT Polymer Compositions

(14) Certain polymer compositions (e.g. PEEK/PPSU/PESU polymer compositions shown in Table 5; PEEK/PPSU/PAES.sub.HT polymer compositions shown in Table 6) were prepared by first tumble blending pellets of the resins to be blended at the desired compositional ratios for about 20 minutes, followed by melt compounding thereby using an 18 mm Leistritz co-rotating partially intermeshing twin screw extruder having an L/D ratio of 30:1. The extruder had 6 barrel sections with barrel sections 2 through 6 being heated (corresponding to Zones 1 through 5, respectively in Table 2). Vacuum venting was applied at barrel section 5 during compounding to strip off moisture and any possible residual volatiles from the compound. The compounding conditions are summarized in Table 2 for the PEEK/PPSU/PESU and PEEK/PPSU/PAES.sub.HT polymer compositions.

(15) General Description of the Compounding Process of the PEEK/PPSU/PESU/Glass Fiber and PEEK/PPSU/PAES.sub.HT/Glass Fibers Polymer Compositions

(16) The PEEK/PPSU/PESU/glass fibers and PEEK/PPSU/PAES.sub.HT/glass fibers polymer composition, as shown in Table 7, were prepared by first tumble blending pellets of the resins to be blended at the desired compositional ratios for about 20 minutes, followed by melt compounding thereby using an Berstorff 25 mm twin-screw co-rotating partially intermeshing extruder. Vacuum venting was applied at barrel section 7 during compounding to strip off moisture and any possible residual volatiles from the compound. The PEEK polymer and the PAES.sub.HT polymer was fed gravimetrically at the right proportion into barrel section 1 (feed throat of the extruder). Fiberglass was fed gravimetrically at the right proportion into barrel section 5. When PPSU was present in the formulation it was pre-blended in pellet form with the PAES.sub.HT polymer pellets and then the mixture was fed at the desired feed rate using a gravimetric feeder. The compounding conditions are summarized in Table 3 for PEEK/PPSU/PESU/glass fibers and PEEK/PPSU/PAES.sub.HT/glass fibers polymer composition.

(17) TABLE-US-00002 TABLE 2 Compounding process conditions used in preparing all polymer compositions (PEEK/PPSU/PESU polymer compositions shown in Table 5 and PEEK/PPSU/ PAES.sub.HT polymer compositions shown in Table 6) Example Set C1 C2 3 C4 C5 6 7 Points Actual Actual Actual Actual Actual Actual Aetna Zone 1 (° C.) 330 330 317 291 318 313 314 286 Zone 2 (° C.) 330 330 330 330 330 360 360 360 Zone 3 (° C.) 335 335 335 335 330 360 360 360 Zone 4 (° C.) 340 340 340 340 340 355 355 355 Zone 5 (° C.) 340 340 340 340 340 350 350 350 Die (° C.) 340 340 340 340 340 298 299 302 Melt Temperature (° C.) — 380 370 368 373 404 407 403 Screw Speed (rpm) — 190 198 197 201 200 200 200 Drive Torque (%) — 62 72 67 66 74 74 73 Feed Rate (lb/hr) — 5 5 5 5 5.0 5.5 5.5 Vacuum Level (mbar) — 850 800 750 800 500 500 700 Die Swell? (Yes/No) Yes, Yes, No Yes, Yes No No Severe Severe Severe

(18) TABLE-US-00003 TABLE 3 Compounding process conditions used in preparing the PEEK/PPSU/ PESU/glass fiber and PEEK/PPSU/PAES.sub.HT/glass fiber polymer compositions as shown in Table 7 Set Points Barrel Section No. 2 Barrel Section No. 3 Barrel Section No. 4 Barrel Section No. 5 Barrel Section No. 6 Barrel Section No. 7 Barrel Section No. 8 Other Extruder Set Points and Readings Adapter Temperature (° C.) 340 Die Temperature (° C.) 340 Melt Temperature (° C.) 390 Screw Speed (rpm) 210 Torque (% of Max Available)  75 Total Feed Rate (lb/hr)  20

(19) The mechanical properties of the polymer compositions prepared were tested according to ASTM standards. For the preparation of the test specimen, in particular 1) Type I tensile bars, 2) 5 inch×0.5 inch×0.125 inch flexural bars, and 3) 4 inch×4 inch×0.125 inch plaques for the instrumented impact (Dynatup) testing.

(20) The polymer compositions were molded on the 150-Ton Toshiba injection molder according to the conditions as shown in Table 4.

(21) TABLE-US-00004 TABLE 4 Tensile and flex bars, and 4 × 4 × ⅛ inch plaques were made with the following conditions : ISO bars Temp ° C. 4 × 4 × ⅛″ plaques 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

(22) The various ASTM test methods employed were the following: Flexural properties: D790 Tensile properties: D638 Notched Izod Impact: D256 Unnotched Izod Impact: D4812 Instrumented impact resistance also known by the name Dynatup impact: D3763 Heat deflection temperature (HDT): D648

(23) The heat deflection temperature (HDT) was measured at an applied stress of 264 psi and using 0.125 in-thick flexural specimens annealed at 200° C. for 2 hours to assure uniform crystallinity and removal of residual molded-in stresses in the parts which can otherwise compromise the accuracy of the measurement.

(24) In addition to mechanical property measurements, thermal characterization of the polymer compositions was also performed using differential scanning calorimetry (DSC) according to ASTM D3418.

(25) Dynamic mechanical analysis (DMA) according to ASTM D4065 was also used as an alternate, more sensitive way to detect and quantify the glass transitions of the polymer compositions, providing hereby information about the compatibility level of these polymer compositions. The glass transitions by the DMA method were defined as the temperatures corresponding to the maximum in the damping coefficient (also known as tan delta) curve.

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

(27) TABLE-US-00005 TABLE 5 Examples N° C1 C2 C3 C4 VERADEL ® A-201 NT PESU 60 50 36.8 40 KETASPIRE ® KT-880 PEEK 40 50 55.2 60 polymer RADEL ® R 5100 PPSU 0 0 8 0 Mechanical polymer composition (C) properties Tensile Strength (psi) 12700 12600 12400 12300 Tensile Modulus (ksi) 448 446 430 427 Tensile Elongation (%) 5.8 5.9 5.9 6.1 Flexural Strength (psi) 98 138 132 110 Flexural Modulus (ksi) 18200 17700 17600 17800 Flexural Elongation (%) 451 441 434 439 Notched Izod Impact (ft-lb/in) 1.28 1.29 1.42 1.32 Unnotched Izod Impact (ft-lb/in) NB NB NB NB Impact resistance properties Heat Deflection Temperature (° C.) 204.2 207 204 210 Dynatup Total Energy (ft-lb) 27.3 2.4 54.2 1.9 Dynatup Maximum Load (lb) 1028 157 1402 147 Dynatup Deflection at Max Load (in) 0.45 0.31 0.68 0.25 Dynatup % Ductile Breaks 0% 0% 100% 0% Thermal polymer composition (C) properties DSC Tg1 (° C.) [2nd Heat] 153.3 152.1 155.4 152.3 DSC Tg2 (° C.) [2nd Heat] 227.3 224.9 225.7 226.5 DSC Tm (° C.) [2nd Heat] 341.6 341.2 340.6 341.7 DSC Tc (° C.) [1st Cool] 264 262.8 261 263 DSC Delta Hf (J/g) [2nd Heat] 27.6 20.7 21.8 18 DSC Delta Hf Normalized to PEEK 46 41.4 39.6 45 Content (J/g) DSC % Absolute Crystallinity 21.2 15.9 16.8 13.8 DSC % Absolute Crystallinity 35.4 31.8 30.5 34.6 Normalized to PEEK Content DMA Tg1 (° C.) [Tan Delta Peak] 162.1 162.7 167.6 160.0 DMA Tg2 (° C.) [Tan Delta Peak] 228 227.0 227.4 228.0 NB refers to No breaks

(28) TABLE-US-00006 TABLE 6 MOLDED ANNEALED.sup.a Examples N° C5 6 7 C8 9 10 EpiSpire ® EP-340 high temperature 60.0 57.6 55.2 60.0 57.6 55.2 sulfone polymer KETASPIRE ® KT-820 PEEK polymer 40.0 38.4 36.8 40.0 38.4 36.8 RADEL ® R 5100 PPSU 0 4.0 8.0 0 4.0 8.0 Mechanical polymer composition (C) properties Tensile Strength (psi) 13700 13600 13300 15000 14700 14600 Tensile Modulus (ksi) 458 457 455 476 473 472 Tensile Elongation (%) 6.8 6.7 6.6 7.2 7.0 6.8 Flexural Strength (psi) 28 33 31 10 16 15 Flexural Modulus (ksi) 18800 18600 18800 15000 14700 14600 Flexural Elongation (%) 454 451 466 476 473 472 Notched Izod Impact (ft-lb/in) 1.72 1.78 1.74 Impact resistance properties Heat Deflection Temperature (° C.) 55.4 58.6 57.4 32.1 53.5 54.8 Dynatup Total Energy (ft-lb) 1550 1600 1590 1470 1570 1580 Dynatup Maximum Load (lb) 46.2 46.1 48.6 31.6 43.1 44.3 Dynatup Deflection at Max Load (in) 0.69 0.68 0.70 0.55 0.62 0.64 Dynatup % Ductile Breaks 100 100 100 0 80 100 .sup.aThe molded test specimens, as described above were further annealed for 4 hours at a temperature of 250° C. with the aim to simulate the impact performance of these materials after they have been exposed to elevated temperature during their normal course of service in high demanding applications such as notably engineering applications.

(29) TABLE-US-00007 TABLE 7 Examples N° 11 C12 13 C14 15 C16 17 C18 VERADEL ® A-301 NT PESU 54.49 59.49 44.49 49.49 EpiSpire ® EP-340 high 56 63 42 49 temperature sulfone polymer KETASPIRE ® KT-880 PEEK 10 10 20 20 7 7 21 21 polymer 910 A Glass Fiber 30 30 30 30 30 30 30 30 RADEL ® R 5100 PPSU 5 0 5 0 7 0 7 0 Other ingredients (PepQ, ZnS, 0.51 0.51 0.51 0.51 — — — — ZnO) Polymer composition (C) properties Tensile Strength (psi) 22900 22100 24000 22900 23500 22500 25400 24900 Tensile Modulus (ksi) 1530 1500 1590 1540 1550 1550 1610 1620 Tensile Elongation (%) 2.5 2.3 2.6 2.3 2.4 2.2 2.7 2.4 Flexural Strength (psi) 33300 31700 35900 33700 33600 31200 36100 35000 Flexural Modulus (ksi) 1500 1480 1540 1500 1420 1370 1430 1430 Flexural Elongation (%) 2.59 2.43 2,76 2.56 2.82 2.68 3.01 2.82 Notched Izod Impact (ft-lb/in) 1.79 1.62 1,90 1.57 1.78 1.44 1.82 1.54 Unnotched Izod Impact (ft-lb/in) 15.1 13.7 17.9 14.8 15.27 14.20 18.80 15.96