Polyolefin composition

Abstract

The invention relates to a composition comprising: (A) a propylene-based polymer which is a propylene homopolymer or a propylene copolymer consisting of at least 90 wt % of propylene monomer units and at most 10 wt % of ethylene monomer units and/or an α-olefin monomer units having 4 to 10 carbon atoms, (B) a terpolymer of propylene, an α-olefin having 4 to 10 carbon atoms and ethylene and (C) a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, wherein the copolymer (C) has a density of at least 0.880 g/cm.sup.3, wherein the amount of the propylene-based polymer (A) is at least 60 wt % with respect to the total composition.

Claims

1. A composition comprising: (A) a propylene-based polymer which is a propylene homopolymer or a propylene copolymer consisting of at least 90 wt % of propylene monomer units and at most 10 wt % of ethylene monomer units and/or an α-olefin monomer units having 4 to 10 carbon atoms, (B) a terpolymer of propylene, an α-olefin having 4 to 10 carbon atoms and ethylene, wherein the amount of ethylene in the terpolymer (B) is 1 to less than 10 wt % with respect to the terpolymer (B), and (C) a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, wherein the copolymer (C) has a density of at least 0.880 g/cm.sup.3, wherein the amount of the propylene-based polymer (A) is at least 60 wt % with respect to the total composition.

2. The composition according to claim 1, wherein the amount of the propylene-based polymer (A) is 60 to 98 wt %, the amount of the terpolymer (B) is 1 to 30 wt % and the amount of the copolymer (C) is 1 to 30 wt %, with respect to the total composition.

3. The composition according to claim 1, wherein the propylene-based polymer (A) is a random propylene-ethylene copolymer consisting of 90-99 wt % of propylene monomer units and 1-10 wt % of ethylene monomer units.

4. The composition according to claim 1, wherein the terpolymer (B) is a terpolymer of propylene, 1-butene and ethylene.

5. The composition according to claim 1, wherein the amount of propylene in the terpolymer (B) is 70 to 90 wt % and the amount of the α-olefin in the terpolymer (B) is 5 to 30 wt %.

6. The composition according to claim 5, wherein the amount of the α-olefin in the terpolymer (B) is 15 to 30 wt % with respect to the terpolymer (B).

7. The composition according to claim 1, wherein the total amount of the terpolymer (B) and the copolymer (C) is 15 to 40 wt % with respect to the total composition and the weight ratio of the terpolymer (B) to the copolymer (C) is 0.5 to 4.

8. The composition according to claim 1, wherein the composition further comprises (D) additives, wherein the total of (A), (B), (C) and (D) is 100 wt % of the total composition and the amount of (D) is up to 5000 ppm of the total composition.

9. The composition according to claim 1, wherein the composition comprises less than 1000 ppm of a nucleating agent or a clarifier with respect to the total composition.

10. The composition according to claim 1, wherein concentrations of Ba, Cu, Pb, Cr, Cd, Sn and Al ions in a solution obtained from a soluble test using a sample made of the composition are measured to be: each of the concentrations of Ba, Cu, Pb and Cr ions is at most 1 ppm, each of the concentrations of Cd and Sn ions is at most 0.1 ppm, and the concentration of Al ion in the solution is at most 0.05 ppm, wherein the soluble test is performed by providing a sample of 5 cm*0.5 cm, 200 micrometer from the composition, rinsing the sample by distilled water and drying at room temperature, putting the sample in a glass bottle of 500 ml and adding 200 ml distilled water and making it hermetic, putting the bottle in a high pressure vaporize sterilization device at 121° C. and heating for 30 minutes, cooling the bottle down to room temperature, and measuring the concentrations of the ions of the solution in the glass bottle.

11. A film prepared from the composition according to claim 1.

12. A medical article comprising the composition according to claim 1.

13. The medical article according to claim 12, wherein the medical article is chosen from the group of intravenous bags, intravenous tubes, intravenous bottles, and dialysis bags.

14. The composition according to claim 1, wherein the amount of the propylene-based polymer (A) is 60 to 98 wt %, the amount of the terpolymer (B) is 1 to 30 wt % and the amount of the copolymer (C) is 1 to 30 wt %, with respect to the total composition, wherein the propylene-based polymer (A) is a random propylene-ethylene copolymer consisting of 90-99 wt % of propylene monomer units and 1-10 wt % of ethylene monomer units, wherein the amount of propylene in the terpolymer (B) is 70 to 90 wt %, the amount of the α-olefin in the terpolymer (B) is 5 to 30 wt % and the amount of ethylene in the terpolymer (B) is 1 to 10 wt %, with respect to the terpolymer (B), wherein the total amount of the terpolymer (B) and the copolymer (C) is 15 to 40 wt % with respect to the total composition and the weight ratio of the terpolymer (B) to the copolymer (C) is 1 to 3.5, and wherein the composition further comprises (D) additives, wherein the total of (A), (B), (C) and (D) is 100 wt % of the total composition and the amount of (D) is up to 5000 ppm of the total composition, and wherein (D) comprises an acid scavenger.

15. The composition according to claim 13, wherein the composition comprises less than 500 ppm of a nucleating agent or a clarifier with respect to the total composition.

16. The composition according to claim 14, wherein (D) comprises an inorganic based acid scavenger and an antioxidant.

17. The composition according to claim 1, wherein the amount of propylene-based polymer (A) is 60 to 90 wt %, the amount of the terpolymer (B) is 5 to 20 wt % and the amount of the copolymer (C) is 5 to 20 wt %, with respect to the total composition.

18. The composition according to claim 1, wherein the composition comprises less than 100 ppm of a nucleating agent or a clarifier with respect to the total composition.

19. The composition according to claim 10, wherein: each of the concentrations of Ba, Cu, Pb and Cr ions is at most 0.9 ppm, each of the concentrations of Cd and Sn ions is at most 0.09 ppm, and the concentration of Al ion in the solution is at most 0.045 ppm.

20. A composition comprising: (A) 75 to 90 wt % of a propylene-based polymer which is a propylene copolymer consisting of at least 90 wt % of propylene monomer units and at most 10 wt % of ethylene monomer units and/or an α-olefin monomer units having 4 to 10 carbon atoms, (B) 5 to 20 wt % a terpolymer of propylene, an α-olefin having 4 carbon atoms and ethylene, wherein the amount of propylene in the terpolymer (B) is 70 to 90 wt %, the amount of the α-olefin in the terpolymer (B) is 5 to 30 wt %, and the amount of ethylene in the terpolymer (B) is 1 to 10 wt %, with respect to the terpolymer (B), and (C) 5 to 20 wt % a copolymer of ethylene and an α-olefin having 4 carbon atoms, wherein the copolymer (C) has a density of at least 0.880 g/cm.sup.3, wherein the amounts are with respect to the total composition.

Description

EXPERIMENTS

(1) Components used in the experiments are summarized in Table 1. In all tables, all % means wt %, unless indicated otherwise.

(2) TABLE-US-00001 TABLE 1 Items Description (A) Propylene- C3-C2 copolymer, MFR: ethylene 8 g/10 min @ 230 C./2.16 kg, copolymer C2%: 3.2%, XS %: 6.08% (B) C3-C4-C2 terpolymer, C3%: 72.73%, Terpolymer 1 C4%: 23%, C2%: 4.27%, MFR: 4 g/10 min @ 230 C./2.16 kg, Density: 0.868 g/cm3 (B) C3-C4-C2 terpolymer, C3%: 72.65%, Terpolymer 2 C4%: 20.75%, C2%: 6.6%, MFR: 6 g/10 min @ 230 C./2.16 kg, Density: 0.867 g/cm3 (B) C3-C4-C2 terpolymer, C3%: 83.68%, Terpolymer 3 C4%: 7.31%, C2%: 9.01%, MFR: 6 g/10 min @ 230 C./2.16 kg, Density: 0.868 g/cm3 (B) C3-C4-C2 terpolymer, C3%: 83.47%, Terpolymer 4 C4%: 7.82%, C2%: 8.71%, MFR: 30 g/10 min @ 230 C./2.16 kg, Density: 0.868 g/cm3 (C) Ethylene- C2-C4 copolymer, C4%: 19.5%, 1-butylene MFR: 6.7 g/10 min @ 230 C./2.16 kg, copolymer 1 Density: 0.885 g/cm3 (C) Ethylene-1- C2-C4 copolymer, C4%: 25.94%, MFR: butylene 6.7 g/10 min @ 230 C./2.16 kg, copolymer 2 Density: 0.87 g/cm3

(3) XS %=xylene soluble in wt %

(4) C2%=ethylene content in wt %

(5) C3%=propylene content in wt %

(6) C4%=butylene content in wt %

(7) Components as shown in Tables 2-4 were premixed together and then dosed into the twin-screw extruder through main feeder. The twin-screw extruder used is ZSK26mc with L/D 40 and screw diameter 26 mm. Melting temperature was 220° C. Shear rate was 400 rpm and output was 20 kg/hr.

(8) After extrusion, the pellets were dried at 70° C. for 4 hrs before injection molding. All testing bars and plaques were molded by FANUC injection molding machine (S-2000i) with proper conditions. Properties of the samples were measured and are summarized in Tables 2-4.

(9) Testing

(10) MFR

(11) MFR was tested according to ISO1133 with condition of 2.16 kg at 230° C. by Toyoseiki Semi-auto MFR F-W01.

(12) Flexural Modulus

(13) Flexural modulus was tested according to ISO178 at 23° C. by ZWICK Z005. Testing specimen is 80*10*4 mm and specimen was conditioned for 72 hr at 23±1° C. and at relative humidity of 50±5% before testing.

(14) Transmittance

(15) Transmittance was tested according to ISO13468 by BYK Haze Gard II. Thickness was 2 mm. Specimens were conditioned for 72 hr at 23±1° C. and at relative humidity of 50±5% before testing.

(16) Haze

(17) Haze was tested according to ISO14782 by BYK Haze Gard II. Thickness was 0.5 mm. Specimens were conditioned for 72 hr at 23±1° C. and at relative humidity of 50±5% before testing.

(18) Notched Charpy Impact Strength

(19) Impact strength was tested according to ISO179 at 23° C. by Toyoseiki Digital Impact DG-UB. Specimen dimension was 80*10*4 mm and specimens were conditioned for 72 hr at 23±1° C. and at relative humidity of 50±5% before testing.

(20) NMR

(21) Composition information of the elastomers was analyzed by NMR. All spectra were recorded on a Bruker AVANCE III HD 600 MHz digital NMR spectrometer equipped with PA BBO 600S3 BBF-H-D-05 Z SP Probe-head (Z114607). The temperature control, data acquisition and processing were performed with TOPSPIN 3.2 software.

(22) 50 mg sample was added into a 5 mm NMR tube with 0.6 mL relaxation solution (60 mM Cr(acac).sub.3 in TCE-d2 solution) to dissolve it under 150° C.; Pulse program: zgig (inverse gated pulse sequence); Recycle delay (d1): 10 sec; Number of scans (NS): 5000.

(23) Xylene Soluble % of C3-C2 Copolymer

(24) Xylene soluble was tested according to ISO16152.

(25) TABLE-US-00002 TABLE 2 CEx CEx CEx CEx CEx CEx CEx CEx 1 2 Ex 3 4 5 Ex 6 7 8 9 10 C3-C2 99.9 89.9 89.9 89.9 69.9 69.9 69.9 49.9 49.9 49.9 copolymer Terpolymer 10 5 30 15 50 25 1 Tafmer PN0040 C2-C4 5 10 15 30 25 50 copolymer 1 Tafmer A4085s Primary 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 antioxidant Secondary 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 antioxidant MFR 9.6 9.7 9.5 10 7.6 8.6 9.4 8.1 7.9 8.2 Haze 35.6 25.6 33.5 19.9 10.3 8.4 11.5 7 7.7 8.9 Tensile 29.1 23 22.3 23.5 15.4 16.4 17.3 10.2 10.8 12 strength Flex 1020 712 842 880 469 541 699 206 294 516 modulus Notched 3.9 7.7 8.3 7.5 18.1 23.5 11.3 74.5 72 61.3 charpy 23° C.

(26) The effect of the addition of C3-C4-C2 terpolymer and/or C2-C4 copolymer is observed varying the amounts of the C3-C4-C2 terpolymer and C2-C4 copolymer added.

(27) The addition of C3-C4-C2 terpolymer and/or C2-C4 copolymer to C3-C2 copolymer leads to an increase in the impact strength and a decrease in the haze.

(28) When the total amount of the C3-C4-C2 terpolymer and the C2-C4 copolymer is 10 wt % (CEx 2, Ex 3, CEx 4) or 30 wt % (CEx 5, Ex 6, CEx 7), the impact strength is better when both C3-C4-C2 terpolymer and C2-C4 copolymer are added compared to when only C3-C4-C2 terpolymer or C2-C4 copolymer is added.

(29) When the total amount of the C3-C4-C2 terpolymer and the C2-C4 copolymer is 50 wt % (CEx 8, CEx 9, CEx 10), no increase in the impact strength is observed when both C3-C4-C2 terpolymer and C2-C4 copolymer are added compared to when only C3-C4-C2 terpolymer or C2-C4 copolymer is added.

(30) When the total amount of the C3-C4-C2 terpolymer and the C2-C4 copolymer is 30 wt % (CEx 5, Ex 6, CEx 7), haze is decreased by the combination of C3-C4-C2 terpolymer and C2-C4 copolymer, compared to when only one of the copolymers is added.

(31) TABLE-US-00003 TABLE 3 CEx CEx CEx CEx CEx CEx 1 11 Ex 12 13 14 15 Ex 16 17 C3-C2 99.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 copolymer Terpolymer 30 15 2 Tafmer PN3560 Terpolymer 30 15 3 Tafmer PN2060 Terpolymer 30 15 4 Tafmer PN20300 C2-C4 15 15 15 30 copolymer 1 Tafmer A4085s Primary 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 antioxidant Secondary 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 antioxidant MFR 9.6 10 9.7 10.2 9.6 15.8 12.1 9.4 Haze 35.6 16.8 10.3 13.4 12.1 9.5 11.1 11.5 Tensile 29.1 15.4 16.3 16.4 16.6 16.5 16.9 17.3 strength Flex 1020 388 491 439 538 436 498 699 modulus Notched 3.9 19 20.3 15 24 13 15.1 11.3 charpy 23° C.

(32) Using different types of C3-C4-C2 terpolymers, the effect of the addition of C3-C4-C2 terpolymer and/or C2-C4 copolymer is observed.

(33) The impact strength is better when both C3-C4-C2 terpolymer and C2-C4 copolymer are added, compared to when only C3-C4-C2 terpolymer or C2-C4 copolymer is added.

(34) When the terpolymer is terpolymer 2, haze is decreased by the combination of C3-C4-C2 terpolymer and C2-C4 copolymer, compared to when only one of the copolymers is added.

(35) TABLE-US-00004 TABLE 4 CEx 5 CEx 18 CEx 19 C3-C2 69.9 69.9 69.9 copolymer Terpolymer 1 30 15 Tafmer PN0040 C2-C4 15 30 Copolymer 2 Tafmer A4070s Irganox1010 0.05 0.05 0.05 Irgafos168 0.05 0.05 0.05 MFR 7.6 8.9 8.9 Haze 10.3 15.8 26.4 Tensile 15.4 15.7 16.3 strength Flex modulus 469 566 659 Notched 18.1 34.7 27.8 charpy 23° C.

(36) Using a different type of C2-C4 copolymer from Table 2, the effect of the addition of C3-C4-C2 terpolymer and/or C2-C4 copolymer is observed.

(37) The impact strength is better when both C3-C4-C2 terpolymer and C2-C4 copolymer are added, compared to when only C3-C4-C2 terpolymer or C2-C4 copolymer is added.

(38) Comparing Ex 6 versus CEx 18, the use of a higher density C2-C4 copolymer 1 (Ex 6) results in a much lower haze than the use of a lower density C2-C4 copolymer 2 (CEx 18) while the other properties are retained at acceptable levels.