THERMOPLASTIC MATERIALS FOR USE IN SLURRY TRANSPORTATION PIPES

Abstract

The present invention relates to a thermoplastic material, wherein the thermoplastic material comprises ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %. The invention also relates to a slurry transportation pipe comprising the thermoplastic material as its inner layer, or consisting of the thermoplastic material.

Claims

1. A thermoplastic material, wherein the thermoplastic material comprises an ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %.

2. The thermoplastic material according to claim 1, wherein the thermoplastic material comprises ≥90.0 wt % of the ethylene-based polymer material.

3. The thermoplastic material according to claim 1, wherein the ethylene-based polymer material has a density of ≥0.875 and ≤0.900 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019).

4. The thermoplastic material according to claim 1, wherein the ethylene-based polymer material is an ethylene-1-octene copolymer having: a density of ≥0.880 and ≤0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); a fraction of moieties derived from 1-octene of ≥20.0 and ≤40.0 wt % with regard to the total weight of the ethylene-1-octene copolymer; and/or a molecular weight distribution M.sub.w/M.sub.n of ≥1.5 and ≤2.5, wherein the weight-average molecular weight M.sub.w and the number average molecular weight M.sub.n are determined in accordance with ASTM D6474 (2012).

5. The thermoplastic material according to claim 1, wherein the ethylene-based polymer material comprise a fraction (A) of a first ethylene-based polymer (P1) and a fraction (B) of a second ethylene based polymer (P2); wherein: the first ethylene-based polymer P1 has a density of <0.880 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); and the second ethylene-based polymer P2 has a density of >0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); wherein the ethylene-based polymer comprises >10.0 wt % and <90.0 wt % of P1, with regard to the sum of the weight of P1 and P2.

6. The thermoplastic material according to claim 5, wherein the thermoplastic material comprises ≥90.0 wt % of the ethylene-based material.

7. The thermoplastic material according to claim 5, wherein P1 and P2 are both ethylene-1-octene copolymers.

8. Thermoplastic material according to claim 5, wherein: P1 has a melt mass-flow rate as determined in accordance with ISO 1133-1 (2011) at 190° C. and under a load of 2.16 kg (MFR2) of ≥0.10 and ≤2.00 g/10 min; P2 has an MFR2 of ≥0.50 g/10 min; and/or P1 has an MFR2 that is at least 0.20 g/min.

9. The thermoplastic material according to claim 5, wherein P1 has a molecular weight distribution M.sub.w/M.sub.n of ≥2.0 and ≤2.5, and/or P2 has a molecular weight distribution M.sub.w/M.sub.n of ≥2.0 and ≤2.5.

10. A pipe comprising an inner layer comprising the thermoplastic material according to claim 1.

11. The pipe according to claim 10, wherein the pipe consists of a single layer the thermoplastic material.

12. The pipe according to claim 10, wherein the pipe has an inner diameter of >0.10 and <1.00 m.

13. Pipe according to claim 10, wherein the inner layer has a thickness of >0.1 and <10.0 cm.

14. A Process for the production of the thermoplastic material according to claim 5, wherein the process comprises polymerisation of reactants in at least two reactors positioned in series, wherein the first ethylene-based polymer P1 is produced by polymerisation of a first reactant mixture in the first reactor, followed by production of the second ethylene-based polymer P2 by polymerisation of a second reactant mixture in the second reactor, wherein the second reactant mixture comprises the first ethylene-based polymer P1.

15. The process for the production of the thermoplastic material according to claim 5, wherein the process comprises combining a quantity of the first ethylene-based polymer P1 and a quantity of the second ethylene-based polymer P2 by means of blending under melt conditions or in a solid phase.

16. The thermoplastic material according to claim 5, wherein P1 comprises ≥30.0 and ≤45.0 wt % of moieties derived from 1-octene.

17. The thermoplastic material according to claim 5, wherein P2 comprises ≥0.5 and ≤10.0 wt % of moieties derived from 1-octene.

Description

[0010] In a particular embodiment, the ethylene-based polymer material has a density of ≥0.875 and ≤0.900 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019). Even more particularly, the ethylene-based polymer may have a density of ≥0.880 and ≤0.890 g/cm.sup.3.

[0011] In certain embodiments, the ethylene-based polymer material may for example be an ethylene-1-octene copolymer having: [0012] a density of ≥0.880 and ≤0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0013] a fraction of moieties derived from 1-octene of ≥20.0 and ≤40.0 wt %, preferably of ≥20.0 and ≤30.0 wt %, with regard to the total weight of the ethylene-1-octene copolymer; and/or [0014] a molecular weight distribution M.sub.w/M.sub.n of ≥1.5 and ≤2.5, wherein the weight-average molecular weight M.sub.w and the number average molecular weight M.sub.n are determined in accordance with ASTM D6474 (2012).

[0015] Particular embodiments of the invention also encompass the thermoplastic material to comprise ethylene-based polymer material comprising a fraction (A) of a first ethylene-based polymer (P1) and a fraction (B) of a second ethylene based polymer (P2); wherein: [0016] the first ethylene-based polymer P1 has a density of <0.880 g/cm.sup.3, preferably of >0.850 and <0.880 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); and [0017] the second ethylene-based polymer P2 has a density of >0.890 g/cm.sup.3, preferably of >0.890 and <0.930 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0018] wherein the ethylene-based polymer comprises >10.0 wt % and <90.0 wt % of P1, with regard to the sum of the weight of P1 and P2.

[0019] The thermoplastic material may for example comprise ≥90.0 wt % of the ethylene-based materials, preferably ≥95.0 wt %, more preferably ≥98.0 wt %, with regard to the total weight of the thermoplastic material. In a further preferred embodiment, the thermoplastic material consists of the ethylene-based polymer material.

[0020] For example, P1 and P2 may both be ethylene-1-octene copolymers. P1 may for example comprise ≥30.0 and ≤45.0 wt % of moieties derived from 1-octene, with regard to the total weight of P1, preferably ≥30.0 and ≤40.0 wt %, more preferably ≥35.0 and ≤40.0 wt %. P2 may for example comprise ≥0.5 and ≤10.0 wt % of moieties derived from 1-octene, with regard to the total weight of P2, preferably ≥5.0 and ≤10.0 wt %. For example, P1 may comprise ≥30.0 and ≤45.0 wt % of moieties derived from 1-octene, and P2 may for example comprise ≥0.5 and ≤10.0 wt % of moieties derived from 1-octene. Preferably, P1 may comprise ≥35.0 and ≤40.0 wt % of moieties derived from 1-octene, and P2 may comprise ≥5.0 and ≤10.0 wt % of moieties derived from 1-octene.

[0021] P1 may for example have a melt mass-flow rate as determined in accordance with ISO 1133-1 (2011) at 190° C. and under a load of 2.16 kg (MFR2) of ≥0.10 and ≤2.00 g/10 min, preferably of ≥0.10 and ≤0.80 g/10 min. P2 may for example have an MFR2 of ≥0.50 g/10 min, preferably of ≥0.85 and ≤2.00 g/10 min. Preferably, P1 has a melt mass-flow rate as determined in accordance with ISO 1133-1 (2011) at 190° C. and under a load of 2.16 kg (MFR2) of ≥0.10 and ≤2.00 g/10 min, preferably of ≥0.10 and ≤0.80 g/10 min, and P2 has an MFR2 of ≥0.50 g/10 min, preferably of ≥0.85 and ≤2.00 g/10 min. For example, P1 may have an MFR2 that is at least 0.20 g/min, preferably at least 0.40 g/10 min, lower than the MFR2 of P2.

[0022] In a particular embodiment of the invention, P1 has a molecular weight distribution M.sub.w/M.sub.n of ≥2.0 and ≤2.5, and/or P2 has a molecular weight distribution M.sub.w/M.sub.n of ≥2.0 and ≤2.5.

[0023] A further particular embodiment of the invention relates to a thermoplastic material, wherein the thermoplastic material comprises ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %, wherein the ethylene-based material is an ethylene-1-octene copolymer having: [0024] a density of ≥0.880 and ≤0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0025] a fraction of moieties derived from 1-octene of ≥20.0 and ≤30.0 wt % with regard to the total weight of the ethylene-1-octene copolymer; and/or [0026] a molecular weight distribution M.sub.w/M.sub.n of ≥1.5 and ≤2.5, wherein the weight-average molecular weight M.sub.w and the number average molecular weight M.sub.n are determined in accordance with ASTM D6474 (2012).

[0027] In a yet further particular embodiment of the invention, the thermoplastic material consists of ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %, wherein the ethylene-based material is an ethylene-1-octene copolymer having: [0028] a density of ≥0.880 and ≤0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0029] a fraction of moieties derived from 1-octene of ≥20.0 and ≤30.0 wt % with regard to the total weight of the ethylene-1-octene copolymer; and/or [0030] a molecular weight distribution M.sub.w/M.sub.n of ≥1.5 and ≤2.5, wherein the weight-average molecular weight M.sub.w and the number average molecular weight M.sub.n are determined in accordance with ASTM D6474 (2012).

[0031] Another embodiment of the invention also relates to a thermoplastic material, wherein the thermoplastic material comprises or consists of ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %, wherein the ethylene-based polymer material comprises a fraction (A) of a first ethylene-based polymer (P1) and a fraction (B) of a second ethylene based polymer (P2); wherein: [0032] the first ethylene-based polymer P1 has a density of <0.880, preferably <0.870 g/cm.sup.3, preferably of >0.850 and <0.880 g/cm.sup.3, more preferably of >0.850 and <0.870 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); and [0033] the second ethylene-based polymer P2 has a density of >0.890, preferably >0.900 g/cm.sup.3, preferably of >0.890 and <0.930 g/cm.sup.3, more preferably >0.900 and <0.930 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0034] wherein the ethylene-based polymer comprises >10.0 wt % and <90.0 wt % of P1, with regard to the sum of the weight of P1 and P2.

[0035] In certain of its embodiments, the present invention also relates to a pipe comprising the thermoplastic material, or consisting of the thermoplastic material. Such pipe may have an inner layer of the thermoplastic material.

[0036] In a particular embodiment, the invention relates to a pipe comprising the thermoplastic material, wherein the thermoplastic material consists of ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %, wherein the ethylene-based material is an ethylene-1-octene copolymer having: [0037] a density of ≥0.880 and ≤0.890 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0038] a fraction of moieties derived from 1-octene of ≥20.0 and ≤30.0 wt % with regard to the total weight of the ethylene-1-octene copolymer; and/or [0039] a molecular weight distribution M.sub.w/M.sub.n of 1.5 and ≤2.5, wherein the weight-average molecular weight M.sub.w and the number average molecular weight M.sub.n are determined in accordance with ASTM D6474 (2012).

[0040] In another embodiment, the invention relates to a pipe comprising the thermoplastic material, wherein the thermoplastic material consists of ethylene-based polymer material, wherein the ethylene-based polymer material has a Vicat softening temperature of ≥50° C. as determined in accordance with ISO 306 (2013), method A50, and a weight loss as determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, of ≤0.50 wt %, wherein the ethylene-based polymer material comprises a fraction (A) of a first ethylene-based polymer (P1) and a fraction (B) of a second ethylene based polymer (P2); wherein: [0041] the first ethylene-based polymer P1 has a density of <0.870 g/cm.sup.3, preferably of >0.850 and <0.870 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); and [0042] the second ethylene-based polymer P2 has a density of >0.900 g/cm.sup.3, preferably of >0.900 and <0.930 g/cm.sup.3, as determined in accordance with ISO 1183-1 (2019); [0043] wherein the ethylene-based polymer comprises >10.0 wt % and <90.0 wt % of P1, with regard to the sum of the weight of P1 and P2.

[0044] For example, the pipe of the invention may comprise an inner layer comprising or consisting of the thermoplastic material. The inner layer may for example have a thickness of >0.05 and <10.0 cm, preferably >0.1 and <2.0 cm. The pipe may for example consist of a single layer of material. The pipe may for example have an inner diameter of >0.02 and <2.00 m, preferably >0.05 and <1.00 m.

[0045] The invention further also relates to a process for the production of the thermoplastic material, wherein the process involves polymerisation of reactants in two or at least two reactors positioned in series, wherein the first ethylene-based polymer P1 is produced by polymerisation of a first reactant mixture in the first reactor, followed by production of the second ethylene-based polymer P2 by polymerisation of a second reactant mixture in the second reactor, wherein the second reactant mixture comprises the first ethylene-based polymer P1.

[0046] Alternatively, the invention relates to a process for the production of the thermoplastic material wherein the process involves combining a quantity of the first ethylene-based polymer P1 and a quantity of the second ethylene-based polymer P2 by means of blending under melt conditions or in the solid phase.

[0047] The invention will now be illustrated by the following non-limiting examples.

Materials Used

[0048]

TABLE-US-00001 C0560D SABIC FORTIFY C0560D, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 145.2 kg/mol, an M.sub.n of 67.7 g/mol, an M.sub.w/M.sub.n of 2.14, a comonomer content of 39 wt % of units derived from 1-octene, a density of 0.864 g/cm.sup.3 and an MFR2 of 0.50 g/10 min. C0570D SABIC FORTIFY C0570D, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 134.8 kg/mol, an M.sub.n of 62.1 g/mol, an M.sub.w/M.sub.n of 2.17, a comonomer content of 36 wt % of units derived from 1-octene, a density of 0.868 g .Math. cm.sup.3 and an MFR2 of 0.50 g/10 min. C1070D SABIC FORTIFY C1070D, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 121.4 kg/mol, an M.sub.n of 57.6 g/mol, an M.sub.w/M.sub.n of 2.11, a comonomer content of 36 wt % of units derived from 1-octene, a density of 0.870 g/cm.sup.3 and an MFR2 of 1.00 g/10 min. C1080D SABIC FORTIFY C1080D, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 116.9 kg/mol, an M.sub.n of 54.0 g/mol, an M.sub.w/M.sub.n of 2.16, a comonomer content of 28 wt % of units derived from 1-octene, a density of 0.881 g/cm.sup.3 and an MFR2 of 0.96 g/10 min. C1085 SABIC FORTIFY C1085, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 110.0 kg/mol, an M.sub.n of 54.9 g/mol, an M.sub.w/M.sub.n of 2.00, a comonomer content of 26 wt % of units derived from 1-octene, a density of 0.887 g/cm.sup.3 and an MFR2 of 0.98 g/10 min. 8102 SABIC COHERE 8102, an ethylene-octene copolymer obtainable from SABIC, having an M.sub.w of 105.0 kg/mol, an M.sub.n of 38.0 g/mol, an M.sub.w/M.sub.n of 2.76, a comonomer content of 18 wt % of units derived from 1-octene, a density of 0.898 g/cm.sup.3 and an MFR2 of 0.94 g/10 min. 8112 SABIC SUPEER 8112, an ethylene-octene copolymer obtainable from SABIC having an M.sub.w of 104.0 kg/mol, an M.sub.n of 38.0 g/mol, an M.sub.w/M.sub.n of 2.73, a comonomer content of 10 wt % of units derived from 1-octene, a density of 0.912 g/cm.sup.3 and an MFR2 of 1.16 g/10 min. 118N SABIC LLDPE 118N, an ethylene-butene copolymer obtainable from SABIC having an M.sub.w of 125.0 kg/mol, an M.sub.n of 30.6 g/mol, an M.sub.w/M.sub.n of 4.08, a comonomer content of 7 wt % of units derived from 1-butene, a density of 0.918 g/cm.sup.3 and an MFR2 of 0.95 g/10 min. B5403 SABIC HDPE B5403, a high-density polyethylene obtainable from SABIC having an M.sub.w of 380.0 kg/mol, an M.sub.n of 21.0 g/mol, an M.sub.w/M.sub.n of 18.10, a comonomer content of 0.3 wt % of units derived from 1-butene, a density of 0.954 g/cm.sup.3 and an MFR5 of 0.14 g/10 min.

[0049] MFR2 is the melt mass-flow rate as determined in accordance with ISO 1133 (2011) at 190° C. under a load of 2.16 kg; likewise, MFR5 is the melt-mass flow rate determined at 190° C. under a load of 5.0 kg. The density is determined in accordance with ISO 1183-1 (2012).

[0050] Using the above materials, polymer formulations were prepared by melt-mixing the materials in a twin-screw melt extruder of type ZSK26Mc, connected with an underwater pelletizing system to form solidified pellets of the polymer formulation. The extruder conditions were as listed below:

TABLE-US-00002 Zone temperatures (° C.) Zone 1 2 3 4 5 6 7 8 9 Die 80 120 160 160 160 160 160 160 160 160 Die gap Screw speed Throughput 3 mm 300 rpm 15 kg/h

[0051] Via this melt mixing, exemplary formulations were produced according to the compositions of materials as set out in the table below:

TABLE-US-00003 Ex. Composition 1 40.0 wt % C0560D, 60.0 wt % 8112 2 45.0 wt % C0560D, 55.0 wt % 8112 3 50.0 wt % C0560D, 50.0 wt % 8112 4 55.0 wt % C0560D, 45.0 wt % 8112 5 60.0 wt % C0560D, 40.0 wt % 8112 6 70.0 wt % C0560D, 30.0 wt % 8112 7 90.0 wt % C0560D, 10.0 wt % 118N 8 80.0 wt % C0560D, 20.0 wt % 118N 9 70.0 wt % C0560D, 30.0 wt % 118N 10 60.0 wt % C0560D, 40.0 wt % 118N 11 90.0 wt % C0560D, 10.0 wt % B5403 12 80.0 wt % C0560D, 20.0 wt % B5403 13 70.0 wt % C0560D, 30.0 wt % B5403 14 60.0 wt % C0560D, 40.0 wt % B5403 15 45.0 wt % C0570D, 55.0 wt % 8102 16 45.0 wt % C1085, 55.0 wt % 8102 17 45.0 wt % C1085, 55.0 wt % 8112 18 100% C1070D 19 100% C1080D 20 100% C1085 21 100% 8102 22 100% 8112 23 100% B5403

[0052] For each of the formulations, material properties were determined as indicated in the table below:

TABLE-US-00004 Weight Tensile Ex. MFR2 Density Vicat Hardness loss modulus 1 0.81 0.896 64.2 91.6 0.521 47.4 2 0.74 0.893 58.4 90.0 0.445 41.7 3 0.70 0.892 53.6 88.7 0.331 33.1 4 0.70 0.888 49.2 86.7 0.275 22.8 5 0.68 0.885 45.5 84.3 0.250 23.9 6 0.63 0.879 41.7 79.9 0.192 15.9 7 0.53 0.872 39.0 70.3 0.110 5.8 8 0.56 0.878 42.0 75.2 0.090 8.8 9 0.57 0.883 47.0 80.1 0.140 13.3 10 0.59 0.888 51.0 84.8 0.260 27.1 11 0.37 0.875 37.7 71.2 0.090 10.3 12 0.28 0.882 40.4 79.7 0.160 15.9 13 0.20 0.889 46.2 87.2 0.190 35.0 14 0.15 0.897 55.1 92.8 0.400 91.0 15 0.73 0.884 58.4 87.7 0.358 30.3 16 1.00 0.894 72.9 91.3 0.617 44.6 17 1.05 0.902 80.9 93.8 0.844 73.4 18 1.00 0.870 37.5 70.7 0.155 5.4 19 0.96 0.881 49.8 83.5 0.310 15.7 20 0.98 0.887 59.6 87.9 0.421 25.5 21 0.94 0.898 83.6 93.5 0.769 64.5 22 1.16 0.912 98.7 95.7 1.549 126.9 23  0.14* 0.954 131.2 96.6 2.715 1187.4 *for example 23, the MFR5 was determined

[0053] Wherein: [0054] The MFR2 and the MFR5 are determined as indicated above, and expressed in g/10 min; [0055] The density is determined as indicated above, and expressed in g/cm.sup.3; [0056] Vicat is the Vicat softening temperature as determined in accordance with ISO 306 (2013), at a heating rate of 50° C./h, and under a load of 10 N; [0057] Hardness is the Shore A hardness as determined in accordance with ISO 868 (dimensionless); [0058] Weight loss is determined on a compression moulded sheet according to ISO 15527 (2010), Annex B, using silica sand/water slurry with a mass ratio of 3:2, test duration 7 h, expressed in wt %; [0059] Tensile modulus is determined in accordance with ISO 527, expressed in MPa.