POLYMER COMPOSITION WITH POLYETHYLENE WITH INCREASED STABILITY

Description

[0001] The present invention relates to a polymer composition comprising a polyethylene having an increased stability, in particular an increased stability when subjected to multiple melt processing steps. The invention in particular relates to a polymer composition comprising recycled polyethylenes.

[0002] Whilst phosphite-type antioxidants may be suitable for providing a certain stabilising effect in polyethylene-based polymer formulations, a detrimental effect of the use of certain phosphite-containing compounds is the occurrence of certain degradation products. For particular applications, such as for example in food contact applications, the occurrence of certain byproducts that come to exist as result of the stabilising action, in which the antioxidant compounds may decompose, is not appropriate. In particular, the occurrence of 2,4-di-t-butyl phenol (CAS reg. nr. 96-76-4) is to be avoided, it being a controlled substance.

[0003] Accordingly, a need exists to obtain polyethylene-based formulations that are adequately stabilised to be used in desirable applications, including food contact applications, wherein formation or release of 2,4-di-t-butyl phenol is avoided.

[0004] In particular, such stabilisation solution may be appropriate for use in polymer formulations that contain recycled polymer, in particular recycled polyethylene, materials. As, in view of materials circularity, there is a growing demand for solutions to help avoiding disposal of polymer materials after their useful service life, such as in packaging applications after use of the therein contained product, stabilisation of such polymer materials becomes increasingly more stringent; after all, re-using of such polymer material via recycling processes means that the polymer materials is subjected to both additional shaping processes, which typically involve melt treatment steps, and to a prolonged service life. The polymer molecule needs to be able to withstand additional harsh exposure for a prolonged time, without inappropriately deteriorating. To be able to achieve that, the molecule may be provided help from stabilising compounds.

[0005] Accordingly, it is an object of the present invention to provide a polymer composition comprising ethylene-based polymer material, that is sufficiently stable to use also in recycling applications, wherein undesirable formation of 2,4-di-t-butyl phenol is prevented.

[0006] This is now achieved by a polymer composition comprising or consisting of: a) a composition comprising at least one ethylene-based polymer; b) an additive composition comprising a compound of formula I: wherein each R is individually selected from 1,1-dimethylpropyl or hydrogen; and c) 2,2-bis(hydroxymethyl)-1,3-propanediol.

[0007] Such polymer composition is appropriately stable, and the generation of 2,4-di-t-butyl phenol due to decomposition of stabiliser compounds is prevented.

[0008] In the context of the present invention, the stability of the polymer composition may be understood as reflected by its vinyl index. The vinyl index indicates the quantity of vinyl unsaturations in the polymer material. The lower the quantity of unsaturations, the more stable the material will perform, and the less the material is prone to degradation. The vinyl index may be calculated from the absorbance spectrum as obtained via Fourier Transform Infrared (FTIR) analysis performed in transmission mode. To obtain the value for the vinyl index on the basis of an FTIR spectrum, the below equation is to be applied: VI = A 908 − A 933 A 1897 − A 1986 wherein A 908 is the absorbance at 908 cm -1< , A 933 is the absorbance at 933 cm -1< , A 1897 is the absorbance at 1897 cm -1< , and A 1986 is the absorbance at 1986 cm -1< of a sample of the material composition.

[0009] The FTIR spectrum of the material to be tested may for example be tested according to the method of ASTM D5576-00 (2006).

[0010] Preferably, the ethylene-based polymer has a density of ≥ 940 and ≤ 975 kg / m 3< , preferably of ≥ 950 and ≤ 970 kg / m 3< , more preferably of ≥ 950 and ≤ 965 kg / m 3< , as determined in accordance with ISO 1183-1 (2019).

[0011] The ethylene-based polymer may for example have a melt mass-flow rate (MFR2) of ≥ 0.1 and ≤ 5.0 g / 10 min, preferably of ≥ 0.1 and ≤ 2.0 g / 10 min, more preferably of ≥ 0.1 and ≤ 1.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.

[0012] The ethylene-based polymer may for example have a melt mass-flow rate (MFR5) of ≥ 1.0 and ≤ 10.0 g / 10 min, preferably of ≥ 1.0 and ≤ 7.5 g / 10 min, more preferably of ≥ 1.5 and ≤ 5.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 5 kg.

[0013] The ethylene-based polymer may for example have a melt mass-flow rate (MFR21) of ≥ 10 and ≤ 100 g / 10 min, preferably of ≥ 20 and ≤ 75 g / 10 min, more preferably of ≥ 25 and ≤ 60 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 21.6 kg.

[0014] For example, the ethylene-based polymer may be an ethylene homopolymer or an ethylene copolymer comprising ≤ 10.0 wt%, preferably ≤ 5.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene.

[0015] In the polymer composition according to the invention, the composition a) preferably comprises a recycled polyethylene formulation. Particularly preferably, the composition a) comprises ≥ 20.0 wt%, more preferably ≥ 40.0 wt%, of a recycled polyethylene formulation, with regard to the total weight of the composition a).

[0016] The recycled polyethylene formulation may for example be a post-consumer recycled polyethylene formulation. The recycled polyethylene formulation may for example have a density of ≥ 940 and ≤ 975 kg / m 3< , preferably of ≥ 950 and ≤ 970 kg / m 3< , more preferably of ≥ 950 and ≤ 965 kg / m 3< , as determined in accordance with ISO 1183-1 (2019). The recycled polyethylene formulation may for example have a melt mass-flow rate (MFR2) of ≥ 0.1 and ≤ 5.0 g / 10 min, preferably of ≥ 0.1 and ≤ 2.0 g / 10 min, more preferably of ≥ 0.1 and ≤ 1.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.

[0017] The recycled polyethylene formulation preferably comprises ≥ 90.0 wt% of ethylene-based polymers, more preferably ≥ 95.0 wt%, with regard to the total weight of the recycled polyethylene formulation. The recycled polyethylene formulation preferably comprises ≤ 10.0 wt% of propylene-based polymers, more preferably ≤ 5.0 wt%, with regard to the total weight of the recycled polyethylene formulation.

[0018] In a particular embodiment, the polymer composition may for example comprise ≥ 95.0 wt% of the composition a), with regard to the total weight of the polymer composition, preferably ≥ 98.0 wt%.

[0019] It is preferred that the polymer composition comprises ≥ 100 and ≤ 5000 ppm by weight of the additive composition b), with regard to the total weight of the polymer composition, more preferably ≥ 200 and ≤ 2000 ppm, even more preferably ≥ 500 and ≤ 1500 ppm.

[0020] The polymer composition may for example comprise ≥ 100 and ≤ 5000 ppm by weight of the 2,2-bis(hydroxymethyl)-1,3-propanediol, with regard to the total weight of the polymer composition, more preferably ≥ 200 and ≤ 2000 ppm, even more preferably ≥ 500 and ≤ 1500 ppm.

[0021] For example, the additive composition b) may comprise: i. tris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite (CAS reg. nr. 1065-97-0); and / or ii. bis[2,4-bis-(1,1-dimethylpropyl)phenyl] [4-(1,1-dimethylpropyl)phenyl] phosphite (CAS reg. nr. 1000027-06-4); and / or iii. bis[4-(1,1-dimethylpropyl)phenyl] [2,4-bis-(1,1-dimethylpropyl)phenyl] phosphite (CAS reg. nr. 1000027-04-2).

[0022] It is preferred that the additive composition b) comprises: i. tris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite; ii. bis[2,4-bis-(1,1-dimethylpropyl)phenyl] [4-(1,1-dimethylpropyl)phenyl] phosphite; and iii. bis[4-(1,1-dimethylpropyl)phenyl] [2,4-bis-(1,1-dimethylpropyl)phenyl] phosphite.

[0023] In a particular embodiment, the additive composition b) may for example comprise ≥ 90.0 wt% of the sum of i., ii, and iii, preferably ≥ 95.0 wt%, more preferably ≥ 98.0 wt%, with regard to the total weight of the additive composition.

[0024] Preferably, the additive composition b) does not contain any phosphite compounds other than i., ii. and iii. In a particularly preferred embodiment, the polymer composition does not contain any phosphite compounds other than i., ii. and iii.

[0025] The additive composition b) may further comprise tris(2-propanol)amine, preferably wherein the additive composition b) comprises ≥ 0 and ≤ 10.0 wt%, more preferably ≥ 0 and ≤ 5.0 wt%, even more preferably ≥ 0 and ≤ 2.0 wt%, of tris(2-propanol)amine, with regard to the total weight of the additive composition b).

[0026] In an embodiment, the invention also relates to the use of a formulation comprising 2,2-bis(hydroxymethyl)-1,3-propanediol and an additive composition comprising a compound of formula I: wherein each R is individually selected from 1,1-dimethylpropyl or hydrogen; to reduce the quantity of vinyl unsaturations in a polymer composition comprising ethylene-based polymers, preferably wherein the polymer composition comprises a recycled polyethylene formulation.

[0027] The invention also relates to an article comprising the polymer composition according to the invention.

[0028] The invention will now be illustrated by the following non-limiting examples.

[0029] A number of polymer compositions were subjected to melt extrusion using a ZSK25 twinscrew melt extruder, having a screw diameter of 25 mm, and an L / D ratio of 40. The extruder was operated at 250 rpm, using the below setpoint temperature profile for each of the zone L1-L10 of the extruder, wherein L1 is the feed zone and L10 is the die zone. Temperatures are indicated in °C. L1L2L3L4L5L6L7L8L9L10160210230240240240250250250250

[0030] The feed rate of material to the extruder was 8.3 kg / h.

[0031] Using the above extrusion conditions, extrusion experiments were conducted of material compositions wherein the below-listed materials were used. PE1An ethylene-based polymer, SABIC B6246LS, obtainable from SABIC, having a density of 962 kg / m 3< and an MFR2 of 0.50.PCRA post-consumer recycled polyethylene formulation having a density of 957 kg / m 3< , comprising 0.3 wt% of polypropylene.AO1Weston 705, a phosphite type antioxidant obtainable from SI Group, CAS reg nr. 1373229-80-1, comprising tris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite, bis[2,4-bis-(1,1-dimethylpropyl)phenyl] [4-(1,1-dimethylpropyl)phenyl] phosphite, and bis[4-(1,1-dimethylpropyl)phenyl] [2,4-bis-(1,1-dimethylpropyl)phenyl] phosphite.AO2Weston 705T, a phosphite type antioxidant obtainable from SI Group, CAS reg nr. 2762929-16-6, comprising tris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite, bis[2,4-bis-(1,1-dimethylpropyl)phenyl] [4-(1,1-dimethylpropyl)phenyl] phosphite, and bis[4-(1,1-dimethylpropyl)phenyl] [2,4-bis-(1,1-dimethylpropyl)phenyl] phosphite, and further comprising tris(2-propanol)amine.AO3Irgafos 168, (2,4-bis(t-butyl))-1,1',1"-phosphite phenol, CAS reg. nr. 31570-04-4BHP2,2-bis(hydroxymethyl)-1,3-propanediol, CAS reg. nr. 115-77-5CaStCalcium stearate, CAS reg. nr. 1592-23-01010Irganox 1010, Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 1, 1'-[2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl] ester, CAS reg. nr. 6683-19-8MD1024Irganox MD 1024, Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]hydrazide, CAS reg. nr. 32687-78-8

[0032] Using the above materials, the following compositions were used in the examples demonstrating the invention. Example123456PE199.7 wt%99.7 wt%99.7 wt%99.6 wt%99.6 wt%99.6 wt%PCRAO1921 ppm921 ppmAO2939 ppm939 ppmAO31000 ppm1000 ppmBHP1000 ppm1000 ppm1000 ppmCaSt1000 ppm1000 ppm1000 ppm1000 ppm1000 ppm1000 ppm1010500 ppm500 ppm500 ppm500 ppm500 ppm500 ppmMD1024200 ppm200 ppm200 ppm200 ppm200 ppm200 ppm Example789101112PE149.7 wt%49.7 wt%49.7 wt%49.6 wt%49.6 wt%49.6 wt%PCR50.0 wt%50.0 wt%50.0 wt%50.0 wt%50.0 wt%50.0 wt%AO1817 ppm817 ppmAO2833 ppm833 ppmAO3887 ppm887 ppmBHP1000 ppm1000 ppm1000 ppmCaSt967 ppm967 ppm967 ppm967 ppm967 ppm967 ppm1010430 ppm430 ppm430 ppm430 ppm430 ppm430 ppmMD1024187 ppm187 ppm187 ppm187 ppm187 ppm187 ppm

[0033] To test the stabilisation properties, each of the formulations 1 through 12 was subjected to extrusion according to the conditions as set out above for 5 cycles, to establish the stability of the formulations when exposed to multiple occasions of melt processing. By so, it was evaluated whether the formulations were of appropriate quality to be used in recycling applications.

[0034] In the table below, results of testing of the vinyl index (VI) of the example formulations are presented. VI123456After 1 st< cycle1.931.791.721.651.561.52After 3 rd< cycle1.831.811.711.581.511.56After 5 th< cycle1.871.791.741.551.511.51 VI789101112After 1 st< cycle1.911.801.731.561.501.49After 3 rd< cycle1.811.821.801.581.451.52After 5 th< cycle1.811.841.791.561.521.51

[0035] The above results demonstrate that the polymer compositions allow for a reduction of the vinyl index, and further ensure the retention of that reduction after multiple iterations of extrusion.

Claims

1. Polymer composition comprising or consisting of: a) a composition comprising at least one ethylene-based polymer; b) an additive composition comprising a compound of formula I: wherein each R is individually selected from 1,1-dimethylpropyl or hydrogen; and c) 2,2-bis(hydroxymethyl)-1,3-propanediol.

2. Polymer composition according to claim 1, wherein the ethylene-based polymer has: • a density of ≥ 940 and ≤ 975 kg / m3, preferably of ≥ 950 and ≤ 970 kg / m3, more preferably of ≥ 950 and ≤ 965 kg / m3, as determined in accordance with ISO 1183-1 (2019); and • a melt mass-flow rate (MFR2) of ≥ 0.1 and ≤ 5.0 g / 10 min, preferably of ≥ 0.1 and ≤ 2.0 g / 10 min, more preferably of 0.1 and ≤ 1.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.

3. Polymer composition according to any one of claims 1-2, wherein the ethylene-based polymer has: • a melt mass-flow rate (MFR5) of ≥ 1.0 and ≤ 10.0 g / 10 min, preferably of ≥ 1.0 and ≤ 7.5 g / 10 min, more preferably of ≥ 1.5 and ≤ 5.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 5 kg; and / or • a melt mass-flow rate (MFR21) of ≥ 10 and ≤ 100 g / 10 min, preferably of ≥ 20 and ≤ 75 g / 10 min, more preferably of ≥ 25 and ≤ 60 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 21.6 kg.

4. Polymer composition according to any one of claims 1-3, wherein the ethylene-based polymer is an ethylene homopolymer or an ethylene copolymer comprising ≤ 10.0 wt%, preferably ≤ 5.0 wt%, of moieties derived from a comonomer selected from 1-butene, 1-hexene and 1-octene.

5. Polymer composition according to any one of claims 1-4, wherein the composition a) comprises a recycled polyethylene formulation, preferably wherein the composition a) comprises ≥ 20.0 wt%, more preferably ≥ 40.0 wt%, of a recycled polyethylene formulation, with regard to the total weight of the composition a).

6. Polymer composition according to claim 5, wherein the recycled polyethylene formulation is a post-consumer recycled polyethylene formulation, preferably having: • a density of ≥ 940 and ≤ 975 kg / m3, preferably of ≥ 950 and ≤ 970 kg / m3, more preferably of ≥ 950 and ≤ 965 kg / m3, as determined in accordance with ISO 1183-1 (2019); • a melt mass-flow rate (MFR2) of ≥ 0.1 and ≤ 5.0 g / 10 min, preferably of ≥ 0.1 and ≤ 2.0 g / 10 min, more preferably of 0.1 and ≤ 1.0 g / 10 min, as determined in accordance with ISO 1133-1 (2011), at 190°C at a load of 2.16 kg.

7. Polymer composition according to any one of claims 5-6, wherein the recycled polyethylene formulation comprises ≥ 90.0 wt% of ethylene-based polymers, preferably ≥ 95.0 wt%, with regard to the total weight of the recycled polyethylene formulation; and / or wherein the recycled polyethylene formulation comprises ≤ 10.0 wt% of propylene-based polymers, preferably ≤ 5.0 wt%, with regard to the total weight of the recycled polyethylene formulation.

8. Polymer composition according to any one of claims 1-7, wherein the polymer composition comprises ≥ 95.0 wt% of the composition a), with regard to the total weight of the polymer composition, preferably ≥ 98.0 wt%.

9. Polymer composition according to any of claims 1-8, wherein the polymer composition comprises ≥ 100 and ≤ 5000 ppm by weight of the additive composition b), with regard to the total weight of the polymer composition, preferably ≥ 200 and ≤ 2000 ppm, more preferably ≥ 500 and ≤ 1500 ppm.

10. Polymer composition according to any one of claims 1-9, wherein the polymer composition comprises ≥ 100 and ≤ 5000 ppm by weight of the 2,2-bis(hydroxymethyl)-1,3-propanediol, with regard to the total weight of the polymer composition, preferably ≥ 200 and ≤ 2000 ppm, more preferably ≥ 500 and ≤ 1500 ppm.

11. Polymer composition according to any one of claims 1-10, wherein the additive composition b) comprises: i. tris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite; ii. bis[2,4-bis-(1,1-dimethylpropyl)phenyl] [4-(1,1-dimethylpropyl)phenyl] phosphite; and iii. bis[4-(1,1-dimethylpropyl)phenyl] [2,4-bis-(1,1-dimethylpropyl)phenyl] phosphite.

12. Polymer composition according to claim 11, wherein the additive composition b) comprises ≥ 90.0 wt% of the sum of i., ii, and iii, preferably ≥ 95.0 wt%, more preferably ≥ 98.0 wt%, with regard to the total weight of the additive composition.

13. Polymer composition according to any one of claims 11-12, wherein the additive composition b) does not contain any phosphite compounds other than i., ii. and iii.

14. Polymer composition according to any one of claims 1-13, wherein the additive composition b) comprises tris(2-propanol)amine, preferably wherein the additive composition b) comprises ≥ 0 and ≤ 10.0 wt%, more preferably ≥ 0 and ≤ 5.0 wt%, even more preferably ≥ 0 and ≤ 2.0 wt%, of tris(2-propanol)amine, with regard to the total weight of the additive composition b).

15. Use of a formulation comprising 2,2-bis(hydroxymethyl)-1,3-propanediol and an additive composition comprising a compound of formula I: wherein each R is individually selected from 1,1-dimethylpropyl or hydrogen; to reduce the quantity of vinyl unsaturations in a polymer composition comprising ethylene-based polymers, preferably wherein the polymer composition comprises a recycled polyethylene formulation.