WO2024104830A1 - Polymer composition comprising polyethylene with increased stability. - Google Patents
Polymer composition comprising polyethylene with increased stability. Download PDFInfo
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- WO2024104830A1 WO2024104830A1 PCT/EP2023/080996 EP2023080996W WO2024104830A1 WO 2024104830 A1 WO2024104830 A1 WO 2024104830A1 EP 2023080996 W EP2023080996 W EP 2023080996W WO 2024104830 A1 WO2024104830 A1 WO 2024104830A1
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- polymer composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000004698 Polyethylene Substances 0.000 title claims description 27
- -1 polyethylene Polymers 0.000 title claims description 27
- 229920000573 polyethylene Polymers 0.000 title claims description 27
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- 239000001257 hydrogen Substances 0.000 claims abstract 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract 2
- 238000009472 formulation Methods 0.000 claims description 29
- 239000000155 melt Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- NQFCQTOKLUYMAY-UHFFFAOYSA-N [2,4-bis(2-methylbutan-2-yl)phenyl] bis[4-(2-methylbutan-2-yl)phenyl] phosphite Chemical compound C1=CC(C(C)(C)CC)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)CC)C(C)(C)CC)OC1=CC=C(C(C)(C)CC)C=C1 NQFCQTOKLUYMAY-UHFFFAOYSA-N 0.000 claims description 4
- AMBPQHRCAUEZKP-UHFFFAOYSA-N bis[2,4-bis(2-methylbutan-2-yl)phenyl] [4-(2-methylbutan-2-yl)phenyl] phosphite Chemical compound C1=CC(C(C)(C)CC)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)CC)C(C)(C)CC)OC1=CC=C(C(C)(C)CC)C=C1C(C)(C)CC AMBPQHRCAUEZKP-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- ZMPODEGAECKFEA-UHFFFAOYSA-N tris[2,4-bis(2-methylbutan-2-yl)phenyl] phosphite Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)CC)C(C)(C)CC)OC1=CC=C(C(C)(C)CC)C=C1C(C)(C)CC ZMPODEGAECKFEA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- 239000002861 polymer material Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940125368 controlled substance Drugs 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
Definitions
- Polymer composition comprising polyethylene with increased stability.
- 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.
- 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.
- 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.
- the occurrence of 2,4-di-t-butyl phenol (CAS reg. nr. 96-76-4) is to be avoided, it being a controlled substance.
- such stabilisation solution may be appropriate for use in polymer formulations that contain recycled polymer, in particular recycled polyethylene, materials.
- recycled polymer in particular recycled polyethylene
- 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.
- 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.
- 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: c) 2,2-bis(hydroxymethyl)-1 ,3-propanediol.
- Such polymer composition is appropriately stable, and the generation of 2,4-di-t-butyl phenol due to decomposition of stabiliser compounds is prevented.
- 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.
- FTIR Fourier Transform Infrared
- a 90 8 is the absorbance at 908 cm -1
- A933 is the absorbance at 933 cm -1
- A1897 is the absorbance at 1897 cm -1
- a se is the absorbance at 1986 cm -1 of a sample of the material composition.
- the FTIR spectrum of the material to be tested may for example be tested according to the method of ASTM D5576-00 (2006).
- 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).
- 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.
- MFR2 melt mass-flow rate
- 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.
- MFR5 melt mass-flow rate
- 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.
- MFR21 melt mass-flow rate
- 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.
- the composition a) preferably comprises a recycled polyethylene formulation.
- 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).
- 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.
- MFR2 melt mass-flow rate
- the recycled polyethylene formulation preferably comprises > 90.0 wt% of ethylenebased 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.
- 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%.
- 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.
- 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.
- 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).
- 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.
- 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.
- the additive composition b) does not contain any phosphite compounds other than i., ii. and iii.
- the polymer composition does not contain any phosphite compounds other than i., ii. and iii.
- 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).
- 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: to reduce the quantity of vinyl unsaturations in a polymer composition comprising ethylenebased polymers, preferably wherein the polymer composition comprises a recycled polyethylene formulation.
- the invention also relates to an article comprising the polymer composition according to the invention.
- a number of polymer compositions were subjected to melt extrusion using a ZSK25 twin- screw 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 LI- LIO of the extruder, wherein L1 is the feed zone and L10 is the die zone. Temperatures are indicated in °C.
- the feed rate of material to the extruder was 8.3 kg/h.
- 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.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to 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. Such polymer composition appropriately stable to use in recycling applications, wherein undesirable formation of 2,4-di-t-butyl phenol is prevented.
Description
Polymer composition comprising polyethylene with increased stability.
[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:
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:
wherein A908 is the absorbance at 908 cm-1, A933 is the absorbance at 933 cm-1, A1897 is the absorbance at 1897 cm-1, and A se 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/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).
[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/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). 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 ethylenebased 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:
to reduce the quantity of vinyl unsaturations in a polymer composition comprising ethylenebased 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 twin- screw 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 LI- LIO of the extruder, wherein L1 is the feed zone and L10 is the die zone. Temperatures are indicated in °C.
[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.
[0032] Using the above materials, the following compositions were used in the examples demonstrating the invention.
[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.
index, and further ensure the retention of that reduction after multiple iterations of extrusion.
Claims
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:
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.
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. 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). 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. 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. 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%. 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.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN202241065650 | 2022-11-16 | ||
| IN202241065650 | 2022-11-16 | ||
| EP23150726.0 | 2023-01-09 | ||
| EP23150726.0A EP4397704A1 (en) | 2023-01-09 | 2023-01-09 | Polymer composition comprising polyethylene with increased stability |
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| Publication Number | Publication Date |
|---|---|
| WO2024104830A1 true WO2024104830A1 (en) | 2024-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2023/080996 WO2024104830A1 (en) | 2022-11-16 | 2023-11-07 | Polymer composition comprising polyethylene with increased stability. |
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| Country | Link |
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| WO (1) | WO2024104830A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326112A1 (en) * | 2006-06-20 | 2009-12-31 | Chemtura Corporation | Liquid amylaryl phosphite compositions |
| US9963561B2 (en) * | 2015-11-25 | 2018-05-08 | Nova Chemicals (International) S.A. | Phenol free stabilization of polyethylene |
-
2023
- 2023-11-07 WO PCT/EP2023/080996 patent/WO2024104830A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326112A1 (en) * | 2006-06-20 | 2009-12-31 | Chemtura Corporation | Liquid amylaryl phosphite compositions |
| US9963561B2 (en) * | 2015-11-25 | 2018-05-08 | Nova Chemicals (International) S.A. | Phenol free stabilization of polyethylene |
Non-Patent Citations (1)
| Title |
|---|
| CAS, no. 1000027-04-2 |
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