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WO2025125045A1 - Articles contenant des ionomères à base de polyéthylène - Google Patents

Articles contenant des ionomères à base de polyéthylène Download PDF

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Publication number
WO2025125045A1
WO2025125045A1 PCT/EP2024/084731 EP2024084731W WO2025125045A1 WO 2025125045 A1 WO2025125045 A1 WO 2025125045A1 EP 2024084731 W EP2024084731 W EP 2024084731W WO 2025125045 A1 WO2025125045 A1 WO 2025125045A1
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Prior art keywords
methyl
ethylene polymer
ipc
monomer
article
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Jerome VACHON
Peter Neuteboom
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/04—High pressure, i.e. P > 50 MPa, 500 bars or 7250 psi

Definitions

  • the invention relates to an article comprising an ethylene polymer derived from ethylene and specific cationic and anionic monomers.
  • the invention further relates to the process of preparing such an article and to the use of the article.
  • BACKGROUND For many products such as in automotive, consumer goods and packaging application – a key design requirement for the manufacture of such products is light weighting while having the desired tensile properties. Yet another requirement in recent years have been to develop material which can be recycled relatively easily. [0003] Light weighting may be achieved by using suitable polymers such as polyethylene for forming such articles.
  • Polyethylene or ethylene polymer is a versatile polymer and finds application in a wide range of application from films to pipes to cable insulation. Products prepared from polyethylene can impart the desired light weighting and has been used in the past as a substitute to metal, rubber and can be easily recycled by conventional mechanical and chemical processing.
  • ethylene polymers impart the desired light weighting, such polymers may not always provide the necessary tensile properties such as tensile stress at break, tensile strain at break and modulus of elasticity (Young’s modulus).
  • fillers such as talc or carbon black or reinforcing fibers such as glass or carbon fibers have to be incorporated into the ethylene polymers.
  • an article comprising an ethylene polymer wherein the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; and (b) polymeric units derived from a cationic monomer represented by formula (I) ⁇ hydrogen or an alkyl group having 1-10 carbon atoms, preferably 1-5 carbon atoms; ⁇ ‘X’ is independently selected from ‘O’ or ‘NH’, preferably ‘X’ is ‘O’; ⁇ R 2 is an alkyl group having 1-40 carbon atoms, preferably 1-5 carbon atoms; ⁇ R3 and R4 are each independently selected from hydrogen or an alkyl group having 1-10 carbon atoms, preferably 1-5 carbon atoms; and ⁇ R 5 is independently selected from hydrogen or an alkyl group having 1-20 carbon atoms, preferably 1-5 carbon atoms, ⁇ preferably wherein each of R3 and R4 is an alkyl group having 1-5 carbon atoms and R 5
  • the article comprises an ethylene polymer wherein the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; and (b) polymeric units derived from a cationic monomer represented by formula (I): POLY0104-WO-ORD 5 ⁇ hydrogen or an alkyl group having 1-10 carbon atoms, preferably 1-5 carbon atoms; ⁇ ‘X’ is independently selected from ‘O’ or ‘NH’, preferably ‘X’ is ‘O’; ⁇ R2 is an alkyl group having 1-40 carbon atoms, preferably 1-5 carbon atoms; ⁇ R 3 and R 4 are each independently selected from hydrogen or an alkyl group having 1-10 carbon atoms, preferably 1-5 carbon atoms; and ⁇ R5 is independently selected from hydrogen or an alkyl group having 1-20 carbon atoms, preferably 1-5 carbon atoms, ⁇ preferably wherein each of R3 and R4 is an alkyl group having 1-5 carbon atoms and R5 is hydrogen;
  • POLY0104-WO-ORD 6 ⁇ where from hydrogen or an alkyl group having 1-10 carbon atoms, preferably 1-5 carbon atoms; ⁇ R8 and R10 are each independently selected from alkyl group having 1-40 carbon atoms; ⁇ ‘Y’, ‘V’ and ‘W’ is independently selected from ‘O’ or ‘NH’; ‘n’ is a number ranging from 1 to 20, preferably 1-10, preferably 1-5; ‘Z’ is independently selected from -SO3 or - C(O)O; ⁇ preferably wherein the anionic monomer is (II) where R6 is an alkyl group having 1-5 carbon atoms, and ⁇ the cationic monomer is where ‘X’ is ‘O’, and each of R2, R3 and R4 is an and R5 is hydrogen; POLY0104-WO-ORD 7 (i) wherein the total content of derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 2.5 and ⁇ 9.0 wt.%, with
  • the article comprises > 80.0 wt.% of the ethylene polymer, with regard to the total weight of the article.
  • R8 and R10 are each independently selected from alkyl group having 1- 20, preferably 1-10, preferably 1-5 carbon atoms.
  • the article comprises ⁇ 88.0 wt.%, preferably ⁇ 90.0 wt.%, preferably ⁇ 95.0 wt.%, preferably ⁇ 95.0 wt.% and ⁇ 100.0 wt.%, of the ethylene polymer, with regard to the total weight of the article.
  • the polymeric units derived from the cationic monomer and the anionic monomer may be derived from specific ion pair compounds, which is copolymerized with ethylene. It is particularly preferred the article is substantially free of fillers selected from talc, carbon black, reinforcing fibers. It is particularly preferred that the ethylene polymer is free of substantially free of fillers selected from talc, carbon black, reinforcing fibers. [0014]
  • the term substantially free as used herein means that the concentration of fillers such as talc, carbon black, reinforcing fibers is less than 100 ppm by weight, preferably 50 ppm by weight, preferably 0 ppm by weight of the article or the ethylene polymer.
  • the inventors surprisingly found that even without using traditional fillers that are typically used to improve tensile and other mechanical properties in a polymer or even without crosslinking the ethylene polymer, the article prepared from the ethylene polymer demonstrated excellent tensile properties.
  • the invention relates to the use of the ethylene polymer defined in the invention for improving the tensile property of a multi-layered sheet or film, preferably wherein the tensile property is any one of tensile modulus, tensile stress at break, and tensile strain at break.
  • POLY0104-WO-ORD 8 [0016]
  • the inventors found that by polymerizing the ethylene polymer with the ionomers in a high pressure reactor at a temperature of ⁇ 150 oC and ⁇ 255 oC, at a pressure of ⁇ 190 MPa and ⁇ 210 MPa and in presence of one or more free-radical initiator present at a concentration of ⁇ 0.27 milli mol.% and ⁇ 0.6 milli mol.% and a chain transfer agent (CTA) in an amount of > 0.01 and ⁇ 0.1 mol%, preferably ⁇ 0.05 and ⁇ 0.1 mol%, with regard to total amount of ethylene monomer in the high pressure reactor, resulted in ethylene polymers with specific melt flow index and ionomer content which helped in imparting the desired properties.
  • CTA chain transfer agent
  • the ethylene polymer is free of cross-linking.
  • the term free of cross-linking means that the ethylene polymer chains are not cross-linked using cross- linking agents such as cross-linking by peroxide or azo compounds.
  • the invention is directed to the use of the article for improving the tensile property of a multi-layered sheet or film.
  • the tensile property for example are tensile modulus, tensile stress at break, and tensile strain at break.
  • the article of the present invention is selected to have: (a) a tensile modulus of ⁇ 550 MPa and ⁇ 1100 MPa, when determined in accordance with ISO 527-1; and (b) a tensile stress at break of ⁇ 150 MPa and ⁇ 300 MPa, when determined in accordance with ISO 527-1; and (c) a tensile strain at break of ⁇ 600 % and ⁇ 1500 %, when determined in accordance with ISO 527-1.
  • the article may be any suitable article that may be prepared by extruding the ethylene polymer.
  • the extrusion process may also include the process of reactive extrusion, co- extrusion, extrusion coating, cast film extrusion.
  • the article is selected from a packaging article, a container, a tube, a hygiene product, an automotive component, a sheet, a hinge component, cable insulation layer, cable jacket, a layer in coextruded multi-layered film or sheet, a multi-layered film or sheet, preferably the article is a multi-layered film or sheet.
  • the article comprises the ethylene polymer
  • the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; (b) polymeric units derived from the anionic monomer represented by the formula: POLY0104-WO-ORD 9 atoms; and (c) polymeric units derived from the cationic monomer represented by the formula: where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl group (i) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 2.5 and ⁇ 9.0 wt.%, preferably ⁇ 3.0 and ⁇ 8.5 wt.%, preferably ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; (ii) wherein the melt flow index (MFI2) of the ethylene polymer ranges from ⁇
  • the article the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; (b) polymeric units derived from the anionic monomer represented by the formula: having 1-5 carbon atoms; and (c) polymeric units derived from the cationic monomer represented by the formula: where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl group (i) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 2.5 and ⁇ 9.0 wt.%, with regard to the total weight of the ethylene polymer; (ii) wherein the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.01 and ⁇ 20.0 dg/min, where MFI2 is the melt flow index determined in accordance with ISO1133-1:2011 at 190 oC and measured at 2.16 kg; and (iii)
  • the article comprising the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; POLY0104-WO-ORD 11 (b) polymeric units derived from anionic monomer represented by the formula: having 1-5 carbon atoms; and (c) polymeric units derived from the cationic monomer represented by the formula: where ‘X’ is ‘O’, and each of R 2 , R 3 and R 4 is an alkyl group (i) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 2.5 and ⁇ 9.0 wt.%, with regard to the total weight of the ethylene polymer; (ii) wherein the melt flow index (MFI2) of the ethylene polymer ranges from ⁇ 0.01 and ⁇ 20.0 dg/min, where MFI 2 is the melt flow index determined in accordance with ISO1133-1:2011 at 190 oC and measured at 2.16 kg; and (iii
  • the cationic monomer and the anionic monomer is present in a stoichiometric ratio of 1:1.
  • POLY0104-WO-ORD 12 [0025] Accordingly, the selection of MFI 2 and the content of cationic monomer and the anionic monomer (IPC) has to be selected such that the value of MFI2/IPC is between ⁇ 0.01 and ⁇ 8.0.
  • the article comprising the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; (b) polymeric units derived from the anionic monomer represented by the formula: having 1-5 carbon atoms; and (c) polymeric units derived from the cationic monomer represented by the formula: where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl group (i) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 8.5 wt.%, preferably ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; (ii) wherein the melt flow index (MFI2) of the ethylene polymer ranges ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0 dg/
  • MFI2 melt flow
  • the article comprising the ethylene polymer comprises or consists of: (a) polymeric units derived from ethylene; (b) polymeric units derived from the anionic monomer represented by the formula: having 1-5 carbon atoms; and (c) polymeric units derived from the cationic monomer represented by the formula: where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl group (i) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 8.5 wt.%, with regard to the total weight of the ethylene polymer; (ii) wherein the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 14.0 dg/min, preferably ⁇ 0.05 and ⁇ 5.0 dg/min, preferably ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0
  • the article comprises > 80.0 wt.% of the ethylene polymer, with regard to the total weight of the article.
  • R2 is ethyl
  • R5 is hydrogen and R3 and R4 are methyl group.
  • R 2 is ethyl
  • R 5 is hydrogen and R 3 and R 4 are methyl group.
  • R 2 is ethyl
  • R 5 is hydrogen and R3 is t-butyl and R4 is a hydrogen.
  • R2 is ethyl and R3, R4 and R5 are hydrogen.
  • MFI2/IPC The value of MFI2/IPC is indicative of the fact that a suitable selection of an ethylene polymer needs to be made - having a certain combination of melt flow index combined with the amount of polymeric units derived from the anionic and cationic monomer. Therefore, only a specific ethylene polymers having only a certain combination of melt flow index (MFI2) and content of polymeric units derived from ion pair compound, would have the desired tensile properties.
  • the ethylene polymer has (i) total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranging from ⁇ 2.5 and ⁇ 9.0 wt.%, preferably ⁇ 3.0 and ⁇ 8.5 wt.%, preferably ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (ii) a total content of polymeric units derived from ethylene ranging from ⁇ 91.0 and ⁇ 97.5 wt.%, preferably ⁇ 91.5 and ⁇ 97.0 wt.%, preferably ⁇ 92.5 and ⁇ 97.0 wt.%, preferably ⁇ 93.0 and ⁇ 96.0 wt.%, with regard to the total weight of the ethylene polymer.
  • IPC anionic monomer
  • the ethylene polymer has (i) total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranging from ⁇ 3.0 and ⁇ 7.5 wt.%, with regard to the total weight of the ethylene polymer; and (ii) a total content of polymeric units derived from ethylene ranging from ⁇ 92.5 and ⁇ 97.0 wt.%, with regard to the total weight of the ethylene polymer.
  • IPC anionic monomer
  • the ethylene polymer has (i) total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranging from ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (ii) a total content of polymeric units POLY0104-WO-ORD 15 derived from ethylene ranging from ⁇ 93.0 96.0 wt.%, with regard to the total weight of the ethylene polymer.
  • IPC anionic monomer
  • melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 14.0 dg/min, preferably ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is ⁇ 0.01 and ⁇ 4.7, preferably ⁇ 0.01 and ⁇ 1.0, preferably ⁇ 0.01 and ⁇ 0.4, where IPC and MFI2 are as defined herein.
  • the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 14.0 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is ⁇ 0.01 and ⁇ 4.7, where IPC and MFI 2 are as defined herein.
  • the melt flow index (MFI2) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 2.0 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI2/IPC is ⁇ 0.01 and ⁇ 1.0, where IPC and MFI2 are as defined herein.
  • the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 14.0 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is ⁇ 0.026 and ⁇ 4.7, where IPC and MFI 2 are as defined herein.
  • the anionic monomer is where R 6 is an alkyl group having 1-5 carbon atoms, and the cationic monomer is where ‘X’ is ‘O’, and each of R 2 , R 3 and R4 is an alkyl hydrogen, (a) wherein the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is ⁇ 0.01 and ⁇ 1.0, preferably ⁇ 0.01 and ⁇ 0.3, where IPC and
  • melt flow index (MFI2) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0 dg/min, preferably ⁇ 0.08 and ⁇ 0.5 dg/min, preferably ⁇ 0.09 and ⁇ 0.5 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is ⁇ 0.01 and ⁇ 0.4, preferably ⁇ 0.01 and ⁇ 0.3, preferably ⁇ 0.02 and ⁇ 0.2, where IPC and MFI2 are as defined herein.
  • the anionic monomer is (II) where R 6 is an alkyl group having 1-5 carbon atoms, and the cationic monomer is where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl R5 is hydrogen, (a) wherein the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.09 and ⁇ 0.5 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI2/IPC is > 0.02 and ⁇ 0.4, where IPC and MFI 2 are as defined herein.
  • MFI 2 melt flow index
  • IPC anionic monomer
  • the anionic monomer is (II) where R 6 is an alkyl group having 1-5 carbon atoms, and the cationic monomer is where ‘X’ is ‘O’, and each of R2, R3 and R4 is an alkyl R5 is hydrogen, (a) wherein the POLY0104-WO-ORD 18 melt flow index (MFI 2 ) of the ethylene ranges from ⁇ 0.09 and ⁇ 0.5 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI 2 /IPC is > 0.01 and ⁇ 0.2, where IPC and MFI2 are as defined herein.
  • MFI 2 melt flow index
  • the article comprises ⁇ 88.0 wt.%, preferably ⁇ 90.0 wt.%, preferably ⁇ 95.0 wt.%, preferably ⁇ 95.0 wt.% and ⁇ 100.0 wt.%, of the ethylene polymer, with regard to the total weight of the article; and/or the article is substantially free of fillers selected from talc, carbon black, and reinforcing fibers.
  • fillers selected from talc, carbon black, and reinforcing fibers.
  • Non-limiting examples of reinforcing fibers include glass including short glass fiber, carbon fiber.
  • the article comprises ⁇ 12.0 wt.%, preferably ⁇ 10.0 wt.%, preferably ⁇ 5.0 wt.%, preferably ⁇ 0 wt.% and ⁇ 5.0 wt.%, with respect to the total weight of the article, of additives selected from color pigment, UV stabilisers, anti-oxidant stabilisers and combinations thereof.
  • the cationic monomer represented by formula (I) may be derived from the quaternarized form of a free base selected from the group consisting of: 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-(tert-butylamino)ethyl methacrylate, N-[3-(hexahydro-1 H-azepin-1 -yl)-1,1-dimethylpropyl]-2-propenamide, N-[2-(tetrahydro-1 ,4-oxazepin-4(5H)-yl)ethyl]- 2-propenamide, N-[2-[methyl(tetrahydro-2H-pyran-4-yl)amino]ethyl]- 2-propenamide, N-[2-[methyl(tetra
  • the cationic monomer of formula (I) is derived from the quaternarized form of the free base selected from the group consisting of 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, 2-(diethylamino)ethyl methacrylate, 2- (dimethylamino)ethyl methacrylate, and 2-(tert-butylamino)ethyl methacrylate.
  • the term “quaternarized form of the free base” means the quaternary compound formed from the free base.
  • the anionic monomer may be derived from the deprotonated form of a free acid selected from the group consisting of: acrylic acid, methacrylic acid, 2-methyl-2-[(1 -oxo-2-propen-1 -yl)amino]- 1 -propanesulfonic acid, 2-methyl-1 -[(1 -oxo-2-propen-1 -yl)amino]- 1 -propanesulfonic acid, 1 -[(1 -oxo-2-propen-1 -yl)amino]-2-butanesulfonic acid 2-[(2-methyl-1 -oxo-2-propen-1 -yl)amino]-2-propanesulfonic acid, 1 -[(1 -oxo-2-propen-1 -yl)amino]-ethanesulfonic acid, 2-(phosphonooxy)ethylester-2-propenoic acid, 2-propenoic acid
  • the anionic monomer is derived from the deprotonated form of any one of acrylic acid, or methacrylic acid.
  • the anionic monomer is derived from the deprotonated form of any one of acrylic acid, or methacrylic acid; and wherein the cationic monomer is derived from the quaternarized form of the free base selected from the group consisting of 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, 2-(diethylamino)ethyl methacrylate, 2- (dimethylamino)ethyl methacrylate, and 2-(tert-butylamino)ethyl methacrylate.
  • the cationic monomer is derived from the quaternarized form of 2- (dimethylamino)ethyl methacrylate and the anionic monomer is derived from the deprotonated form of methacrylic acid.
  • the cationic monomer is derived from the quaternarized form of 2- (dimethylamino)ethyl methacrylate and the anionic monomer is derived from the deprotonated form of methacrylic acid (a) wherein the melt flow index (MFI2) of the ethylene polymer ranges from ⁇ 0.01 and ⁇ 20.0 dg/min, preferably ⁇ 0.01 and ⁇ 15.0 dg/min, preferably ⁇ 0.08 and ⁇ 14.0 dg/min, preferably ⁇ 0.05 and ⁇ 5.0 dg/min, preferably ⁇ 0.08 and ⁇ 3.0 dg/min, preferably ⁇ 0.08 and ⁇ 2.0 dg/min, preferably ⁇ 0.08 and ⁇ 0.5 dg/min where MFI2 is the melt flow index determined in accordance with ISO1133-1:2011 at 190 oC and measured at 2.16 kg; and (b) wherein the total content of polymeric units derived from the cationic monomer ranges from
  • the cationic is derived from the quaternarized form of 2- (dimethylamino)ethyl methacrylate and the anionic monomer is derived from the deprotonated form of methacrylic acid; and (a) wherein the melt flow index (MFI 2 ) of the ethylene polymer ranges from ⁇ 0.08 and ⁇ 3.0 dg/min; preferably ⁇ 0.08 and ⁇ 0.5 dg/min, preferably ⁇ 0.09 and ⁇ 0.5 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 3.0 and ⁇ 7.5 wt.%, preferably ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI2/IPC is ⁇ 0.01 and ⁇ 1.0, preferably
  • the cationic monomer is derived from the quaternarized form of 2- (dimethylamino)ethyl methacrylate and the anionic monomer is derived from the deprotonated form of methacrylic acid; and (a) wherein the melt flow index (MFI2) of the ethylene polymer ranges from ⁇ 0.09 and ⁇ 0.5 dg/min; and (b) wherein the total content of polymeric units derived from the cationic monomer and the anionic monomer (IPC) ranges from ⁇ 4.0 and ⁇ 7.0 wt.%, with regard to the total weight of the ethylene polymer; and (c) wherein the value of MFI2/IPC is > 0.01 and ⁇ 0.2, where IPC and MFI 2 are as defined herein.
  • MFI2 melt flow index
  • IPC anionic monomer
  • the ethylene polymer is obtained by copolymerizing ethylene with cationic monomer and the anionic monomer. It is preferred that the cationic monomer and the anionic monomer is in the form of ion pair compound, with the opposite charges counter balancing each other.
  • the term “ion pair compound” as used herein means ion pair compound according to patent application WO2021009274A1.
  • the molar ratio of cationic monomer and the anionic monomer that may be copolymerized with ethylene can be in amount of 10:1 to 1:10, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, more preferably 1.1:1 to 1:1.1.
  • molar ratio of cationic monomer and the anionic monomer is in the ratio of 3:1 to 1:1, more preferably 2.5:1 to 1.5:1, more preferably 2.1:1 to 1.9:1.
  • POLY0104-WO-ORD 22 It is preferred that the cationic monomer and the anionic monomer are present in the ethylene polymer in a stoichiometric amount.
  • the cationic monomer and the anionic monomer are present in a stoichiometric amount with a stoichiometric ratio of 1:1 or 1:2 depending on the ion pair formed.
  • the cationic monomer and the anionic monomer can be of the form given as the form below: with the cationic monomer is represented by the methacrylate and the anionic monomer is represented by the deprotonated form of methacrylic acid.
  • the ionic pair compound may also be represented by the formula below: with the cationic monomer represented by the quaternary form and the anionic monomer is represented by the deprotonated form of methacrylic acid.
  • the ionic pair compound may also be represented by the formula below: with the cationic monomer represented by the methacrylate and the anionic monomer is represented by the deprotonated form of methacrylic acid.
  • the ion pair compound may be denoted as: O O O O O O [0060]
  • the ion pair compound may be represented by – POLY0104-WO-ORD 23
  • the ethylene polymer used in the present application is obtained by copolymerizing ethylene and an ion pair compound consisting of a cation of formula (I) and an acid anion of formula (II).
  • the ion pair compound according to the invention can be dissolved in various types of common polar organic solvents such as isopropanol, acetonitrile, ethyl acetate and injected in the polymerization reactor as a solution.
  • the copolymerization may be performed under known processes. However, the present inventors found that the ethylene polymer as used in the article according to the invention is obtained when the polymerization is carried out using a combination of suitable amounts of free- radical initiator, chain transfer agent and conducting the polymerization at a suitable temperature. [0064] Preferably, the ethylene polymer according to the invention are produced in a high- pressure free-radical polymerization process. An advantage of polymerization in such high-pressure free-radical process is that the polymerization may be performed without the need for a catalyst being present.
  • a further advantage of preparing the ethylene polymer in a high-pressure free- radical polymerization process is that the resultant polymer has a certain degree of long-chain branching.
  • ethylene polymers are required to have a certain degree of such long-chain branching. The presence of such long-chain branching is understood to contribute to the desired melt processing POLY0104-WO-ORD 24 properties.
  • ethylene copolymer according to the present invention is prepared via a high-pressure free-radical polymerisation process.
  • the pressure in such high-pressure free-radical polymerization process is preferably in the range of ⁇ 180 MPa and ⁇ 350 MPa, preferably ⁇ 190 MPa and ⁇ 210 MPa, preferably ⁇ 200 MPa and ⁇ 300 MPa.
  • the pressure in such high-pressure free-radical polymerization process is in the range of ⁇ 190 MPa and ⁇ 210 MPa.
  • Tubular reactor may for example be a reactor such as described in Nexant PERP Report 2013-2, ’Low Density Polyethylene’, pages 31-48.
  • Such tubular reactor may for example be operated at pressures ranging from 150 to 300 MPa.
  • the tubular reactor may have a tube length of for example ⁇ 1000 m and ⁇ 5000 m.
  • the tubular reactor may for example have a ratio of length to inner diameter of ⁇ 1000:1, alternatively ⁇ 10000:1, alternatively ⁇ 25000:1, such as ⁇ 10000:1 and ⁇ 50000:1, alternatively ⁇ 25000:1 and ⁇ 35000:1.
  • the residence time in the tubular reactor may for example be ⁇ 30 s and ⁇ 300 s, alternatively ⁇ 60 s and ⁇ 200 s.
  • Such tubular reactors may for example have an inner tubular diameter of ⁇ 0.01 m and ⁇ 0.20 m, alternatively ⁇ 0.05 m and ⁇ 0.15 m.
  • the tubular reactor may for example have one or more inlet(s) and one or more outlet(s).
  • the feed composition may for example be fed to the tubular reactor at the inlet of the tubular reactor.
  • the stream that exits the tubular reactor from the outlet may for example comprise the ethylene copolymer.
  • the stream that exits the tubular reactor from the outlet may for example comprise unreacted feed composition.
  • the high-pressure free-radical polymerization process is performed in the presence of one or more free-radical initiator.
  • the free-radical initiator is selected from organic peroxides and/or azo compounds.
  • POLY0104-WO-ORD 25 [0073]
  • the free radical composition is selected from 2,5-dimethyl-2,5- di(tert-butylperoxy)hexane, t-butyl peroxy pivalate (t-BPP) and/or t-butyl peroxy benzoate (t-BPB).
  • Such initiators may for example be fed to the tubular reactor in a pure form or as a solution in a solvent.
  • solvent for example a C 2 -C 20 normal paraffin or C 2 -C 20 isoparaffin may be used.
  • such solution may comprise ⁇ 2.0% and ⁇ 65.0 % by weight of initiator, alternatively ⁇ 5.0% and ⁇ 40.0% by weight, alternatively ⁇ 10.0% and ⁇ 30.0% by weight, compared to the total weight of the solution.
  • Such initiators may for example be introduced into the polymerization reactor in quantities of ⁇ 300 ppm, preferably ⁇ 200 ppm, compared to the total weight of the materials fed to the polymerization reactor.
  • modifiers may be fed to the tubular or the autoclave reactor.
  • modifiers may include inhibitors, scavengers and/or chain transfer agents, such as alcohols, aldehydes, ketones and aliphatic hydrocarbons.
  • Such modifiers may for example be fed to the tubular reactor or the autoclave in a pure form or as a solution in a solvent.
  • the high-pressure free-radical polymerization process is performed in the presence of one or more free-radical initiator.
  • the free-radical initiator is selected from organic peroxides and/or azo compounds.
  • the polymerization is performed in the presence of a chain transfer agent (CTA) selected from the group consisting of methanol, propanal, propionaldehyde, n-heptane, propane, isopropanol and acetone.
  • CTA chain transfer agent
  • the quantity of the chain transfer agent is preferably in the range between 0.01 and 2.0 mole.%, preferably between 0.01 and 0.1 mole.%, compared to the total weight of the ethylene monomer fed to the polymerization reactor.
  • extrusion process may include co-extrusion.
  • the various resins may be first melted in separate extruders and then brought together in a feed block.
  • the feed block is a series of flow channels which bring the layers together into a uniform stream. From this feed block, this multi-layer material then flows through an adapter and out a film die.
  • the blown film die may be an annular die.
  • This ratio can be just a few percent to for example more POLY0104-WO-ORD 27 than 300 percent of the original diameter.
  • the rolls flatten the bubble into a double layer of film whose width (called the “layflat”) is equal to 1 ⁇ 2 of the circumference of the bubble.
  • This film may then be spooled or printed on, cut into shapes, and heat sealed into bags or other items.
  • cast film extrusion may be used. The process of cast film extrusion can be in accordance with “Processing Plastics” by Roy J. Crawford, Peter J. Martin, in Plastics Engineering (Fourth Edition), 2020.
  • the ethylene polymer is subjected to extrusion coating such the conditions may be used as described in the publication Crystalline Olefin Polymers, Part II, by R. A. V. Raff and K. W. Doak (Interscience Publishers, 1964), pages 478 to 484, or in Vieweg, Schley and Schwarz: Kunststoff Handbuch, Band IV, Polyolefine, Carl Hanser Verlag (1969), 20, pages 412 to 420.
  • the invention relates to an article obtained by or obtainable by the process of the present invention.
  • the invention will now be demonstrated with the following non-limiting examples.
  • the samples IE1-IE5 represents the inventive sample specimens, in accordance with the present invention while samples CE1 to CE6 derived from the ethylene polymer having properties outside the scope of the invention.
  • Preparation of the ion pair compound comprising the cationic monomer an anionic monomer [0092] In a round bottom flask having an ice bath, which contained methacrylic acid (510.9 g, 5.935 mol), 2-(dimethylamino)ethyl methacrylate (1000 mL, 5.935 mol) was added dropwise to it while maintaining the temperature below 20 °C. No purification was required and the ion pair compound was obtained at a quantitative yield (1.44 kg, 100%).
  • the melt flow index and the final content of the comonomer was controlled by adjusting the various process parameters including (i) temperature of reaction inside the reactor with the adjustment made between the monomers, (ii) concentration of chain transfer agent (CTA), and (iii) peroxide initiators added in the reactor.
  • the table below (Table 1) shows the value of the different processing conditions.
  • the total content of polymeric units (IPC) derived from the cationic monomer and the anionic monomer and melt flow index (MFI2) for the ethylene polymer was determined.
  • the reaction scheme may be shown by the diagram below - and the anionic monomer present in the ethylene polymer were determined using known techniques such as elemental analysis or 1 H NMR.
  • Extruder temperature was set from 155 to 170 °C and films with a thickness of 50 mm were prepared for each sample IE1-IE5, CE1-CE6.
  • Tensile Performance [0099] The ethylene polymer samples obtained were compression molded and the tensile tests were performed on them. [00100] Tensile test was carried out in accordance with ISO 527-1. In particular, the tensile tests were performed with a Zwick type Z020 tensile tester equipped with a 1 kN load cell. The tests were performed on film strips with dimensions of 40 mm (length) x 5 mm (height) x 0.05 mm (width). A grip-to-grip separation of 20 mm was used.
  • the samples were pre-stressed to 0.1 N and then loaded with a constant crosshead speed of 500 mm ⁇ min .
  • the Melt Flow Index (MFI 2 ) is determined in accordance with ISO1133-1:2011 at 190 oC and measured at 2.16 kg.
  • the term Melt Flow Index and Melt Flow Rate (MFR) can be used interchangeably for the purposes of the present invention.
  • the results from the above tests are reported below - Table 2.
  • the balance of properties was particularly significant for the samples IE1 and IE4 with the desired levels of tensile stress at break while maintaining tensile POLY0104-WO-ORD 31 modulus and tensile strain.
  • properties were obtained without the need of using mechanical fillers such as carbon black, glass and other equivalent fillers.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un article comprenant un polymère d'éthylène, le polymère d'éthylène comprenant ou étant constitué de : a) motifs polymères dérivés de l'éthylène ; b) motifs polymères dérivés d'un monomère cationique ; c) motifs polymères dérivés d'au moins un monomère anionique ; (i) la teneur totale en motifs polymères dérivés du monomère cationique et du monomère anionique (IPC) étant supérieure ou égale à 2,5 et inférieure ou égale à 9,0 % en poids, par rapport au poids total du polymère d'éthylène ; (ii) l'indice de fluidité (MFI2) du polymère d'éthylène étant supérieur ou égal à 0,01 et inférieur ou égal à 20,0 dg/min, MFI2 représentant l'indice de fluidité déterminé conformément à la norme ISO1133-1:2011 à 190 °C et mesuré à 2,16 kg ; et (iii) la valeur de MFI2/IPC étant supérieure ou égale à 0,01 et inférieure ou égale à 8,0, IPC et MFI2 étant tels que définis dans la description.
PCT/EP2024/084731 2023-12-11 2024-12-04 Articles contenant des ionomères à base de polyéthylène Pending WO2025125045A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018094018A1 (fr) * 2016-11-16 2018-05-24 Dow Global Technologies Llc Composition dotée d'un équilibre entre le facteur de dissipation et l'acceptation d'additif
WO2021009274A1 (fr) 2019-07-18 2021-01-21 Sabic Global Technologies B.V. Copolymère d'éthylène et composé de paire d'ions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018094018A1 (fr) * 2016-11-16 2018-05-24 Dow Global Technologies Llc Composition dotée d'un équilibre entre le facteur de dissipation et l'acceptation d'additif
WO2021009274A1 (fr) 2019-07-18 2021-01-21 Sabic Global Technologies B.V. Copolymère d'éthylène et composé de paire d'ions

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Film Extrusion Manual", 2005, TAPPI PRESS, pages: 413 - 435
R. A. V. RAFFK. W. DOAK: "Crystalline Olefin Polymers", 1964, INTERSCIENCE PUBLISHERS, pages: 478 - 484
ROY J. CRAWFORDPETER J. MARTIN: "Processing Plastics", PLASTICS ENGINEERING, 2020
SILVIA D'AURIA: "Polyethylene Based Ionomers as High Voltage Insulation Materials", ADVANCED FUNCTIONAL MATERIALS, vol. 33, no. 36, 30 May 2023 (2023-05-30), DE, XP093154876, ISSN: 1616-301X, DOI: 10.1002/adfm.202301878 *
SILVIA D'AURIA: "Polyethylene Based Ionomers as High Voltage Insulation Materials", ADVANCED FUNCTIONAL MATERIALS, vol. 33, no. 36, 30 May 2023 (2023-05-30), DE, XP093155187, ISSN: 1616-301X, DOI: 10.1002/adfm.202301878 *
VIEWEGSCHLEYSCHWARZ: "Kunststoff Handbuch", vol. 20, 1969, CARL HANSER VERLAG, article "Polyolefine", pages: 412 - 420

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