WO2024037851A1 - Utilisation d'additifs pour améliorer le traitement de polyéthylènes - Google Patents

Utilisation d'additifs pour améliorer le traitement de polyéthylènes Download PDF

Info

Publication number
WO2024037851A1
WO2024037851A1 PCT/EP2023/070833 EP2023070833W WO2024037851A1 WO 2024037851 A1 WO2024037851 A1 WO 2024037851A1 EP 2023070833 W EP2023070833 W EP 2023070833W WO 2024037851 A1 WO2024037851 A1 WO 2024037851A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
acid
tert
substituted
amino
Prior art date
Application number
PCT/EP2023/070833
Other languages
English (en)
Inventor
Daniel Mueller
Wiebke Wunderlich-Wippert
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2024037851A1 publication Critical patent/WO2024037851A1/fr

Links

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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Definitions

  • the present invention is directed to the processing of polyethylenes. Specifically, the invention concerns the use of certain additives for improving the melt strength and/or the melt elasticity and/or the drawability of a polyethylene.
  • the inventors have particularly found that one or more of these properties are improved in regard to extrusion techniques, for instance film and fibre preparation, especially blown polyethylene film production. Improvements have been found particularly for mono- and biaxial orientated polyethylene films (BOPE).
  • BOPE mono- and biaxial orientated polyethylene films
  • Polyethylene can be used in a wide variety of applications. Typically, this can include a number of different articles such as films, extrudates and pipes and many more. Different types of polyethylenes can be produced by a number of processes including low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high density polyethylene (HDPE).
  • LDPE low density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE high density polyethylene
  • Polyethylene may for instance be processed by blown moulding, blown film or by the extrusion techniques.
  • properties such as melt strength and melt elasticity are often important.
  • Properties such as drawability can also be important during the processing of polyethylene, especially when producing fibres, typically as spun melt or continuous filament, or when producing blown films, typically involving extrusion of the polyethylene through a blown film extruder machine.
  • US 2011/0171407 A1 discloses a method for increasing the melt strength of a polyethylene resin by reacting the polyethylene resin with an alkoxy amine derivative of the formula: (R1) (R2) N - O - R3 where R1 and R2 are each independently of one another hydrogen, C4-C42 alkyl or C4-C42 aryl or substituted hydrocarbon groups comprising O and/or N, and where R1 and R2 may form a ring structure together; and where R3 is hydrogen, a hydrocarbon or a substituted hydrocarbon group comprising O and/or N.
  • melt strength is a practical measurement that can predict material performance when submitted at elongational deformations.
  • US 10865298 B2 describes a composition that includes polyethylene, a multifunctional co-agent having a functionality of 3 or greater, where the multifunctional co-agent is from 100 to 2000 ppm based upon the polyethylene, and a free radical generator, where the fee radical generator is from 5 to 100 ppm based upon the polyethylene.
  • This reference describes that in addition to an improved gel count, high melt strengths may be desirable for polyethylene.
  • US 10844210 B2 teaches a method for increasing the melt strength and/or low shear viscosity of a polyethylene resin.
  • the method comprises: a) providing a first polyethylene resin having a density ranging from 0.900 g/cm 3 to 0.970 g/cm 3 , a melt index ranging from 0.01 g/10 min to 30 g/10 min, and at least 0.20 vinyl groups per 1000 total carbons; b) providing a masterbatch composition comprising a free radical generator and a second polyethylene resin.
  • the free radical generator has a half-life at 220°C, of less than 200 seconds, and a decomposition energy higher than -250 kJ/mol.
  • the second polyethylene has a density ranging from 0.900 g/cm 3 to 0.970 g/cm 3 , melt index ranging from 0.01 g/10 min to 100 g/10 min.
  • the first polyethylene resin is reacted with the masterbatch composition to form a modified polyethylene resin.
  • WO 2014/043184 A1 relates to a film structure comprising an outer layer, a core and an inner layer (or sealant layer).
  • the outer layer comprises a polyolefinic material having a Vicat softening temperature of 85°C or greater, most preferably 90°C or greater, and a total crystallinity in the range of 25 to 45%.
  • the core is a linear low- density polyethylene having a density of 0.925 g/cm 3 or less, and a melt index of 4.0 g/10 min or less.
  • the inner layer (or sealant layer) comprises linear low-density polyethylene having a density of from 0.865 to 0.926 g/cm 3 and a melt index of less than 4.0/10 minutes.
  • the films are said to be further characterised by having the total amount of polyethylene having a density of 0.930 g/cm 3 or greater which makes up the film being of less than 25% by weight of the entire film.
  • the description reveals that the core may comprise a single layer or, more preferably, multiple layers, with additional layers adding functionality such as barrier properties, melt strength or additional toughness depending on the intended application for the film.
  • nucleating agents may in this context be referred to as clarifying agents.
  • WO 2007/039471 A1 describes a process for improving the flow properties of a melt containing a thermoplastic polymer.
  • the process comprises incorporating 0.005% to 0.5% by weight, relative to the weight of the thermoplastic polymer, of one or more additives selected from the group consisting of organic and inorganic compounds with needle-like morphology in their solid-state into the thermoplastic polymer prior to or during melt processing.
  • the disclosure describes employing an additive which is an organic compound containing polar moieties and shielding nonpolar hydrophobic groups on the outer molecule sphere.
  • the reference proposes as the additive a range of different multiple amide derivatives of aliphatic or aromatic polycarboxylic acids; multiple amide derivatives of aliphatic or aromatic polyamines; multiple amide derivatives of aliphatic or aromatic amino carboxylic acids; and sorbitol acetals.
  • EP 1674447 B1 discloses amide mixtures, polyolefin resin compositions and polyolefin resin moulded products. This document refers to an objective of providing a mixture of amide compounds which has improved thermal stability and alkali resistance, and which can produce a moulded product with further improved transparency, crystallizability (heat resistance) and rigidity.
  • the reference is directed to a mixture of at least two amide based compounds having the general formula R 1 - (CONHR 2 ) a , where a represents an integer of 2 to 6; R 1 is an aliphatic polycarboxylic acid; R 2 is a trans-2-alkylcyclohexylamine residue or a cis-2-alkylcyclohexylamine residue in which the trans-2-alkylcyclohexylamine residue accounts for at least 70% by mole of all of the 2-alkylcyclohexylamine residues contained in the mixture.
  • the reference further describes a polyolefin resin composition containing the aforesaid mixture and mouldings of the compositions.
  • EP 2204408 A1 concerns a polyolefin having a high crystallisation temperature which is described as having excellent transparency.
  • the polyolefin composition comprises 0.01 to 10 parts by mass of a methylenebisanilide compound.
  • US 9278487 B1 discloses an extruded air-cooled blown film having a) a total thickness of 5 to 500 pm, b) a monolayer structure of 2 to 9 co-extruded layers, c) at least one layer containing a polymer selected from polypropylene homopolymers, polypropylene random copolymers, hetero phasic polypropylene block polymers, or any mixtures, and optionally d) a modulus according to EN ISO 527 enhanced by at least 10% versus a reference film without the nucleating agent.
  • the polymer of the at least one layer has a melt flow rate, according to ASTM D-1238, of 0.1 to 10 dg/min at 230°C and 2.16 kg.
  • the layer further contains 0.001 to 2%, relative to the weight of the polymer, of a particular nucleating agent.
  • the nucleating agents include compounds having 2 to 6 amide groups based on polycarboxylic acids, polyamines or amino carboxylic acids.
  • the disclosure refers to clarified films containing polypropylene as principal component and improved stiffness of the blown films without impairing their elasticity.
  • WO 2017/156099 relates to trisamide compounds and compositions containing them.
  • the trisamide compounds are based on benzenetrisamides in which at least one of the amide groups has a cyclohexyl substituent. They can be employed as functional substances for use with a broad range of materials, including glassy and semi crystalline polymers, elastomers, rubbers, thermosets. These trisamide compounds can be used by themselves or in combination with other functional substances and are said to enhance thermal, optical, electrical, cosmetic and other characteristics, mechanical properties of materials to which they are applied.
  • the composition preferably includes a polymer which is a thermoplastic polymer, such as a polyolefin, polyester, polyamides, polylactic acid, polycarbonate, acrylic polymer, or mixtures.
  • a polymer which is a thermoplastic polymer, such as a polyolefin, polyester, polyamides, polylactic acid, polycarbonate, acrylic polymer, or mixtures.
  • the preferred polymer is a polyolefin polymer such as polypropylene polymer, a polyethylene polymer, polymethylpentene polymer, a polybutylene polymer, a poly (vinyl cyclohexane) polymer.
  • WO 2012/045288 discloses a method of preparing nucleated semi-crystalline polyolefin by coordination polymerization.
  • the nucleating agent is dosed in the form of the suspension or the solution in a nonpolar hydrocarbon solvent or in concentrated organoaluminium as part of the catalyst system for the alpha-olefin polymerization.
  • Suitable nucleating agents include compounds based on benzene trisamides.
  • the reference describes polymer suitable for in situ nucleation involves ethylene and propylene homopolymers as well as mutual copolymers.
  • WO 2004/072168 describes a composition containing a) a natural or synthetic polymer and b) one or more compounds based on benzene trisamide structures.
  • the compositions are said to have excellent crystallizability, high transmittance, low haze and/or improved thermal stability.
  • Examples of synthetic polymers are said to be polymers of monoolefins preferably being polyethylene and polypropylene.
  • An objective of the present invention is to provide improvements to melt strength and/or melt elasticity and/or the drawability of polyethylenes.
  • Such improvements are desirable for mono and biaxial orientated polyethylene films (BOPE).
  • an additive for increasing the melt strength and/or melt elasticity and/or the drawability of a polyethylene, wherein the additive is selected from at least one compound selected from the group consisting of bisamides, trisamides, tetraamides and sorbitol acetals.
  • the invention also provides a method for increasing the melt strength and/or melt elasticity and/or the drawability of polyethylene by adding an additive to the polyethylene, wherein the additive is selected from the group consisting of bisamides, trisamides, tetraamides and sorbitol acetals.
  • an additive selected from the group consisting of bisamides, trisamides, tetraamides and sorbitol acetals.
  • the polyethylene may be any of ultrahigh molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE or PE-WAX), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), high density cross-linked polyethylene (HDXLPE), cross-linked polyethylene (PEX or XLPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE) or chlorinated polyethylene (CPE).
  • UHMWPE ultrahigh molecular weight polyethylene
  • ULMWPE or PE-WAX high molecular weight polyethylene
  • HMWPE high density polyethylene
  • HDXLPE high density cross-linked polyethylene
  • PEX or XLPE cross-linked polyethylene
  • MDPE medium density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • VLDPE very low density polyethylene
  • CPE chlorinated polyethylene
  • the polyethylene has a density of from 0.915 to 0.960 g/cm 3 , preferably from 0.915 to 0.950 g/cm 3 .
  • the polyethylene may be an ultrahigh molecular weight polyethylene (UHMWPE).
  • UHMWPE ultrahigh molecular weight polyethylene
  • Such UHMWPE may have a molecular weight of several million, for instance from 3.5 to 7.5 million g/mol.
  • the density tends to be less than high density polyethylene and may be in the range of from 0.930 to 0.935 g/cm 3 .
  • High density polyethylene may also be processed in accordance with the present invention, especially if the density does not exceed 0.960 g/cm 3 .
  • HDPE has a density of greater than 0.941 g/cm 3 .
  • Another suitable polyethylene which may be processed according to the present invention includes low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • Low density polyethylene may be characterised by having a high degree of short and long chain branching.
  • LDPE may have a density in the range of from 0.910 to 0.940 g/cm 3 .
  • the density would be in the range of from 0.915 to 0.940 g/cm 3 .
  • the polyethylene employed in accordance with the present invention may be a medium density polyethylene (MDPE).
  • MDPE medium density polyethylene
  • MDPE may have a density in the range of from 0.926 to 0.940 g/cm 3 .
  • the polyethylene is a linear low-density polyethylene (LLDPE).
  • LLDPE linear low-density polyethylene
  • LLDPE may be characterised by being a substantially linear polymer but can have numerous short branches.
  • the density of LLDPE is typically in the range of from 0.915 to 0.925 g/cm 3 .
  • the additive is desirably a bisamide, a trisamide or a tetraamide of any of the formulae (IA), (IB), and (IC) wherein x and y are 2 or 3 or 4; z’ and z” independently of one another are 1 or 2 or 3 with the proviso that the sum of z’ and z” is either 2 or 3 or 4;
  • Xo is a residue which is formed by elimination of x carboxyl groups of a saturated or unsaturated aliphatic polycarboxylic acid having 3 to 25 carbon atoms, a residue which is formed by elimination of x carboxyl groups of a saturated or unsaturated alicyclic polycarboxylic acid having 7 to 25 carbon atoms or a residue which is formed by elimination of x carboxyl groups of an aromatic polycarboxylic acid having 8 to 25 carbon atoms; any of said polycarboxylic acids optionally contains further hetero atoms in its skeleton; the radicals Xi independently of one another are
  • Yo is a residue which is formed by elimination of y amino groups of a saturated or unsaturated aliphatic polyamine having 3 to 25 carbon atoms, a residue which is formed by elimination of y amino groups of a saturated or unsaturated alicyclic polyamine having 6 to 25 carbon atoms or a residue which is formed by elimination of y amino groups of an aromatic polyamine having 6 to 25 carbon atoms; any of said polyamines optionally contains further hetero atoms in its skeleton;
  • Zo is a residue which is formed by elimination of z' amino groups and z" carboxyl groups of an unsaturated or saturated aliphatic amino carboxylic acid having 2 to 25 carbon atoms, a residue which is formed by elimination of z' amino groups and z" carboxyl groups of a saturated or unsaturated alicyclic amino carboxylic acid having 7 to 25 carbon atoms or a residue which is formed by elimination of z' amino groups and z" carboxyl groups of an aromatic amino carboxylic acid having 7 to 25 carbon atoms; any of said amino carboxylic acids optionally contains further hetero atoms in its skeleton; the radicals Z1 and Z2 independently of one another have the same definition given for Xi.
  • Examples of a saturated or unsaturated aliphatic polycarboxylic acid having 3 to 25, preferably 3 to 16, in particular 4 to 12, carbon atoms and x carboxyl groups and optionally containing further hetero atoms in its skeleton are malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 ,12-dodecanedioic acid, 1 ,14-tetradecanedioic acid, 1 ,18-octadecanedioic acid, citric acid, methanetricarboxylic acid, tricarballylic acid, propenetricarboxylic acid, pentanetricarboxylic acid, ethanetetracarboxylic acid, propanetricarboxylic acid (
  • Examples of a saturated or unsaturated alicyclic polycarboxylic acid having 7 to 25, preferably 8 to 16, carbon atoms and x carboxyl groups and optionally containing further hetero atoms in its skeleton are 1 ,2-cyclohexane dicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cy clo hexa netetra carb oxy lie acid, tetrahydrofurantetracarboxylic acid, 5-(succinic acid)-3-methyl-3-cylohexene-1 ,2- dicarboxylic acid, bicyclo[2,2,2]octa-7-ene-2,3,5,6-tetracarboxylic acid, 5,6,9,10- tetracar
  • Examples of an aromatic polycarboxylic acid having 8 to 25, preferably 8 to 22, in particular 8 to 17, carbon atoms and x carboxyl groups and optionally containing further hetero atoms in its skeleton are p-phenylenediacetic acid, p- phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1 ,8- naphthalic acid, 1 ,4- naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, diphenic acid, 3,3'-biphenyldicarboxylic acid, 4,4'- biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis(3- carboxyphenyl)methane, bis(4-carboxyphenyl
  • linear or branched alkyl having up to 20 carbon atoms and being optionally substituted by one or more hydroxy, amino and/or nitro groups are ethyl, n-propyl, 1 -methylethyl, n-butyl, 2-methylpropyl, 1 -methyl propyl, tert-butyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1 -dimethylpropyl, 1- ethylpropyl, tert-butyl methyl, hexyl, 1 -methylpentyl, heptyl, isoheptyl, 1- ethylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, isononyl, neononyl, 2,4,4- trimethylpentyl, undecyl, tridecyl, pentadecyl
  • Branched C 3 -Cioalkyl is particularly preferred.
  • One of the preferred meanings of the radicals Xi, Yi, Zi and Z2 is branched C3-C10 alkyl with a quaternary C atom in position 1 , in particular -C(CHs)2-H or -C(CH 3 )2-(Ci-C 7 alkyl).
  • C 2 -C 2 oalkyl interrupted by oxygen or sulfur are t-butoxym ethyl, t- butoxyethyl, t-butoxypropyl, t-butoxybutyl, (H 3 C) 3 C-S-CH 2 -, (H 3 C) 3 C-S-C 2 H 4 -, (H 3 C)3C-S-C 3 H5- and (H 3 C) 3 C-S-C 4 H 8 -.
  • Ci-Csalkoxy examples are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy. Methoxy is particularly preferred.
  • Ci-Csalkylthio examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio and octylthio.
  • Ci-Csalkylsulfoxy examples are methylsulfoxy, ethylsulfoxy, propylsulfoxy, butylsulfoxy, pentylsulfoxy, hexylsulfoxy, heptylsulfoxy and octylsulfoxy.
  • Ci-C 2 oalkenyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups are 9-decenyl, 8-heptadecenyl, 11-hydroxy-8- heptadecenyl and 11-amino-8-heptadecenyl.
  • Ci- C 2 oalkyl unsubstituted or substituted by one or more Ci- C 2 oalkyl, e.g. 1 , 2, 3 or 4 Ci-C 4 alkyl, are cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4- tert-butylcyclohexyl and cycloheptyl.
  • Ci-C 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
  • Ci-C 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
  • Ci-C 2 oalkyl examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g.
  • phenyl-Ci-C 2 oalkyl unsubstituted or substituted by one or more radicals selected from Ci-C2oalkyl, C3-Ci2cycloalkyl, phenyl, Ci-C2oalkoxy, amino, hydroxy and nitro, preferably Ci-C4alkyl, Cs-Cscycloalkyl, phenyl, Ci-C4alkoxy and hydroxy, are benzyl, a-cyclohexylbenzyl, diphenylmethyl, 1 -phenylethyl, a- hydroxybenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 3-methylbenzyl, 3,4-dimethoxybenzyl and 2-(3,4-dimethoxyphenyl)ethyl.
  • phenylethenyl unsubstituted or substituted by one or more Ci- C 2 oalkyl e.g. 1 , 2 or 3 C1-C4alkyl
  • 2-(4-methylphenyl)ethenyl is 2-(4-methylphenyl)ethenyl.
  • biphenyl-(Ci-C 10 alkyl) unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, is 4-biphenylmethyl.
  • Examples of naphthyl unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are 1 -naphthyl and 2-naphthyl.
  • Examples of naphthyl-Ci-C 20 alkyl unsubstituted or substituted by one or more Ci- C 20 alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are 1 -naphthylmethyl and 2-naphthylmethyl.
  • Ci- C 20 alkyl e.g. 1 , 2 or 3 Ci-C4alkyl
  • Ci- C 20 alkyl e.g. 1 , 2 or 3 Ci-C4alkyl
  • biphenylenyl, fluorenyl or anthryl is 2-biphenylenyl, 9-fluorenyl, 1- fluorenyl or 9-anthryl, respectively.
  • Examples of a 5- to 6-membered heterocyclic radical unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are 3-pyridinyl, 4-pyridinyl, 2-hydroxypyridin-3-yl, 3-quinolinyl, 4-quinolinyl, 2-furyl, 3-furyl and 1-methyl-2- pyrryl.
  • Ci-C 20 hydrocarbon radical containing one or more halogen or pseudo halogen e.g. 1 , 2, 3, 4, 5, or 6 -F, -Cl or -I
  • halogen or pseudo halogen e.g. 1 , 2, 3, 4, 5, or 6 -F, -Cl or -I
  • tri(Ci-Ci O alkyl)silyl is (H 3 C)3Si-.
  • tri(Ci-Cioalkyl)silyl(Ci-Cioalkyl) is (HsC)3Si-(CH2)2-.
  • Examples of a saturated or unsaturated aliphatic polyamine having 3 to 25 carbon atoms and y amino groups and optionally containing further hetero atom in its skeleton are 1 ,3-diaminopropane, 1 ,4-diaminobutane and 1 ,5- diaminopentane.
  • Examples of a saturated or unsaturated alicyclic polyamine having 6 to 25, preferably 6 to 13, carbon atoms and y amino groups and optionally containing further hetero atom in its skeleton are 1 ,2-diaminocyclohexane, 1 ,4- diaminocyclohexane, 4,4'-diaminodicyclohexyl, 4,4'-diamino-3,3'- dimethyldicyclohexyl, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3' dimethyldicyclohexylmethane, 1 ,3-bis(aminomethyl)cyclohexane, 1 ,4- bis(aminomethyl)cyclohexane, isophoronediamine, menthenediamine, melamine, 1 ,3,5-triaminocyclohexane, 1 ,2,4-triaminocyclohexan
  • Examples of an aromatic polyamine having 6 to 25, preferably 6 to 17, in particular s to 13, carbon atoms and y amino groups and optionally containing further hetero atoms in its skeleton are o-phenylenediamine, m- phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4- diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 4,6-dimethyl-m- phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5-dimethyl-o- phenylenediamine, 2,4-diaminomesitylene, 2,3-diaminopyridine, 2,6- diaminopyridine, 3,4-diaminopyridine, 1 ,5-diaminonaphthalene, 1 ,8- diaminonaphthalene, 2,3-
  • Examples of an unsaturated or saturated aliphatic amino carboxylic acid having 2 to 25, preferably 2 to 12, in particular 2 to 5, carbon atoms, z' amino groups and z" carboxyl groups and optionally containing further hetero atoms in its skeleton are aminoacetic acid, alpha-aminopropionic acid, beta-aminopropionic acid, alpha-aminoacrylic acid, alpha-aminobutyric acid, beta-aminobutyric acid, gamma-aminobutyric acid, alpha-amino-alpha-methylbutyric acid, gamma- amino-alpha-methylbutyric acid, alpha-aminoisobutyric acid, beta aminoisobutyric acid, alpha-amino-n-valeric acid, delta-amino-n-valeric acid, beta-aminocrotonic acid, alpha-amino-beta-methylvaleric acid, alphaaminoisovaleric acid, 2-amino
  • Examples of a saturated or unsaturated alicyclic amino carboxylic acid having 7 to 25, preferably 7 to 9, carbon atoms, z' amino groups and z" carboxyl groups and optionally containing further hetero atoms in its skeleton care 1 -aminocyclohexanecarboxylic acid, 2- aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4- aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, 3,5- diaminocyclohexanecarboxylic acid, 1-amino-1 ,3-cyclohexanedicarboxylic acid and the like.
  • Examples of an aromatic amino carboxylic acid having 7 to 25, preferably 7 to 15, in particular 7 to 11 , carbon atoms, z' amino groups and z" carboxyl groups and optionally containing further hetero atoms in its skeleton are alphaaminophenylacetic acid, alpha-amino-beta-phenylpropionic acid, 2-amino-2- phenylpropionic acid, 3-amino-3-phenylpropionic acid, alpha-amino cinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-amino-3- methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino
  • halogen or pseudo-halogen are -F, -Cl, -Br, -I, -CN, -CNO, -OCN, - SCN and -CNS.
  • the additive is a trisamide or a tetraamide according to formula (IA).
  • x is an integer of 3 or 4;
  • Xo is a residue obtained by removing all of the carboxyl groups from 1 ,2,3- propanetricarboxylic acid or 1 ,2,3,4-butanetetracarboxylic acid;
  • Xi is represented by the formula (ID) and the three or four X2S are the same or different, and each independently represent a hydrogen atom or a C1-C10, linear or branched alkyl group.
  • Examples of a C1-C10, linear or branched alkyl group include methyl, ethyl, n-propyl, 1- methylethyl, n-butyl, 2-methylpropyl, 1 -methylpropyl, tert-butyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1 -dimethylpropyl, 1 -ethylpropyl, tertbutylmethyl, hexyl, 1 -methylpentyl, heptyl, isoheptyl, 1 -ethylhexyl, 2-ethylpentyl, 1 -propylbutyl, octyl, nonyl, isononyl, neononyl and 2,4,4-trimethylpentyl.
  • the additive is an aromatic bisamide, an aromatic trisamide or an aromatic tetraamide.
  • the additive is a bisamide, a trisamide or a tetraamide according to any of the formulae (IA), (IB), and (IC).
  • x, y or the sum of z’ and z” are 2
  • Xo, Yo, and Zo are the group of the formula (II), (III), (IV A) or (IV B) wherein R represents a hydrogen atom, C1-C4 alkyl which is optionally substituted or branched, C3-C12 cycloalkyl which is optionally substituted, or C6-C20 aryl which is optionally substituted.
  • C1-C4 alkyl examples include methyl, ethyl, n-propyl, 1 -methylethyl, n-butyl, 2- methylpropyl, 1 -methylpropyl and tert-butyl.
  • C3-Ci2cycloalkyl optionally substituted examples include cyclopropyl, 3-methylcyclopropyl, 2, 2,3,3- tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1 -methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-m ethylcyclohexyl, 4-tert- butylcyclohexyl and cycloheptyl.
  • C6-C20 aryl which is optionally substituted include phenyl, 3-methylphenyl, 3-methoxyphenyl, 4-methylphenyl, 4- ethylphenyl, propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4- isopropoxyphenyl, 2,3-dimethoxyphenyl, 2-nitrophenyl, 3-methyl-6-nitrophenyl, 4- dimethylaminophenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,4- dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl and 3,5-di-tert-butyl-4- hydroxyphenyl, benzyl, 0 cyclohexyl benzyl, diphenylmethyl, 1 -phenylethyl, a-phen
  • One group of particularly suitable additives is aromatic bisamides based on formula (VI): wherein R1 and R2 are each independently selected from C1-C5 linear or branched alkyl or substituted or unsubstituted C3-C6 cycloalkyl, preferably R1 and R2 both being tertiary butyl. In this case, R1 and R2 represent each Y1 of formula (IB).
  • One preferred compound according to formula (II) is the compound of formula (XI).
  • One preferred compound according to formula (VI) is the compound of formula (XII).
  • One preferred compound according to formula (IV A) is the compound of formula (XIII).
  • Another preferred compound according to formula (IV A) is the compound of formula (XIV).
  • the additive is a trisamide according to any of the formulae (IA), (IB), and (IC).
  • x, y or the sum of z’ and z” are 3, Xo, Yo, and Zo are the group of the formula (V)
  • More preferred embodiments according to formula (V) include compounds according to the structures (V A), (V B), (V C) or (V D).
  • the additive is a bisamide or a trisamide of formula (IB) wherein when the additive is a bisamide Yo is represented by formula (III) or formula (II) and when the additive is a trisamide Yo is represented by formula (V). More preferably, the additive is a trisamide of formula (IB) wherein Yo is represented by formula (V). It is particularly preferred that the additive is an aromatic trisamide of formula (VII), in which R1 , R2 and R3 each independently selected from C1-C5 linear or branched alkyl or substituted or unsubstituted C3-C6 cycloalkyl, preferably R1 , R2 and R3 all being tertiary butyl. In this case, R1 , R2 and R3 represent each Y1 of formula (IB).
  • R1 is a substituted cyclohexyl group.
  • R1 has the structure shown in formula (VII A):
  • W may be selected from C1-C10 linear or branched substituted or unsubstituted alkyl and may be in any substitution position of the cyclohexyl group, preferably in the para-position.
  • R2 and R3 would have the same definitions given for the structure of formula (VII).
  • W is located in the para- position and is in the cis-position relative to the bond of the carbonyl carbon attached to the cyclohexanediyl ring.
  • W is located in the para-position and is in the trans-position relative to the bond of the carbonyl carbon attached to the cyclohexanediyl ring.
  • R2 has independently of R1 the same definition as ascribed to R1 as represented by formula (VII A).
  • both R2 and R3 independently of each other and R1 have the same definition as ascribed to R1 as represented by formula (VII A).
  • the additive is an aromatic trisamide having the formula (VII B): wherein each V group is independently selected from C1-C5 linear or branched alkyl, preferably C3 or C4 branched alkyl, more preferably the V groups all being tertiary butyl.
  • One specific suitable compound according to formula (VII B) is 1 ,3,5-tris[cis-4-tert- butylcyclohexylcarbonylamino]benzene, illustrated by formula (XV):
  • a further specific suitable compound according to formula (VII B) is cis-4-tert- butylcyclohexylcarbonylamino-3,5-bis[trans-4-tert-butylcyclohexylcarbonylamino] benzene, illustrated by formula (XVII):
  • a still further specific suitable compound according to formula (VII B) is 1 , 3, 5- tris[trans-4-tert-butylcyclohexylcarbonylamino] benzene, illustrated by formula
  • Additional specific suitable compounds according to formula (VII B) are 1 ,3,5-tris[cis- 4-iso-propycyclohexylcarbonylamino]benzene, trans-4-iso- propylylcyclohexylcarbonylamino-3,5-bis [cis-4-iso-propylcyclohexylcarbonylamino] benzene, trans-4-iso-propylcyclohexylcarbonylamino-3,5-bis [cis-4-iso-propyl cyclohexylcarbonylamino] benzene and 1 , 3, 5-tris[trans-4-iso-propylcyclohexyl carbonylamino] benzene.
  • the additive may desirably be a sorbitol acetal.
  • the sorbitol acetal is a compound based on formula (VIII): wherein p is zero or 1 ; m and n independently of one another are an integer from 0 to 3; each radical R independently one another are Ci-Cs alkyl, Ci-Cs alkoxy, hydroxy, halogen, pseudo-halogen, Ci-Cs alkylthio, Ci-Cs alkylsulfoxy or 2 radicals R form together with two adjacent carbon atoms of the unsaturated parent ring a 5 to 7 membered carbocyclic or heterocyclic ring and R1 is selected from hydrogen or Ci- C3 alkyl.
  • halogen or pseudo-halogen examples include -F, -Cl, -Br, -I, -CN, -CNO, - OCN, -SCN and -CNS.
  • a compound according to formula (VIII) includes two radicals R forming together with two adjacent carbon atoms of the unsaturated parent ring a 5 to 7-membered carbocyclic or heterocyclic ring is represented by formula (XX):
  • the additive may be added to the polyethylene melt in any suitable amount.
  • the polyethylene comprises the additive in an amount of from 0.001 to 1 .0%, suitably from 0.002 to 0.75% weight of additive to weight of polyethylene, preferably from 0.005 to 0.5%.
  • One particularly suitable range may for instance be from 0.005 to 0.05%.
  • Another particularly suitable range may be for instance from 0.05 to 0.5%.
  • Bisamides, trisamides and tetraamides may suitably be added in any of these ranges.
  • bisamides, trisamides and tetraamides may be added in the range from 0.005 to 0.1 % more preferably from 0.005 to 0.02%.
  • Sorbitol acetals may suitably be added in any of these ranges.
  • sorbitol acetals may be added in the range from 0.1 to 0.6%, more preferably from 0.15 to 0.5%.
  • the polyethylene produced according to the present invention may be produced as a polyethylene film, a polyethylene fiber or other articles of polyethylene.
  • the polyethylene produced according to the present invention is a polyethylene film.
  • the polyethylene melt may optionally contain one or more co-additives commonly used in the plastics’ industry.
  • co-additives may be at least one selected from the group consisting of UV absorbers and light stabilisers; antioxidants; vis-breaking agents; metal deactivators; phosphites and phosphonites; nitrones; thiosynergists; peroxide scavengers; basic co-stabilisers; nucleating agents; fillers and reinforcing agents; other additives; and benzofuranones and indolinones.
  • co- additives include slip additives, acid scavengers, for instance as described in Chapter 4 of the Plastic Additives Handbook; lubricants, for instance as described in Chapter 5 of the Plastic Additives Handbook polymer processing aids, for instance as described in Chapter 6 of the Plastic Additives Handbook; anti blocking additives, for instance as given in Chapter ? of the Plastic Additives Handbook; and antifogging additives, for instance as given in Chapter 9 of the Plastic Additives Handbook.
  • slip additives for instance as described in Chapter 4 of the Plastic Additives Handbook
  • lubricants for instance as described in Chapter 5 of the Plastic Additives Handbook
  • polymer processing aids for instance as described in Chapter 6 of the Plastic Additives Handbook
  • anti blocking additives for instance as given in Chapter ? of the Plastic Additives Handbook
  • antifogging additives for instance as given in Chapter 9 of the Plastic Additives Handbook.
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2- tert-butyl-4,6-di methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4- n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4- methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl phenol, 2,6-dioctadecyl-4- methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-T
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert- butylphenol, 2,4-dioctyl thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6- ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert- butyl-4-methoxy phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert- amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert- butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
  • 2,6-di-tert- butyl-4-methoxy phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert- amylhydroquinone, 2,6-diphen
  • Tocopherols for example a-tocopherol, -tocopherol, y-tocopherol, o- tocopherol and mixtures thereof (vitamin E).
  • 1 .5. Hydroxylated thiodiphenyl ethers for example 2'-thiobis(6-tert-butyl-4- methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3- methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec- amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4- methylphenol), 2,2'methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4- methyl-6-(a-methylcyclohexyl) phenol], 2,2'-methylenebis(4-methyl-6- cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'- methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a- methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-
  • N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl- 4,4'-dihydroxydi benzyl ether, octadecyl-4-hydroxy-3,5- dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert- butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl- 4-hydroxy- benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4- hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl-2, 2-bis(3, 5- di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate, di dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4- hydroxybenzyl)malonate, bis[4-( 1 , 1 ,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di- tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1 , 3, 5-tris(3, 5-di-tert- butyl-4-hydroxy benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4- hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert- butyl-4-hydroxy anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-1 ,3,5-tri azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy)-
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3- methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3, 5-di-tert- butyl-4-hydroxybenzylphosphonic acid.
  • esters of 13-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3- thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4- hydroxymethyl-1-phospha-2,6,7-trio
  • esters of 13-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly hydric alcohols e.g. with methanol, ethanol, n-octanol, i- octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- triox
  • esters of 13-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]oct
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy droxym ethyl- 1- phospha-2,6,7-trioxabicyclo
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p- phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'- bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p phenylenediamine, N- isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-
  • 2-(2'-Hydroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'- methylphenyl)-benzo triazole, 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2- (2'-hydroxy-5'-(1 , 1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(2' hydroxy-4'
  • R 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a- dimethylbenzyl)-5'-(1 , 1 ,3,3-tetramethylbutyl)-phenyl] benzotriazole; 2-[2'- hydroxy-3'-(1 , 1 ,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)-phenyl]ben zotriazole.
  • Esters of substituted and unsubstituted benzoic acids for example 4- tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert- butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4- hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis[4-(1 , 1 ,3,3- tetramethyl butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n butylamine, triethanolamine or N- cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert butylbenzylphosphonic acid, nickel complexes of ketoxi mes, e.g. of 2-hydroxy-4- methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5- hydroxypyrazole, with or with out additional ligands.
  • additional ligands such as n butylamine, triethanolamine or N- cyclohexyldiethanol
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 , 2, 2,6,6- pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4- piperidyl) n-butyl-3,5-di-tert- butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert octyla
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'- diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3- dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p- methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'- salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • N,N'-diphenyloxamide
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4- methylphenyl)pentaerythritol diphos
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos®168, BASF SE), tris(nonylphenyl) phosphite,
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N- diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N dihexadecylhydroxylamine, N,N- dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox ylamine, N- heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine or derived from vegetable source.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha- methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N- tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecylnitrone, N- octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N- ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta decylnitrone, N- octadecyl-alpha-hexadecylnitrone, nitrone derived from
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3- (dodecylthio)propionate] or distearyl disulfide.
  • Peroxide scavengers for example esters of -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(p -dodecylmercapto)propionate.
  • esters of -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis(p -dodecyl
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4- tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4- tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copoly
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • Other additives may also include anti-block additives, as referred to above, which are used in films to reduce the negative adhesion of two polyethylene surfaces to one another which would otherwise result in difficulties separating the films.
  • Further additives include slip additives, as referred to above, which are used to help the film surfaces slide over each other.
  • Antifogging agents as referred to above, may also be added.
  • Benzofuranones and indolinones for example those disclosed in U.S. 4,325,863; U.S.
  • Vis-breaking agents or generally radical initiators typically, this includes organic or inorganic peroxides, which are widely used in industry, bis azo compounds,
  • Suitable peroxides as vis-breaking agents include 2,5-dimethyl-2,5-di(t- butylperoxy)hexane, 2,5- dimethyl-2,5-di(t-butylperoxy)hexyne-3, 3, 6, 6,9,9- pentamethyl-3-(ethyl acetate)-1 ,2,4,5- tetraoxy cyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyldiperoxide, t-butyl cumyl peroxide; t-butyl hydroxyethyl peroxide, di-t- amyl peroxide and 2,5- dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulphon
  • Such azo compounds are for example 2,2'-azobisisobutyronitrile, 2,2'-azobis(2- methylbutyronitrile ), 2,2'-azobis(2,4-dimethylvaleronitrile ), 2,2'-azobis( 4-methoxy- 2,4-dimethylvaleronitrile ), 1 , 1 '-azobis(1 -cyclohexanecarbonitrile ), 2,2'- azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl 2,2'-azobisisobutyrate, 2-( carbamoylazo )isobutyronitrile, 2,2'-azobis(2,4,4- trimethylpentane ), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'- dimethyleneisobutyramidine) as free base or hydrochloride, 2,2'azobis(2- amidinoprop
  • the co-additive is for example present in the polymer melt in an amount of 0.001 to 10 % by weight, preferably 0.001 to 5 % by weight, relative to the weight of the polyethylene.
  • Conventional fillers or reinforcing agents may be present in the polymer melt in amounts of 0.1 to 10 % by weight, preferably 1 to 5 % by weight, in certain cases in amounts up to 70 % by weight, relative to the weight of the polyethylene.
  • the test temperature was 230°C.
  • the sample was drawn uniaxial ly to a set of accelerating nips located 100 mm below the die, with an acceleration of 2.4 mm/s2.
  • the tensile force (cN) was recorded as a function of the take-up speed of the nip rolls. The higher the value the better improvement in terms of melt strength.
  • Drawability was reported as the maximum ratio of drawing versus initial extrusion rate v/vo before appearance of draw resonance as an indication for draw turbulences and limit for increased throughput. Melt strength is the plateau force before the strand breaks. The higher the ratio v/vo (draw speed I initial extrusion speed at time zero) the better.
  • Example 1 LLDPE Exxonmobil LL 1002YB Cast, ground
  • F35 MTU highspeed mixer F35 MTU from the company MTI in Germany.
  • the mixtures were compounded at 230°C with a double screw compounding unit 25/42D from Collin in Germany to get well homogenized granules.
  • 120micron films were produced on a Colling Cast film line CR 136 / 230 at 230°C.
  • the films were drawn offline on a MDO stretch line, Type MDO-ll-350 from Collin in Germany.
  • the films were stretched at 75°C in two steps with stretch factor 1 :2 in first stretch and with continuous increase in stretch factor in step 2. The total stretch achieved before break was noted down.

Landscapes

  • 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

La présente invention concerne des améliorations dans le traitement de polyéthylènes. L'invention concerne spécifiquement une utilisation d'un additif pour augmenter la résistance à l'état fondu et/ou l'élasticité à l'état fondu et/ou l'aptitude à l'étirage d'un polyéthylène. L'additif est choisi parmi au moins un composé choisi dans le groupe constitué par les bisamides, les trisamides, les tétraamides et les acétals de sorbitol. L'invention concerne également un procédé pour augmenter la résistance à l'état fondu et/ou l'élasticité à l'état fondu et/ou l'aptitude à l'étirage du polyéthylène. L'invention concerne en outre un polyéthylène ayant une résistance à l'état fondu et/ou une élasticité à l'état fondu et/ou une aptitude à l'étirage améliorées.
PCT/EP2023/070833 2022-08-19 2023-07-27 Utilisation d'additifs pour améliorer le traitement de polyéthylènes WO2024037851A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22191286 2022-08-19
EP22191286.8 2022-08-19

Publications (1)

Publication Number Publication Date
WO2024037851A1 true WO2024037851A1 (fr) 2024-02-22

Family

ID=83593818

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/070833 WO2024037851A1 (fr) 2022-08-19 2023-07-27 Utilisation d'additifs pour améliorer le traitement de polyéthylènes

Country Status (2)

Country Link
TW (1) TW202424092A (fr)
WO (1) WO2024037851A1 (fr)

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325863A (en) 1979-02-05 1982-04-20 Sandoz Ltd. Benzofuranone or indolinone compounds useful as stabilizers for organic materials
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
US5216052A (en) 1991-07-01 1993-06-01 Ciba-Geigy Corporation Bisbenzofuran-2-ones
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
DE4316611A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Acyloxyphenyl)benzofuran-2-one als Stabilisatoren
DE4316876A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Alkoxyphenyl)benzofuran-2-one als Stabilisatoren
DE4316622A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Carboxymethoxyphenyl)benzofuran-2-one als Stabilisatoren
EP0589839A1 (fr) 1992-09-23 1994-03-30 Ciba-Geigy Ag 3-(Dihydrobenzofuranne-5-yl)benzofuranne-2-ones stabilisateurs
EP0591102A1 (fr) 1992-09-23 1994-04-06 Ciba-Geigy Ag 3-(2-Acyloxyéthoxyphényl)benzofuran-2-ones en tant que stabilisateurs
EP1291384A1 (fr) 2001-09-11 2003-03-12 Ciba SC Holding AG Benzofuran-2-ones en tant que stabilisateurs pour polymères synthétiques
WO2004072168A2 (fr) 2003-02-14 2004-08-26 Ciba Specialty Chemicals Holding Inc. Compositions de resine
WO2007039471A1 (fr) 2005-09-28 2007-04-12 Ciba Specialty Chemicals Holding Inc. Procédé pour améliorer les propriétés d'écoulement de bains de polymère
EP2204408A1 (fr) 2007-09-28 2010-07-07 Adeka Corporation Composition de résine polyoléfine
US20110171407A1 (en) 2010-01-11 2011-07-14 Dow Global Technologies Inc. Method for preparing polyethylene with high melt strength
WO2012045288A1 (fr) 2010-10-05 2012-04-12 Polymer Institute Brno, Spol. S R.O. Procédé de préparation d'un polymère semi-cristallin nucléé
EP1674447B1 (fr) 2003-10-17 2013-05-08 New Japan Chemical Co., Ltd. Mélanges d'amides, compositions de résines polyoléfiniques, pièces moulées en résines polyoléfiniques
WO2014043184A1 (fr) 2012-09-13 2014-03-20 Dow Global Technologies Llc Films à base de polyoléfine appropriés pour un thermoformage
WO2015121445A1 (fr) 2014-02-17 2015-08-20 Basf Se Dérivés de 3-phényl-benzofuran-2-one contenant du phosphore en tant que stabilisants
US9278487B2 (en) 2006-05-16 2016-03-08 Basf Se Mono-and multi-layer blown films
WO2017025431A1 (fr) 2015-08-10 2017-02-16 Basf Se Dérivés 3-phényl-benzofuran-2-one contenant du phosphore comme agents stabilisants
WO2017156099A1 (fr) 2016-03-09 2017-09-14 Milliken & Company Composés triamide et compositions les comprenant
EP3587425A1 (fr) 2018-06-26 2020-01-01 Chitec Technology Co., Ltd. Composé absorbant les ultraviolets et leurs applications
US10844210B2 (en) 2016-03-31 2020-11-24 Dow Global Technologies Llc Modified polyethylene resins and method for making the same
US10865298B2 (en) 2016-08-31 2020-12-15 Dow Global Technologies Llc Modified polyethylenes
WO2021126419A1 (fr) * 2019-12-16 2021-06-24 Dow Global Technologies Llc Films de polyéthylène orientés et articles les comprenant

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325863A (en) 1979-02-05 1982-04-20 Sandoz Ltd. Benzofuranone or indolinone compounds useful as stabilizers for organic materials
US4338244A (en) 1979-02-05 1982-07-06 Sandoz Ltd. Benzofuran(2)one or indolin(2)one compounds useful as stabilizers for organic materials
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
US5216052A (en) 1991-07-01 1993-06-01 Ciba-Geigy Corporation Bisbenzofuran-2-ones
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
DE4316876A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Alkoxyphenyl)benzofuran-2-one als Stabilisatoren
DE4316622A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Carboxymethoxyphenyl)benzofuran-2-one als Stabilisatoren
DE4316611A1 (de) 1992-05-22 1993-11-25 Ciba Geigy 3-(Acyloxyphenyl)benzofuran-2-one als Stabilisatoren
EP0589839A1 (fr) 1992-09-23 1994-03-30 Ciba-Geigy Ag 3-(Dihydrobenzofuranne-5-yl)benzofuranne-2-ones stabilisateurs
EP0591102A1 (fr) 1992-09-23 1994-04-06 Ciba-Geigy Ag 3-(2-Acyloxyéthoxyphényl)benzofuran-2-ones en tant que stabilisateurs
EP1291384A1 (fr) 2001-09-11 2003-03-12 Ciba SC Holding AG Benzofuran-2-ones en tant que stabilisateurs pour polymères synthétiques
WO2004072168A2 (fr) 2003-02-14 2004-08-26 Ciba Specialty Chemicals Holding Inc. Compositions de resine
EP1674447B1 (fr) 2003-10-17 2013-05-08 New Japan Chemical Co., Ltd. Mélanges d'amides, compositions de résines polyoléfiniques, pièces moulées en résines polyoléfiniques
WO2007039471A1 (fr) 2005-09-28 2007-04-12 Ciba Specialty Chemicals Holding Inc. Procédé pour améliorer les propriétés d'écoulement de bains de polymère
US9278487B2 (en) 2006-05-16 2016-03-08 Basf Se Mono-and multi-layer blown films
EP2204408A1 (fr) 2007-09-28 2010-07-07 Adeka Corporation Composition de résine polyoléfine
US20110171407A1 (en) 2010-01-11 2011-07-14 Dow Global Technologies Inc. Method for preparing polyethylene with high melt strength
WO2012045288A1 (fr) 2010-10-05 2012-04-12 Polymer Institute Brno, Spol. S R.O. Procédé de préparation d'un polymère semi-cristallin nucléé
WO2014043184A1 (fr) 2012-09-13 2014-03-20 Dow Global Technologies Llc Films à base de polyoléfine appropriés pour un thermoformage
WO2015121445A1 (fr) 2014-02-17 2015-08-20 Basf Se Dérivés de 3-phényl-benzofuran-2-one contenant du phosphore en tant que stabilisants
WO2017025431A1 (fr) 2015-08-10 2017-02-16 Basf Se Dérivés 3-phényl-benzofuran-2-one contenant du phosphore comme agents stabilisants
WO2017156099A1 (fr) 2016-03-09 2017-09-14 Milliken & Company Composés triamide et compositions les comprenant
US10844210B2 (en) 2016-03-31 2020-11-24 Dow Global Technologies Llc Modified polyethylene resins and method for making the same
US10865298B2 (en) 2016-08-31 2020-12-15 Dow Global Technologies Llc Modified polyethylenes
EP3587425A1 (fr) 2018-06-26 2020-01-01 Chitec Technology Co., Ltd. Composé absorbant les ultraviolets et leurs applications
WO2021126419A1 (fr) * 2019-12-16 2021-06-24 Dow Global Technologies Llc Films de polyéthylène orientés et articles les comprenant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAS , no. 106917-31-1

Also Published As

Publication number Publication date
TW202424092A (zh) 2024-06-16

Similar Documents

Publication Publication Date Title
EP2026965B1 (fr) Films souffles mono- et multi-couches
US20130210973A1 (en) Process for improving the flow properties of polymer melts
US11021585B2 (en) Light stabilized polyolefin films, tapes and monofilaments
US20230272171A1 (en) Additive mixtures for rheology modification of polymers
WO2024037851A1 (fr) Utilisation d'additifs pour améliorer le traitement de polyéthylènes
WO2024133667A1 (fr) Procédé d'amélioration du traitement du polyéthylène
RU2800783C1 (ru) Смесь светостабилизаторов для полиолефиновой пленки, ленты или мононити
WO2024052176A1 (fr) Modification rhéologique de polymères à l'aide d'un initiateur radicalaire et de thiouréthane
EP4110862A1 (fr) Compositions de polyoléfine

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23749008

Country of ref document: EP

Kind code of ref document: A1