EP4573154A1 - Use of additives for improving the processing of polyethylenes - Google Patents

Use of additives for improving the processing of polyethylenes

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Publication number
EP4573154A1
EP4573154A1 EP23749008.1A EP23749008A EP4573154A1 EP 4573154 A1 EP4573154 A1 EP 4573154A1 EP 23749008 A EP23749008 A EP 23749008A EP 4573154 A1 EP4573154 A1 EP 4573154A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
acid
tert
substituted
amino
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23749008.1A
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German (de)
French (fr)
Inventor
Daniel Mueller
Wiebke Wunderlich-Wippert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Milliken Europe BV
Original Assignee
BASF SE
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Publication date
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Publication of EP4573154A1 publication Critical patent/EP4573154A1/en
Pending legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene

Definitions

  • 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.
  • 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.
  • 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.
  • 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).
  • 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 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.
  • 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.
  • tri(Ci-Ci O alkyl)silyl is (H 3 C)3Si-.
  • 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-
  • 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).
  • 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.
  • 120micron films were produced on a Colling Cast film line CR 136 / 230 at 230°C.

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Abstract

The present invention is directed to improvements in the processing of polyethylenes. Specifically provided is a use of an additive for increasing the melt strength and/or melt elasticity and/or the drawability of a polyethylene. 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 the melt elasticity and/or the drawability of polyethylene. Additionally provided is a polyethylene having improved melt strength and/or melt elasticity and/or drawability.

Description

Use of additives for improving the processing of polyethylenes
Field of the Invention
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).
Background of the Invention
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).
Polyethylene may for instance be processed by blown moulding, blown film or by the extrusion techniques. During such processing techniques, especially for blown moulding, blown film and extrusion, 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. This disclosure recognised that 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/cm3 to 0.970 g/cm3, 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/cm3 to 0.970 g/cm3, 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/cm3 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/cm3 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/cm3 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.
In the production of polyolefins in general, it is known to add a wide variety of different additives for different purposes. For instance, it is known to add nucleating agents during the processing to improve the crystallisation and in particular in relation to improving clarity. Such 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 R1 - (CONHR2)a, where a represents an integer of 2 to 6; R1 is an aliphatic polycarboxylic acid; R2 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. 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. In particular, there is a desire to improve melt strength and/or melt elasticity and/or drawability of polyethylene during processing, especially during the extrusion of polyethylene, and more especially during the extrusion of polyethylene to produce films or fibres. This would particularly be the case for blown ethylene film production. Such improvements are desirable for mono and biaxial orientated polyethylene films (BOPE).
Summary of the Invention
In accordance with the present invention, we provide a use of 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. Additionally provided in accordance with the present invention is a polyethylene of improved melt strength and/or melt elasticity and/or drawability, comprising an additive for increasing the melt strength and/or melt elasticity and/or the drawability of the polyethylene, which additive is selected from the group consisting of bisamides, trisamides, tetraamides and sorbitol acetals.
Detailed Description of the Invention
Inventors have found that compounds in the categories of bisamides, trisamides, tetraamides and sorbitol acetals can be used in the processing of polyethylene to achieve the aforementioned objectives. The incorporation of bisamides, trisamides, tetraamides or sorbitol acetals into the polyethylene processing can improve the melt strength as well after melt elasticity and can improve the drawability of the molten polyethylene.
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).
Preferably, the polyethylene has a density of from 0.915 to 0.960 g/cm3, preferably from 0.915 to 0.950 g/cm3.
Suitably the polyethylene may be an ultrahigh molecular weight polyethylene (UHMWPE). Such UHMWPE may have a molecular weight of several million, for instance from 3.5 to 7.5 million g/mol. Typically, the density tends to be less than high density polyethylene and may be in the range of from 0.930 to 0.935 g/cm3.
High density polyethylene (HDPE) may also be processed in accordance with the present invention, especially if the density does not exceed 0.960 g/cm3. Typically, HDPE has a density of greater than 0.941 g/cm3. Another suitable polyethylene which may be processed according to the present invention includes low density polyethylene (LDPE). Low density polyethylene may be characterised by having a high degree of short and long chain branching.
Typically, LDPE may have a density in the range of from 0.910 to 0.940 g/cm3.
Where LDPE is been processed, desirably the density would be in the range of from 0.915 to 0.940 g/cm3.
More suitably the polyethylene employed in accordance with the present invention may be a medium density polyethylene (MDPE). Typically, such a medium density polyethylene (MDPE) may have a density in the range of from 0.926 to 0.940 g/cm3.
It is particularly preferred that the polyethylene is a linear low-density polyethylene (LLDPE). 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/cm3.
In one preferred aspect according to the present invention, 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
C1-C20 alkyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups;
C2-C20 alkenyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups;
C2-C20 alkyl interrupted by oxygen or sulfur;
C3-C12 cycloalkyl unsubstituted or substituted by one or more C1-C20 alkyl; bis[Cs-Ci2 cyclo alky I]— C1-C10 alkyl unsubstituted or substituted by one or more C1- C20 alkyl; a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more C1-C20 alkyl; phenyl unsubstituted or substituted by one or more radicals selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, di-(Ci-C2o alkyl)amino, amino, hydroxy and nitro; phenyl-Ci-C2o alkyl unsubstituted or substituted by one or more radicals selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, di-(Ci-C2o alkyl)amino, amino, hydroxy and nitro; phenylethenyl unsubstituted or substituted by one or more C1-C20 alkyl; biphenyl-(Ci- C10 alkyl) unsubstituted or substituted by one or more C1-C20 alkyl; naphthyl unsubstituted or substituted by one or more C1-C20 alkyl; naphthyl-Ci-C2o alkyl unsubstituted or substituted by one or more C1-C20 alkyl; naphthoxymethyl and substituted or substituted by one or more C1-C20 alkyl; biphenylenyl, fluorenyl, anthryl; a 5 to 6 membered heterocyclic radical unsubstituted or substituted by one or more C1-C20 alkyl; a C1-C20 hydrocarbon radical containing one or more halogen or pseudo-halogen; tri(Ci-Cw alkyl)silyl; or tri(Ci-Cw alkyl)silyl(Ci-Cio alkyl);
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 (particularly 1 , 2, 3-propanetricarboxylic acid), propanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid (particularly 1 ,2,3, 4-butanetetracarboxylic acid), dodecanetetracarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethyleneglycolbis[beta- aminoethylether]N,N,N',N'-tetraacetic acid, N-hydroxyethylethylenediamine- N,N',N'-triacetic acid, 1 ,3-diaminopropane-2-ol-N,N,N',N'- tetraacetic acid, 1 ,2- diaminopropane-N,N,N',N'-tetraacetic acid, nitrilotripropionic acid, 1 ,6- hexanediaminetetraacetic acid, N-(2-carboxyethyl)iminodiacetic acid and the like.
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- tetracarboxytricyclo[6.2.2.0.sup.2,7 ]dodeca- 2,11 -diene which may have a lower alkyl group as a substituent (such as a methyl group at the 3-, 8- 11- or 12- position), 1 ,2-cyclohexanediaminetetraacetic acid, 2,3,5- tricarboxycyclopentylacetic acid, 6-methyl-4-cyclohexene-1 ,2,3-tricarboxylic acid, 3,5,6- tricarboxynorbomene-2-acetic acid, thiobis(norbornene-2,3-dicarboxylic acid), bicyclo[4.2.0]octane-3,4,7,8-tetracarboxylic acid, 1 ,1 '-bicyclopropane- 2,2',3,3'-tetracarboxylic acid, 1 ,2-bis(2,3-dimethyl-2,3- dicarboxycyclobutyl)ethane, pyrazine-2,3,5,6-tetracarboxylic acid, tricyclo[4.2.2.0.sup.2,5 ]decane-9-ene-3,4,7,8-tetracarboxylic acid, 3,4- dicarboxy- 1 ,2, 3, 4-tetrahydro-1 -naphthalenesuccinic acid which may have a lower alkyl group as a substituent (such as a methyl group at the 1-, 5-, 6- or 7- position), 2,3,4,5,6,7,12,13- octahydrophenanthrene-3,4,5,6-tetracarboxylic acid and the like.
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)methane, 2,2-bis(3- carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)propane, 3,3'-sulfonyldibenzoic acid, 4, 4, -sulfonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-thiodibenzoic acid, 4,4'-(p-phenylenedioxy)dibenzoic acid, 4,4'- isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid, dithiosalicylic acid, benzenetricarboxylic acid such as trimesic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylmethanetetracarboxylic acid, perylenetetracarboxylic acid, naphthalenetetracarboxylic acid, 4,4'-dinaphthalic acid, benzidine-3,3'-dicarboxyl- N,N'-tetraacetic acid, diphenylpropanetetracarboxylic acid, anthracenetetracarboxylic acid, phthalocyaninetetracarboxylic acid, ethyleneglycol-trimellitic acid diester, benzenehexacarboxylic acid, glycerinetrimellitic acid triester and so on.
Examples of 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, heptadecyl, hydroxymethyl, 1- hydroxyethyl and 1 -aminoethyl. Branched C3-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(CH3)2-(Ci-C7alkyl). Examples of C2-C2oalkyl interrupted by oxygen or sulfur are t-butoxym ethyl, t- butoxyethyl, t-butoxypropyl, t-butoxybutyl, (H3C)3C-S-CH2-, (H3C)3C-S-C2H4-, (H3C)3C-S-C3H5- and (H3C)3C-S-C4H8-.
Examples of Ci-Csalkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy. Methoxy is particularly preferred.
Examples of Ci-Csalkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio and octylthio.
Examples of Ci-Csalkylsulfoxy are methylsulfoxy, ethylsulfoxy, propylsulfoxy, butylsulfoxy, pentylsulfoxy, hexylsulfoxy, heptylsulfoxy and octylsulfoxy.
Examples of Ci-C2oalkenyl 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.
Examples of C3-Ci2cycloalkyl unsubstituted or substituted by one or more Ci- C2oalkyl, e.g. 1 , 2, 3 or 4 Ci-C4alkyl, 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.
An example of bis[C3-C12cycloalkyl]-CiCioalkyl unsubstituted or substituted by one or more Ci-C2oalkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, is dicyclohexylmethyl.
Examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C2oalkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are
and
Examples of phenyl unsubstituted or substituted by one or more radicals selected from Ci-C2oalkyl, Ci-C2oalkoxy, Ci-C2oalkylamino, di(Ci-C2oalkyl)amino, amino, hydroxy and nitro, preferably Ci-C4alkyl, Ci-C4alkoxy, Ci-C4alkylamino, di(Ci- C4alkyl)amino, hydroxy and nitro, are 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.
Examples of phenyl-Ci-C2oalkyl 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. An example of phenylethenyl unsubstituted or substituted by one or more Ci- C2oalkyl, e.g. 1 , 2 or 3 C1-C4alkyl, is 2-(4-methylphenyl)ethenyl.
An example of biphenyl-(Ci-C10alkyl) unsubstituted or substituted by one or more Ci-C2oalkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, is 4-biphenylmethyl.
Examples of naphthyl unsubstituted or substituted by one or more Ci-C20alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are 1 -naphthyl and 2-naphthyl.
Examples of naphthyl-Ci-C20alkyl unsubstituted or substituted by one or more Ci- C20alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, are 1 -naphthylmethyl and 2-naphthylmethyl.
An example of naphthoxymethyl unsubstituted or substituted by one or more Ci- C20alkyl, e.g. 1 , 2 or 3 Ci-C4alkyl, is 1 -naphthoxymethyl.
An example of 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-C20alkyl, 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.
Examples of a Ci-C20hydrocarbon radical containing one or more halogen or pseudo halogen, e.g. 1 , 2, 3, 4, 5, or 6 -F, -Cl or -I, are 1-bromo-2-methylpropyl, dichloromethyl, pentafluoroethyl, 3,5-bis[trifluoromethyl]phenyl, 2, 3,5,6- tetrafluoro-p-tolyl, 2,3-dichlorophenyl, 3,4-dichlorophenyl and 2,4- bis[trifluoromethyl]phenyl.
An example of tri(Ci-CiOalkyl)silyl is (H3C)3Si-.
An example of 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-triaminocyclohexane, 1 , 2,4,5- tetraaminocyclohexane and the like.
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-diaminonaphthalene, 2,7-diaminonaphthalene, 9,10- diaminophenanthrene, 3,3',5,5'-tetramethylbenzidine, 3,3' dimethyl-4,4'- diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'- diaminodiphenylmethane, 4,4' methylenedi-o-toluidine, 4,4'-methylenedi-2,6- xylidine, 4,4'-methylenedi-2,6-diethylaniline, 4,4'-diamino-1 ,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminostilbene, 3,4'-diamino-2,2- diphenylpropane, 4,4'-diamino-2,2-diphenylpropane, 4,4' diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'- dithiodianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'- diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, o- tolidinesulfone, 2,7-diaminofluorene, 3,7-diamino-2-methoxyfluorene, bis-p aminophenylaniline, 1 ,3-bis(4-aminophenylpropyl)benzene, 1 ,4-bis(4- aminophenylpropyl)benzene, 1 ,3-bis(4-aminophenoxy)benzene, 1 ,4-bis(4- aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4- aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]sulfone, 9,9-bis(4- aminophenyl)fluorene-1 ,2,4,5-tetraaminobenzene, 1 ,3,5-triaminobenzene, 1 ,2,4- triaminobenzene, Para Rosaniline, 2,4,6-triaminophenol, 3,3'-diaminobenzidine, tris(4-aminophenyl)methane, 2,4,6-triaminopyrimidine, and the like.
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-4-pentenoic acid, alpha-amino-n-caproic acid, 6- aminocaproic acid, alpha-aminoisocaproic acid, 7-aminoheptanoic acid, alpha- amino-n-caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11- aminoundecanoic acid, 12-aminododecanoic acid, 2- aminoadipic acid, arginine, asparagine, aspartic acid, cystine, glutamic acid, glutamine, ornithine, creatine, aminomalonic acid, and the like.
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-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3-amino- 4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3- methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4-(4- aminophenyl)butyric acid, 4-aminomethylbenzoic acid, 4- aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p- aminocinnamic acid, p-aminohippuric acid, 2-amino-1 -naphthoic acid, 3-amino-1- naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6-amino-1- naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1-amino-2- naphthoic acid, 3-amino-2-naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2- naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid, 8-amino-2- naphthoic acid, 3,5-diaminobenzoic acid, 3,5-dicarboxyaniline, 4,4' diamino-3,3'- dicarboxydiphenylmethane and the like.
Examples of halogen or pseudo-halogen are -F, -Cl, -Br, -I, -CN, -CNO, -OCN, - SCN and -CNS.
In one desirable embodiment the additive is a trisamide or a tetraamide according to formula (IA). In this desirable embodiment 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; and 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.
Preferably the additive is an aromatic bisamide, an aromatic trisamide or an aromatic tetraamide.
In a preferred embodiment, the additive is a bisamide, a trisamide or a tetraamide according to any of the formulae (IA), (IB), and (IC). In one such preferred embodiment 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.
Examples of C1-C4 alkyl include methyl, ethyl, n-propyl, 1 -methylethyl, n-butyl, 2- methylpropyl, 1 -methylpropyl and tert-butyl. Examples of C3-Ci2cycloalkyl optionally substituted 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. Examples of 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-hydroxybenzyl, 2- phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 3-methylbenzyl, 3,4- dimethoxybenzyl and 2-(3,4-dimethoxyphenyl)ethyl, 2-(4-methylphenyl)ethenyl, 4-biphenylmethyl, naphthyl, 1 -naphthyl, 2-naphthyl, 1 -naphthylmethyl, 2- naphthylmethyl, 1 -naphthoxymethyl, 2-biphenylenyl, 9-fluorenyl, 1-fluorenyl and 9-anthryl.
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).
In a preferred embodiment, the additive is a trisamide according to any of the formulae (IA), (IB), and (IC). In one such preferred embodiment 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).
(V C) (V D) wherein each Xi, each Yi, each Zi and each Z2 independently of one another have the same meanings ascribed to them as previously provided.
Preferably, 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).
In one desirable embodiment R1 is a substituted cyclohexyl group. Suitably R1 has the structure shown in formula (VII A):
(VII A) wherein 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. In this instance R2 and R3 would have the same definitions given for the structure of formula (VII). Preferably, 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. Preferably, 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.
In a further preferred embodiment R2 has independently of R1 the same definition as ascribed to R1 as represented by formula (VII A).
In a still further preferred embodiment both R2 and R3 independently of each other and R1 have the same definition as ascribed to R1 as represented by formula (VII A).
Thus, according to the still further preferred embodiment 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):
Another specific suitable compound according to formula (VII B) is trans-4-tert- butylcyclohexylcarbonylamino-3,5-bis [cis-4-tert-butylcyclohexylcarbonylamino] benzene, illustrated by formula (XVI):
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
(XVIII):
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.
As indicated above the preferred embodiment of compounds of formula (VII) are where R1 , R2 and R3 are all tertiary butyl. Such particularly preferred compound has the structure according to formula (XIX).
In a further embodiment of the present invention the additive may desirably be a sorbitol acetal. Preferably 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. Examples of halogen or pseudo-halogen are -F, -Cl, -Br, -I, -CN, -CNO, - OCN, -SCN and -CNS. One such example of 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):
One particularly suitable sorbitol acetal based on formula (VIII) is the compound of formula (IX):
Another particularly suitable sorbitol acetal based on formula (VIII) is the compound of formula (X):
The additive may be added to the polyethylene melt in any suitable amount. Preferably 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. Preferably, however, 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. Preferably, however, 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. Preferably, 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. Such 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. Other examples of 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. Each refers to Plastic Additives Handbook, 5th Edition, Edited by Hans Zweifel, Hanser Munich, ISBN 3-446-21654-5.
Specific examples of these co-additives are shown below.
1 . Antioxidants
1.1. 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- yl)phenol, 2,4-dimethyl-6-(1 ' methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'- methyltridec-1'-yl)phenol and mixtures thereof.
1 .2. 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.
1 .3. 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.
1.4. 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.
1 .6. 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- nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert- butyl-2-methylphenol), 1 , 1 -bis(5-tert butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1 ,1 ,3-tris(5-tert- butyl-4-hydroxy-2-methylphenyl)butane, 1 ,1-bis(5-tert-butyl-4- hydroxy-2-methyl- phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert butyl-4'- hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl- phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert- butyl-4-methylphenyl]terephtha late, 1 ,1-bis-(3,5-dimethyl-2- hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2- bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5- tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1 .7. 0-, 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. 1 .8. 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.
1 .9. 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.
1.10. 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)-
1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1 ,3,5- tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris-
15 (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5-di-tert- butyl-4-hydroxy-phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5- dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. 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.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4- hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. 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-trioxabicyclo[2.2.2]octane.
1.14. 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- trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert butyl-4-hydroxy-5- methylphenyl)propionyloxy}-1 , 1-dimethylethyl]-2,4,8, 10- tetraoxaspiro[5.5] undecane.
1.15. 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]octane.
1.16. 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[2.2.2]octane.
1.17. Amides of 13-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'- bis(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)trimethylenediamide, N,N'-bis(3,5- di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl- 4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau gard®XL-1 , supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. 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'-phenyl-p- phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N- cyclohexyl-N' phenyl-p-phenylenediamine, 4-(p- toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-
5 sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4- isopropoxydiphenyl amine, N-phenyl-1 -naphthylamine, N-(4-tert-octylphenyl)-1- naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl aminophenol, 4- butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4- dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'- diaminodiphenylmethane, N,N,N',N'-tetra methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenyl amino)propane, (o- tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N phenyl-1- naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3,3-dimethyl-4H-1 ,4- benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert- octylphenothiazines, a mixture of mono- and dialkylated tert-octyl- phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2- ene.
2. UV absorbers and light stabilizers
2.1 . 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'-octyloxyphenyl)benzotriazole, 2- (3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(a,a- dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyl oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl ethyl)phenyl)benzotriazole, 2- (3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'- hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1 ,1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; - [- R-CH2CH2COO-CH2CH2 -]2 - , where
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.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4- octyloxy, 4-decyl oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'- hydroxy-4,4'-dimethoxy derivatives. 2.3. 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.
2.4. Acrylates/Cinnamates, for example ethyl a-cyano-p,p- diphenylacrylate, isooctyl a-cyano-p,p-diphenylacrylate, methyl a- carbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinnamate, butyl a-cyano-p,p-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycin- namate, N-(p-carbomethoxy- p -cyanovinyl)-2-methylindoline, neopentyl tetra(o- cyano-p,p-diphenylacrylate. Other cyanoacrylates may also be used and such compounds are given in EP 3587425.
2.5. 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.
2.6. 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 octylamino-2,6-dichloro-1 ,3,5-triazine, tris(2,2,6,6-tetramethyl-4- piperidyl)nitrilotriacetate, tetrakis(2, 2,6, 6-tetramethyl-4-piperidyl)-1 , 2,3,4- butanetetracarboxylate, 1 ,1'-(1 ,2-ethanediyl) bis(3, 3,5,5- tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2.2.6.6-tetramethylpiperidine, bis(1 , 2,2,6, 6-pentamethylpiperidyl)-2-n-butyl-2-(2- hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8- triazaspiro[4.5]decane-2, 4-dione, bis(1 -octyloxy-2, 2, 6, 6- tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2, 2,6,6- tetramethylpiperidyl)succinate, linear or cyclic condensates of N, N'-bis(2, 2,6,6- tetramethyl-4- piperidyl)hexamethylenediamine and 4-morpholino-2,6- dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-
2.2.6.6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3- aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-
1.2.2.6.6-pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3- aminopropylamino)ethane, 8- acetyl-3-dodecyl-7,7,9,9-tetramethyl-1 ,3,8- triazaspiro[4.5]decane-2, 4-dione, 3-dodecyl-1 - (2,2,6,6-tetramethyl-4- piperidyl)pyrrolidine-2, 5-dione, 3-dodecyl-1-( 1 , 2,2,6, 6-pentamethyl-4- piperidyl)pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-
2.2.6.6- tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 ,3,5- triazine, a condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro- 1 ,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1 ,6-hexanediamine and 2,4,6-trichloro-
1 ,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2, 2,6,6- tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6- tetramethyl-4- piperidyl)-n-dodecylsuccinimide, N-(1 , 2,2,6, 6-pentamethyl-4-piperidyl)-n- dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo- spiro[4,5]decane, a reaction product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1 - oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 , 1-bis(1 ,2,2,6,6- pentamethyl-4-piperidyloxycarbonyl)-2-(4- methoxyphenyl)ethene, N,N'-bis- formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa methylenediamine, a diester of 4-methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl- 4- hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4- piperidyl)]siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1 ,2,2,6, 6-pentamethyl- 4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4- yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1 ,3,5-triazine, 1-(2-hydroxy-2- methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2- ethylhexanoyl) oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor 3058 (Clariant; CAS Reg. No. 106917-31-1 ] 1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4- yl)-3-dodecylpyrrolidine-2, 5-dione, , the reaction product of 2,4-bis [(1- cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazine with N,N'- bis(3-ami nopropyl)ethylenediamine), 1 ,3,5-tris(N-cyclohexyl-N-(2,2,6,6- tetramethylpiperazine-3-one-4- yl)amino)-s-triazine, 1 ,3,5-tris(N-cyclohexyl-N- (1 ,2,2,6,6-pentamethylpiperazine-3-one-4-yl) amino)-s-triazine.
2.7. 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.
2.8. 2-(2-Hydroxyphenyl)-1 ,3, 5-th azines, for example 2,4,6-tris(2-hydroxy- 4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4- dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3- butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5- triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4- dimethyl)-1 ,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2- hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[2-hydroxy-4-(2- hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl phenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydr oxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3- butoxy-2- hydroxypropoxy)phenyl]-1 , 3, 5-triazine, 2-(2-hydroxyphenyl)-4-(4- methoxyphenyl)-6-phenyl-1 ,3, 5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1 -oxy)-2- hydroxypropyloxy ]pheny l}-4 ,6-bis(2,4-dimethylphenyl)-1 ,3, 5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4- methoxyphenyl)-1 ,3, 5-triazine.
3. 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.
4. 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 diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6- methylphenyl)ethyl phosphite, 6-fluoro-2,4,8, 10-tetra-tert-butyl-12-methyl- dibenz[d,g]-1 ,3,2-dioxaphosphocin, 2,2',2"-nitrilo [triethyltris(3,3',5,5'-tetra-tert- butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te tra-tert-butyl-1 ,T- biphenyl-2 ,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-
1 ,3,2-dioxaphosphirane, poly(4,4'{-isopropylidenediphenol}-octylphosphite), poly(4,4'- {isopropylidenebis[2,6-dibromophenol]}-octylphosphite), poly(4,4'- {2,2 - dimethyl-5,5'-di-t-butylphenylsulfide}-pentaerythrityl diphosphite), phosphorous acid, mixed 2,4-bis(1 ,1-dimethylpropyl)phenyl and 4-(1 ,1-dimethylpropyl)phenyl triesters (CAS No. 939402-02-5), phosphorous acid, triphenyl ester, polymer with alpha-hydro-omega-hydroxypoly[oxy(methyl-1 ,2-ethanediyl)], C10-16alkyl esters (CAS No. 1227937-46-3).
The following phosphites are especially preferred: Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos®168, BASF SE), tris(nonylphenyl) phosphite,
5. 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.
6. 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 N,N-dialkylhydroxyl amine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3- (dodecylthio)propionate] or distearyl disulfide.
8. 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.
9. 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.
10. 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).
11 . 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.
12. Other 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. 13. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE- A-4316611 ; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP- A-1291384 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7- di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-di methylphenyl)-5,7-di-tert- butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di tert- butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5- isooctylphenyl)-5-isooctyl benzofuran-2-one. Suitable benzofuranones also include compounds identified in WO2015/121445 and WO2017/025431.
14. Vis-breaking agents
Vis-breaking agents or generally radical initiators. Typically, this includes organic or inorganic peroxides, which are widely used in industry, bis azo compounds,
14.1 Peroxides
Examples of 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, acetylcyclohexanesulphonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl-perneodecanoate, tert- butylperpivalate, tertamylperpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2- methylbenzoyl)peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, bis(4-chlorobenzoyl) peroxide, tertbutyl perisobutyrate, tert-butyl permaleate, 1 ,1-bis(tert-butylperoxy)-3,5,5- trimethylcyclohexane, 1 , 1 -bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl perisononaoate, 2,5-di- methylhexane 2,5- dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl per- benzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis (tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,5-di-tert-butylperoxid, 3-tert-butylperoxy-3-phenyl phthalide, di-tert-amyl peroxide, a,a’-bis(tert-butylperoxyisopropyl) benzene, 3,5- bis(tert-butylperoxy)-3,5-di- methyl-1 ,2-dioxolane, di-tert-butyl peroxide, 2,5- dimethylhexyne 2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1 ,2,4,5- tetraoxacyclononane, p-menthane hydroperoxide, pinane hy- droperoxide, diisopropylbenzene mono-a-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.
14.2. Bis azo compounds
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- amidinopropane) as free base or hydrochloride, 2,2'-azobis{2-methyl-N-[1 , 1- bis(hydroxymethyl)ethyl]propionamide} or 2,2'-azobis{2-methyl-N-[1 , 1- bis(hydroxymethyl)-2-hydroxyethyl]propionamide.
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 following examples illustrate the present invention. All parts and percentages given by weight unless indicated otherwise. Examples
Additives used:
Table 1
Polypropylene Moplen HP 561 R from LYB, ground (PP 2)
Example 1
Preparation:
Mixtures were produced using the additives as indicated above in LLDPE (Exxonmobil LL 1002YB Cast, ground) as basis in a 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.
Testing of drawability and melt strength:
Drawability and melt strength of the compounds were tested with a rheotense test device connected with a single screw extruder from Gdttfert in Germany.
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.
Results:
Table 2
The above results showed that either the drawability and/or the melt strength of the so treated Polyethylenes according to the invention were better than the reference formulation and overall better than the comparative products.
Example 2
Test of max drawability of LLDPE films on a MDO stretch line:
Mixtures were produced using the additives as indicated above in Example 1 LLDPE (Exxonmobil LL 1002YB Cast, ground) as basis in a 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.
Testing:
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.
Results:
Table 3
The above results showed that the inventive Polyethylene films had better drawability than the reference formulation and the comparative formulations.

Claims

Claims
1 . A use of 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.
2. The use according to claim 1 , wherein the polyethylene has a density of from 0.915 to 0.960 g/cm3, preferably from 0.915 to 0.950 g/cm3.
3. The use according to claim 1 or claim 2, wherein the additive is 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
C1-C20 alkyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups;
C2-C20 alkenyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups;
C2-C20 alkyl interrupted by oxygen or sulfur;
C3-C12 cycloalkyl unsubstituted or substituted by one or more C1-C20 alkyl; bis[Cs-Ci2 cycloalkyl]-Ci-Cw alkyl unsubstituted or substituted by one or more C1- C20 alkyl; a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more C1-C20 alkyl; phenyl unsubstituted or substituted by one or more radicals selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, di-(Ci-C2o alkyl)amino, amino, hydroxy and nitro; phenyl-Ci-C2o alkyl unsubstituted or substituted by one or more radicals selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, di-(Ci-C2o alkyl)amino, amino, hydroxy and nitro; phenylethenyl unsubstituted or substituted by one or more C1-C20 alkyl; biphenyl-(Ci- C10 alkyl) unsubstituted or substituted by one or more C1-C20 alkyl; naphthyl unsubstituted or substituted by one or more C1-C20 alkyl; naphthyl-Ci-C2o alkyl unsubstituted or substituted by one or more C1-C20 alkyl; naphthoxymethyl and substituted or substituted by one or more C1-C20 alkyl; biphenylenyl, fluorenyl, anthryl; a 5 to 6 membered heterocyclic radical unsubstituted or substituted by one or more C1-C20 alkyl; a C1-C20 hydrocarbon radical containing one or more halogen or pseudo-halogen; tri(Ci-C alkyl)silyl; or tri(Ci-Cw alkyl)silyl(Ci-Cio alkyl); 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;
Yi has the same definition as Xi;
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 Zi and Z2 independently of one another have the same definition given for Xi .
4. The use according to claim 3, wherein the additive is a trisamide or a tetraamide according to formula (I A) , wherein x is an integer of 3 or 4;
Xo is a residue obtained by removing all of the carboxyl groups from 1 ,2,3- propanecarboxylic acid or 1 ,2,3,4-butanetetracarboxylic acid; and 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.
5. The use according to claim 3, wherein when 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, and when x, y or the sum of z’ and z” are 3, Xo, Yo, and Zo are the group of the formula (V)
6. The use according to claim 5, wherein 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).
7. The use according to any of claims 1 to 3 or claim 5 or claim 6, wherein the additive is an aromatic bisamide of the 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.
8. The use according to any of claims 1 to 3 or claim 5 or claim 6, wherein the additive is an aromatic trisamide of the formula (VII) wherein R1 , R2 and R3 are 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.
9. The use according to claim 1 or claim 2, wherein the additive is a sorbitol acetal of the 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 C1- C3 alkyl.
10. The use according to claim 9, wherein the additive is a sorbitol acetal of the formula (IX)
11. The use according to claim 9, wherein the additive is a sorbitol acetal of the formula (X)
12. The use according to any of claims 1 to 11 , wherein the polyethylene comprises the additive in an amount of from 0.005 to 0.5 wt. %.
13. The use according to any of claims 1 to 12, wherein the polyethylene is a polyethylene film.
14. The use according to any of claims 1 to 13, wherein at least one selected from the group consisting of light stabiliser, antioxidant, vis-breaking agents; metal deactivators; phosphites and phosphonites; nitrones; thiosynergists; peroxide scavengers; basic co-stabilisers; nucleating agents; fillers and reinforcing agents; benzofuranones; indolinones; slip additives; acid scavengers; anti blocking additives; and antifogging additives.
15. 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.
16. A polyethylene of improved melt strength and/or melt elasticity and/or drawability, comprising an additive for increasing the melt strength and/or melt elasticity and/or the drawability of the polyethylene, which additive is selected from the group consisting of bisamides, trisamides, tetraamides and sorbitol acetals.
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