Process for improving processing of polyethylene

Abstract

The present invention relates to a process for increasing the tensile property and / or melt strength and / or melt elasticity of a polyethylene, comprising the step of mixing the polyethylene with a compound selected from the group consisting of polypropylene, at least one hydroxylamine ester of formula (I), or a combination thereof. The invention further relates to a polyethylene composition comprising polyethylene and a compound selected from the group consisting of: polypropylene; hydroxylamine esters of formulae (I), (IA), (IA '), (IA' '), (IA' ''), or a mixture of two or more thereof, or a combination thereof The invention also relates to the use of polypropylene and / or hydroxylamine esters of formulae (I), (IA), (IA '), (IA' '), (IA'''), or a mixture of two or more thereof for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, which method comprises the step of mixing the polyethylene with a compound selected from: polypropylene, at least one hydroxylamine ester having the formula (I), or a combination thereof. The present invention further relates to a polyethylene composition comprising polyethylene and a compound selected from: polypropylene; a hydroxylamine ester having the formula (I), (IA), (IA'), (IA"), (IA"'); or a mixture of two or more thereof; or a combination thereof. The present invention also relates to the use of polypropylene and / or a hydroxylamine ester having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene. Background Art

[0002] Polyethylene can be used in a variety of applications. Typically, this can include many different articles such as films, extrudates and pipes as well as many other articles. Different types of polyethylene can be produced by a variety of processes including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE).

[0003] Polyethylene can be processed, for example, by blow molding, blown film or by extrusion techniques. During such processing techniques, in particular for blow molding, 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 fibers (typically as spunbond or continuous filaments), or when producing blown film (typically involving extrusion of polyethylene through a blown film extruder).

[0004] US2011 / 0171407 A1 discloses a method for increasing the melt strength of a polyethylene resin by reacting the polyethylene resin with an alkoxyamine derivative having the following formula: (R1)(R2)N-O-R3, where R1 and R2 are each independently of one another hydrogen, C4-C 42 alkyl or C4-C 42 aryl or a substituted hydrocarbon group containing O and / or N, and where R1 and R2 can together form a ring structure; and where R3 is hydrogen, a hydrocarbon or a substituted hydrocarbon group containing O and / or N. This disclosure recognizes that melt strength is a practical measure that can predict the material properties when subjected to elongational deformation.

[0005] US 7,030,196 B2 relates to the use of hydroxyamine esters as polymerization initiators and to their use for the controlled degradation of polypropylene and for the controlled increase in molecular weight or crosslinking of polyethylene. Examples of the use show, under item C), the controlled degradation of polypropylene by hydroxyamine esters (NOR compounds). The addition of the NOR compound causes the polypropylene used to undergo increased degradation, which is reflected in a higher MFR value compared to the starting polymer. Hydroxyamine esters produce significantly greater polymer degradation (higher MFR value at the same concentration of use) compared to alkylated hydroxylamines.

[0006] The object of the present invention is to provide a method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene. In particular, it is desirable to increase the melt strength and / or melt elasticity and / or drawability of polyethylene during the processing of polyethylene, especially during the extrusion of polyethylene, and more especially during the extrusion of polyethylene to produce films or fibers. This is especially the case in the production of blown polyethylene films. Such improvements are desired for mono-oriented polyethylene films (MOPE) and biaxially oriented polyethylene films (BOPE). Summary of the Invention

[0007] Surprisingly, it has been found that when mixed with polyethylene, polypropylene and hydroxyamine esters of formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof increase the drawability and / or melt strength and / or melt elasticity of polyethylene.

[0008] Thus, in one aspect, the invention claimed herein relates to a method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, the method comprising the step of mixing polyethylene with 0.1 to 10 wt% of polypropylene, based on the total weight of the mixture, and at least one hydroxyamine ester of formula (I), or a combination thereof.

[0009] In another aspect, the invention claimed herein relates to a polyethylene composition comprising: 80 to 99.8 wt% of polyethylene, based on the total weight of the composition; 0.1 to 10 wt% of polypropylene, based on the total weight of the composition, and 0.001 to 1 wt% of hydroxyamine esters, which are selected from sterically hindered amines of formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof.

[0010] In yet another aspect, the invention claimed herein relates to the use of polypropylene and hydroxyamine esters for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, which hydroxyamine esters are selected from sterically hindered amines of formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof. Detailed Embodiments

[0011] Before describing the compositions and formulations of the present invention, it should be understood that the present invention is not limited to the specific compositions and formulations described, as such compositions and formulations can of course vary. It should also be understood that since the scope of the invention claimed herein will be defined only by the appended claims, the terminology used herein is not intended to be limiting.

[0012] If in the following a group is defined as comprising at least a certain number of embodiments, this means that groups consisting preferably only of these embodiments are also covered. In addition, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. in the present specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that the terms used in this way are interchangeable where appropriate, and the embodiments of the present invention described herein are capable of operating in other orders than those described or illustrated herein. If the terms "first", "second", "third" or "(A)", "(B)" and "(C)" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or measurement, there is no temporal or chronological coherence between these steps, that is, these steps can be carried out simultaneously or there can be a time interval of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application described above or below.

[0013] In the following paragraphs, different aspects of the present invention are defined in more detail. Each aspect so defined can be combined with any one or more other aspects unless explicitly indicated to the contrary. In particular, any feature indicated as preferred or advantageous can be combined with any one or more other features indicated as preferred or advantageous.

[0014] References to "an embodiment" or "preferred embodiment" in the present specification mean that the particular features, structures, or characteristics described in connection with that embodiment are included in at least one embodiment of the invention claimed herein. Thus, the phrases "in one embodiment" or "in a preferred embodiment" or "in another embodiment" that appear in various places throughout this specification do not necessarily all refer to the same embodiment, but may. Additionally, in one or more embodiments, the particular features, structures, or characteristics may be combined in any suitable manner, as will be apparent to those skilled in the art from this disclosure. Further, although some embodiments described herein include some features (but not other features included in other embodiments), combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments, as will be understood by those in the art. For example, any of the claimed embodiments may be used in any combination in the appended claims.

[0015] In addition, ranges defined throughout this specification also include the end values, i.e., a range of 1 to 10 means both 1 and 10 are included in the range. To avoid doubt, the applicant is entitled to any equivalent manner under applicable law.

[0016] Certain terms are first defined to make it easier to understand this disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of this invention belong.

[0017] In one aspect, the invention claimed herein relates to a method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, the method comprising the step of mixing polyethylene with a compound selected from: polypropylene in an amount of 0.1 to 10 wt% based on the total weight of the mixture, at least one hydroxylamine ester having the formula (I), or a combination thereof

[0018]

[0019] wherein R a represents an acyl group;

[0020] R b and one of R c represents hydrogen, a hydroxyl group, or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group, a C1-C6 alkoxy group, a C6-C 10 aryloxy group, selected from -O-C(=O)-H, -O-C(=O)-C1-C 19 alkyl group, -O-C(=O)-C1-C 54 alkenyl group, -O-C(=O)-C6-C 10 aryl group, -O-C(=O)-C1-C36 alkenyl-C6-C 10 aryl, -O-C(=O)-O-C1-C 19 alkyl, -O-C(=O)-O-C6-C 10 aryl, -O-C(=O)-NH-C1-C6alkyl, -O-C(=O)-NH-C6-C 10 acyloxy groups, C1-C6alkylamino, di-C1-C6alkylamino, C6-C 10 arylamino, selected from the group consisting of -NH-C(=O)-H, -NH-C(=O)-C1-C 19 alkyl, -NH-C(=O)-C1-C 54 alkenyl, -NH-C(=O)-C6-C 10 aryl, -NH-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl, -NH-C(=O)-O-C1-C 19 alkyl, -NH-C(=O)-O-C6-C 10 aryl, -NH-C(=O)-NH-C1-C6alkyl, -NH-C(=O)-NH-C6-C 10 acylamino groups consisting of aryl and -NH-C(=O)-N(C1-C6alkyl)2, selected from the group consisting of -N[-C(=O)-C1-C 19 alkyl]2 and -N[-C(=O)-C6-C 10 aryl]2, or N-acyl-N-C1-C6alkylamino; or

[0021] R b and R c both represent hydrogen, hydroxyl, or substituents that are the same as or different from those defined above; or

[0022] R b and R c are a 5- or 6-membered ring having the following general formula

[0023]

[0024] wherein, (*) indicates the attachment position,

[0025] R' and R''' are C1-C4 alkyl, and

[0026] R'' and R'''' are C1-C4 alkylene-hydroxy, C4-C 32 acyloxy, or C4-C 32 acyloxy-C1-C4 alkylene;

[0027] Each of R1 - R4 independently represents a C1 - C6 alkyl group; and

[0028] Each of R5 and R6 independently represents hydrogen, a C1 - C6 alkyl group or

[0029] a C6 - C 10 aryl group; or

[0030] R5 and R6 together represent oxygen. In an embodiment, the method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene includes the step of mixing polyethylene with 0.1 to 10 wt% of polypropylene based on the total weight of the mixture.

[0031] In an embodiment, the method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene includes the step of mixing polyethylene with at least one hydroxylamine ester having the formula (I).

[0032] In an embodiment, the method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene includes the step of mixing polyethylene with 0.001 to 1 wt% of at least one hydroxylamine ester having the formula (I) based on the total weight of the mixture. In an embodiment, the method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene includes the step of mixing polyethylene with polypropylene and at least one hydroxylamine ester having the formula (I).

[0033] In another embodiment, the method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene includes the step of mixing polyethylene with a compound selected from: 0.1 to 10 wt% of polypropylene based on the total weight of the mixture, 0.001 to 1 wt% of at least one hydroxylamine ester having the formula (I), or a combination thereof.

[0034] Polyethylene:

[0035] In an embodiment, the polyethylene is ultra - high 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).

[0036] In a preferred embodiment, the polyethylene is ultra-high molecular weight polyethylene (UHMWPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), or medium density polyethylene (MDPE).

[0037] In a more preferred embodiment, the polyethylene is linear low density polyethylene (LLDPE), or low density polyethylene (LDPE).

[0038] In an embodiment, the polyethylene has a density of 0.910 to 0.960 g / cm 3 and preferably 0.915 to 0.950 g / cm 3 .

[0039] The polyethylene is ultra-high molecular weight polyethylene (UHMWPE). Such UHMWPE has a molecular weight of several million, for example 3.5 to 7.5 million g / mol. Typically, the density tends to be less than that of high density polyethylene and can be in the range of 0.930 to 0.935 g / cm 3 .

[0040] High density polyethylene (HDPE) can also be processed according to the present invention, especially if the density does not exceed 0.960 g / cm 3 . Typically, HDPE has a density greater than 0.941 g / cm 3 .

[0041] LLDPE can be characterized in that it is a substantially linear polymer, but can have many short branches. The density of LLDPE typically ranges from 0.915 to 0.925 g / cm 3 .

[0042] Low density polyethylene can be characterized by having a high degree of short and long chain branching. Typically, LDPE can have a density in the range of 0.910 to 0.940 g / cm 3 . In the case of processing LDPE, desirably, the density is in the range of 0.915 to 0.940 g / cm 3 .

[0043] Suitably, the polyethylene used according to the present invention can be medium density polyethylene (MDPE). Typically, such medium density polyethylene (MDPE) has a density in the range of 0.926 to 0.940 g / cm 3 .

[0044] In an embodiment, the polyethylene is a recyclate.

[0045] In another embodiment, the polyethylene is virgin polyethylene, polyethylene recyclate, or a mixture thereof.

[0046] Recycled polyethylene may contain other polymers, such as polyolefins.

[0047] Recycled polyethylene can be obtained from domestic, commercial and industrial waste or from collections of useful materials. Recycled polyethylene can originate from separation and sorting, or from specific industrial sectors and return obligations, such as from the automotive industry, the electrical / electronic industry, construction, agriculture and the textile industry, or from domestic and commercial (e.g., supermarkets).

[0048] Polypropylene:

[0049] In an embodiment, polypropylene is selected from the group consisting of: polypropylene homopolymers, or polypropylene copolymers.

[0050] In an embodiment, polypropylene has a melt flow index greater than or equal to 0.5 g / 10 min.

[0051] In a preferred embodiment, polypropylene has a melt flow index greater than or equal to 2 g / 10 min.

[0052] In a more preferred embodiment, polypropylene has a melt flow index in the range of 0.5 to 2500 g / 10 min.

[0053] In a most preferred embodiment, polypropylene has a melt flow index in the range of 2 to 2500 g / 10 min.

[0054] The melt flow index (MFI) is measured at 230 °C with a load of 2.16 kg according to EN ISO 1133.

[0055] In an embodiment, the weight ratio of the total amount of polypropylene to the total amount of polyethylene is in the range of 0.5:99.5 to 10:90.

[0056] In a preferred embodiment, the weight ratio of the total amount of polypropylene to the total amount of polyethylene is in the range of 1:99 to 5:95.

[0057] The polypropylene-based polymers to be degraded according to the present invention may cover propylene homopolymers, or propylene copolymers. Propylene copolymers may contain various proportions of comonomers, for example up to about 90%, or up to about 50%. Examples of such comonomers are: olefins, such as 1-olefins, for example ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene, isobutene; cycloolefins, for example cyclopentene, cyclohexene, norbornene or ethylidene norbornene; dienes, such as butadiene, isoprene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene or norbornadiene; and also acrylic derivatives and unsaturated carboxylic anhydrides such as maleic anhydride.

[0058] Hydroxamic esters:

[0059] In an embodiment, the at least one hydroxylamine ester having the formula (I) is as follows:

[0060]

[0061] wherein R a represents an acyl group;

[0062] R b and one of R c represents hydrogen, a hydroxyl group, or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group, a C1-C6 alkoxy group, a C6-C 10 aryloxy group, selected from the group consisting of -O-C(=O)-H, -O-C(=O)-C1-C 19 alkyl group, -O-C(=O)-C1-C 54 alkenyl group, -O-C(=O)-C6-C 10 aryl group, -O-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl group, -O-C(=O)-O-C1-C 19 alkyl group, -O-C(=O)-O-C6-C 10 aryl group, -O-C(=O)-NH-C1-C6 alkyl group, -O-C(=O)-NH-C6-C 10 aryl group and -O-C(=O)-N(C1-C6 alkyl)2, acyloxy group, C1-C6 alkylamino group, di-C1-C6 alkylamino group, C6-C 10 arylamino group, selected from the group consisting of -NH-C(=O)-H, -NH-C(=O)-C1-C 19 alkyl group, -NH-C(=O)-C1-C 54 alkenyl group, -NH-C(=O)-C6-C 10 aryl group, -NH-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl group, -NH-C(=O)-O-C1-C 19 alkyl group, -NH-C(=O)-O-C6-C 10 aryl group, -NH-C(=O)-NH-C1-C6 alkyl group, -NH-C(=O)-NH-C6-C 10 aryl group and -NH-C(=O)-N(C1-C6 alkyl)2, acylamino group, selected from the group consisting of -N[-C(=O)-C1-C 19 alkyl]2 and -N[-C(=O)-C6-C 10 aryl]2, diacylamino group, or N-acyl-N-C1-C6 alkylamino group; or

[0063] R b and R c both represent hydrogen, a hydroxyl group, or a substituent that is the same as or different from those defined above; or

[0064] R b and R c are 5- or 6-membered rings having the following general formula

[0065]

[0066] wherein, (*) indicates the attachment position,

[0067] R' and R''' are C1-C4 alkyl groups, and

[0068] R'' and R'''' are C1-C4 alkylene-hydroxy, C4-C 32 acyloxy, or C4-C 32 acyloxy-C1-C4 alkylene;

[0069] R1-R4 each independently represent a C1-C6 alkyl group; and

[0070] R5 and R6 each independently represent hydrogen, a C1-C6 alkyl group or

[0071] C6-C 10 aryl; or

[0072] R5 and R6 together represent oxygen.

[0073] In the hydroxylamine ester having formula (I), with respect to the definition of R a the term acyl group preferably represents an acyl group selected from the group consisting of:

[0074] -C(=O)-H, -C(=O)-C1C 19 alkyl, -C(=O)-C2-C 19 alkenyl, -C(=O)-C2-C4 alkenyl-C6-C 10 aryl, -C(=O)-C6-C 10 aryl, -C(=O)-O-C1-C6 alkyl, -C(=O)-O-C6-C 10 aryl, -C(=O)-NH-C1-C6 alkyl, -C(=O)-NH-C6-C 10 aryl and -C(=O)-N(C1-C6 alkyl)2;

[0075] acyl R a the C1-C 19The alkyl group is, for example, a C1-C6 alkyl group such as methyl, ethyl, n-propyl or isopropyl, or n-butyl, sec-butyl or tert-butyl or a straight-chain or branched pentyl or hexyl group, or a C7-C 19 alkyl group, such as a straight-chain or branched heptyl, octyl, isooctyl, nonyl, tert-nonyl, decyl or undecyl group, or a straight-chain C 11 -C 19 alkyl group which, together with the -(C=O)- group, forms a C having an even number of C atoms 12 -C 20 alkanoyl group, such as lauroyl (C 12 ), myristoyl (C 14 ), palmitoyl (C 16 ) or stearoyl (C 18 ).

[0076] C6-C 10 The aryl group is, for example, a carbocyclic monoaryl or diaryl group, preferably a monoaryl group such as phenyl, which may be mono- or disubstituted by suitable substituents such as C1-C4 alkyl groups such as methyl, ethyl or tert-butyl, C1-C4 alkoxy groups such as methoxy or ethoxy, or halogen such as chlorine. In the case of disubstitution, the 2-position and the 6-position are preferred.

[0077] The acyl group R a mentioned above may be substituted at the free valence by suitable substituents (e.g., fluorine or chlorine) and is preferably formyl, acetyl, trifluoroacetyl, pivaloyl, acryloyl, methacryloyl, oleoyl, cinnamoyl, benzoyl, 2,6-dimethylbenzoyl, tert-butoxycarbonyl, ethylcarbamoyl or phenylcarbamoyl.

[0078] The C1-C6 alkyl group as R1-R4 is preferably a C1-C4 alkyl group, more preferably a C1-C2 alkyl group such as methyl or ethyl.

[0079] In a preferred embodiment, R1-R4 are methyl or ethyl. Alternatively, one to three of the substituents R1-R4 are ethyl. The remaining substituents are then methyl.

[0080] R5 and R6 are preferably hydrogen. The C1-C6 alkyl or C6-C 10 aryl group as R5 and R6 is preferably methyl or phenyl.

[0081] The hydroxylamine ester having the formula (I) is known or can be prepared by known methods, for example, by introducing the group R a in a conventional esterification reaction with an acid R a corresponding to the acyl group-OH, or a reactive functional derivative thereof (e.g., acyl halide R a-X, such as an acyl chloride) or an acid anhydride (such as (R a )2O) by acylating the corresponding >N-OH compound, and the acyl group is selected from the group consisting of, for example: -C(=O)-H, -C(=O)-C2-C 19 alkyl, -C(=O)-C2-C 19 alkenyl, -C(=O)-C2-C4 alkenyl-C6-C 10 aryl, -C(=O)-C6-C 10 aryl, -C(=O)-O-C1-C6 alkyl, -C(=O)-O-C6-C 10 aryl, -C(=O)-NH-C1-C6 alkyl, -C(=O)-NH-C6-C 10 aryl, and -C(=O)-N(C1-C6 alkyl)2. The hydroxamic acid esters of formula (I) and their preparation methods are described in WO 01 / 90113.

[0082] In the examples, the hydroxamic acid esters of formula (I) are selected from the group consisting of sterically hindered amine derivatives of formula (IA)

[0083]

[0084] wherein, R a represents an acyl group, R1’, R2’ and R3’ are each independently of the others hydrogen or methyl, and ALK represents a C2-C 10 alkylene or a C3-C 10 alkylene substituted by at least one substituent selected from the group consisting of: C1-C4 alkylene-hydroxy, C4-C 32 acyloxy, and C4-C 32 acyloxy-C1-C4 alkylene.

[0085] Examples of alkylene having up to 10 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, and decyl.

[0086] Examples of acyloxy having up to 32 carbon atoms are acetoxy, propionyloxy, butyryloxy, pentyryloxy, etc.

[0087] In a preferred embodiment, the hydroxamic acid esters of formula (I) are selected from the group consisting of sterically hindered amine derivatives of formula (IA’):

[0088]

[0089] wherein R1’ and R2’ independently of one another represent hydrogen or methyl;

[0090] R a represents a C2-C8 acyl group and

[0091] R a ’ represents a C8-C 22 acyl group.

[0092] Examples of acyl groups having up to 22 carbon atoms are acetyl, propionyl, butyryl, valeryl, and the like.

[0093] In a more preferred embodiment, the hydroxylamine ester having the formula (I) is selected from the sterically hindered amine derivatives having the formula (IA”)

[0094]

[0095] C1 to C 21 Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, and henicosanyl.

[0096] In a most preferred embodiment, the hydroxylamine ester having the formula (I) is a compound having the formula (IA”’)

[0097]

[0098] In an embodiment, a method of increasing the drawability and / or melt strength and / or melt elasticity of polyethylene comprises the step of mixing polyethylene with a compound selected from: polypropylene, a hydroxylamine ester as defined above in an amount of 0.001 to 1 wt% based on the total weight of the mixture, or a combination thereof, said hydroxylamine esters being selected from sterically hindered amines having the formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof.

[0099] In an embodiment, the mixing step comprises mixing polypropylene and / or a hydroxylamine ester as defined above with polyethylene sequentially or simultaneously, the hydroxylamine esters being selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), or (IA”’) or a mixture of two or more thereof.

[0100] In another embodiment, the mixing step comprises mixing a premixed polyethylene and polypropylene with a hydroxylamine ester as defined above selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), or (IA”’) or a mixture of two or more thereof.

[0101] In an embodiment, the weight ratio of the total amount of the hydroxylamine esters selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof as defined above to the total amount of polyethylene is in the range of 0.001:99.999 to 0.05:99.95.

[0102] In a preferred embodiment, the weight ratio of the total amount of the hydroxylamine esters selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof as defined above to the total amount of polyethylene is in the range of 0.01:99.99.

[0103] In a more preferred embodiment, the weight ratio of the total amount of the hydroxylamine esters selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof as defined above to the total amount of polyethylene is in the range of 0.013:99.97.

[0104] In an embodiment, the weight ratio of the total amount of the compounds selected from the following to the total amount of polyethylene is in the range of 0.01:99.99 to 10:90: polypropylene, a hydroxylamine ester selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof as defined above, or a combination thereof.

[0105] In a preferred embodiment, the weight ratio of the total amount of the compounds selected from the following to the total amount of polyethylene is in the range of 0.01:99.99 to 6:94: polypropylene, a hydroxylamine ester selected from sterically hindered amines having formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof as defined above, or a combination thereof.

[0106] In an embodiment, the mixing step further comprises an additive selected from the group consisting of a light stabilizer, an antioxidant, a visbreaking agent other than the hydroxylamine ester of formula (I), a metal deactivator, a phosphite and phosphonite, a nitrone, a sulfur synergist, a peroxide scavenger, a basic co-stabilizer, a nucleating agent, a filler and a reinforcing agent, a benzofuranone, an indolinone, a slip additive, an acid scavenger, a lubricant, a polymer processing aid, an anti-blocking additive, an anti-fogging additive, an activator, or a mixture of two or more thereof.

[0107] These additives are commonly used in the plastics industry. Examples of slip additives and acid scavengers are described in Chapter 4 of the Plastic Additives Handbook

[0108] [Plastic Additives Handbook]; examples of lubricants are described in Chapter 5 of the Plastic Additives Handbook; polymer processing aids are described in Chapter 6 of the Plastic Additives Handbook; examples of anti-blocking additives are given in Chapter 7 of the Plastic Additives Handbook;

[0109] and examples of anti-fogging additives are given in Chapter 9 of the Plastic Additives Handbook. Each is referenced to the Plastic Additives Handbook

[0110] [Plastic Additives Handbook], 5th Edition, edited by Hans Zweifel, Hanser Munich, ISBN 3-446-21654-5.

[0111] Specific examples of the above-mentioned additives are given below.

[0112] 1. Antioxidants

[0113] 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 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-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched in the side chain nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecan-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

[0114] 1.2. Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-bis(dodecylthiomethyl)-4-nonylphenol.

[0115] 1.3. Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 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.

[0116] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).

[0117] 1.5. Hydroxylated thiodiphenyl ethers, such as 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.

[0118] 1.6. Alkylene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-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'-ethylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-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-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 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-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0119] 1.7. O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl 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-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0120] 1.8. Hydroxybenzylated malonic acid esters, such as dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, bis(2-mercaptoethyl)dodecyl 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.

[0121] 1.9. Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-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.

[0122] 1.10. Triazine compounds, such as 2,4-bis(octylthio)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylthio-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylthio-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(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0123] 1.11. Benzylphosphonic acid esters, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

[0124] 1.12. Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0125] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with: monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, isooctanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(2-hydroxyethyl)isocyanurate, N,N'-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0126] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with: monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, isooctanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(2-hydroxyethyl)isocyanurate, N,N'-bis(2-hydroxyethyl)oxalamide, 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)propanoyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0127] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, such as esters with: methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(2-hydroxyethyl)isocyanurate, N,N'-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0128] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with: monohydric or polyhydric alcohols, such as methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(2-hydroxyethyl)isocyanurate, N,N'-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0129] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)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( XL-1, supplied by Uniroyal).

[0130] 1.18. Ascorbic acid (vitamin C)

[0131] 1.19. Amine antioxidants such as N,N'-diisopropyl-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-toluenesulfonyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 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'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octyldiphenylamines, mixtures of monoalkylated and dialkylated nonyldiphenylamines, mixtures of monoalkylated and dialkylated dodecyldiphenylamines, mixtures of monoalkylated and dialkylated isopropyl / isopropyldiphenylamines, mixtures of monoalkylated and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octylphenothiazines, mixtures of monoalkylated and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0132] 2. UV absorbers and light stabilizers

[0133] 2.1.2-(2'-Hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 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'-octoxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexoxy)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-octoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexoxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctoxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-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'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0134] 2.2.2-Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0135] 2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, cetyl 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.

[0136] 2.4. Acrylate / cinnamate, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β,β-methyl-p-methoxycinnamate, methyl α-methoxycarbonyl-p-methoxycinnamate, N-(β-methoxycarbonyl-β-cyanoethenyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate). Other cyanoacrylates can also be used and such compounds are given in EP 3587425.

[0137] 2.5. Nickel compounds, such as nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid such as methyl ester or ethyl ester, nickel complexes of ketoximes such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

[0138] 2.6. Sterically hindered amines, such as 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-hydroxybenzyl malonate, condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensate 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 condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 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, 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, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,Condensates of 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); condensates of 1,6-hexanediamine, 2,4,6-trichloro-1,3,5-triazine, N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [192268-64-7]); reaction products of 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, 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)ethylene; N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine; diesters of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine; poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane; reaction products of maleic anhydride-a-olefin copolymers and 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-tetramethylpiperidin-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 Registry No. 106917-31-1), 1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-3-dodecylpyrrolidine-2,5-dione, reaction products of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine and N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine.,

[0139] 2.7. Oxamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethyloxy-2'-ethyl oxanilide, N,N'-bis(3-dimethylaminopropyl) oxamide, 2-ethyloxy-5-tert-butyl-2'-ethyl oxanilide and mixtures thereof with 2-ethyloxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of ortho- and para-methoxy-disubstituted oxanilides, and mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

[0140] 2.8.2-(2-Hydroxyphenyl)-1,3,5-triazine, such as 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-propoxyphenyl)-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-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octoxypropoxy)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-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-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-hydroxypropoxy]phenyl}-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.

[0141] 3. Metal deactivators, such as N,N'-diphenyl oxamide, N-salicylaldehyde-N'-salicylhydrazide, N,N'-bis(salicyl)hydrazide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, 3-salicylamido-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl diphenylhydrazide, N,N'-diacetyladipic dihydrazide, N,N'-bis(salicyl)oxalyl dihydrazide, N,N'-bis(salicyl)thiopropionyl dihydrazide.

[0142] 4. Phosphites and phosphonites, such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecoxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetra(2,4-di-tert-butylphenyl) 4,4'-biphenylylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[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-dibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2',2"-nitrilo[triethyl tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, poly(4,4'-{isopropylidenediphenol}-octyl phosphite), poly(4,4'-{isopropylidenebis[2,6-dibromophenol]}-octyl phosphite), poly(4,4'-{2,2'-dimethyl-5,5'-di-tert-butylphenyl sulfide}-pentaerythritol diphosphite), mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl phosphite triesters (CAS No. 939402-02-5), triphenyl phosphite polymer with α-hydro-ω-hydroxy poly[oxy(methyl-1,2-ethanediyl)] C 10-16 alkyl ester polymer (CAS No. 1227937-46-3).

[0143] Particularly preferred are the following phosphites:

[0144] Tris(2,4-di-tert-butylphenyl) phosphite ( 168, BASF SE), tris(nonylphenyl) phosphite,

[0145]

[0146]

[0147] 5. Hydroxylamines, such as N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dicetylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamines derived from hydrogenated tallow amine or derived from plant sources.

[0148] 6. Nitrones, such as N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-dodecyl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0149] 7. Thio synergists, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate] or distearyl disulfide.

[0150] 8. Peroxide scavengers, such as esters of β-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl ester or tridecyl ester, mercaptobenzimidazole, or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, distearyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0151] 9. Basic co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids (such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate), antimony pyrocatecholate or zinc pyrocatecholate.

[0152] 10. Nucleating agents, such as inorganic substances like talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulfates of alkaline earth metals; organic compounds, such as monocarboxylic or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ion copolymers (ionomers). Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(p-methylbenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.

[0153] 11. Fillers and reinforcing agents, such as calcium carbonate, silicates, surface-treated silica (as described, for example, in US-A-2007 / 60,697 and US-A-2009 / 111,918), glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and powders or fibers of other natural products, synthetic fibers.

[0154] 12. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents. Other additives may also include anti-blocking additives as mentioned above, which are used in the film to reduce the negative adhesion of two polyethylene surfaces to each other (otherwise this would lead to difficulties in separating the film). Further additives include slip additives as mentioned above, which are used to help the film surfaces slide over each other. Anti-fogging agents as mentioned above can also be added.

[0155] 13. Benzofuranones and indolinones, such as those disclosed in the following: 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-stearoyloxyethoxy)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-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-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-isooctylbenzofuran-2-one. Suitable benzofuranones also include the compounds identified in WO 2015 / 121445 and WO 2017 / 025431.

[0156] 14. Visbreaking agent

[0157] A visbreaking agent or a typical free radical initiator. Typically, this includes organic or inorganic peroxides, azo compounds, and cumene widely used in industry.

[0158] 14.1 Peroxides

[0159] Examples of peroxides suitable as visbreaking agents include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, 3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxacyclononane, tert-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl diperoxide, tert-butyl cumyl peroxide, tert-butyl hydroxyethyl peroxide, di-tert-amyl peroxide, and 2,5-dimethylhex-2-ene-2,5-diisononanoate, acetylcyclohexanesulfonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl perneodecanoate, tert-butyl perpivalate, tert-amyl perpivalate, 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, tert-butyl 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 perisononanoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,5-di-tert-butylperoxide, 3-tert-butylperoxy-3-phenylphthalide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, 3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylhexyne 2,5-di-tert-butylperoxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide, or tert-butyl hydroperoxide.

[0160] 14.2. Di-azo compounds

[0161] 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-methoxypentanenitrile, 2,2'-azobis(isobutyric acid dimethyl ester), 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethylisobutamidine) in free base or hydrochloride form, 2,2'-azobis(2-amidinopropane) in free base or hydrochloride form, 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}.

[0162] 14.3 Cumene

[0163] Examples of cumene as a visbreaking agent include 2,3-dimethyl-2,3-diphenylbutane, or 3,4-dimethyl-3,4-diphenylhexane.

[0164] 15. Activator

[0165] Examples of activators are thiols, disulfides, thioesters, or thiourethanes.

[0166] 15.1 Thiol

[0167] Examples of thiols and dithiols as suitable activators have the following formula

[0168] R-S-A

[0169] or

[0170] R-S-S-R

[0171] where

[0172] R is a monovalent, divalent, trivalent or tetravalent hydrocarbon group attached to the sulfur atom by a carbon atom, and A is hydrogen or -SO3 - , B + is an organic or inorganic cation.

[0173] Also included are thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles and sulfenamides.

[0174] R as a hydrocarbon group attached to the sulfur atom by a carbon atom is, for example, C8-C 22alkyl, hydroxy-C2-C8 alkyl, mercapto-C2-C8 alkyl, mercapto-C8-C into which one or more -NH- groups are inserted 20 alkyl, mercapto-C8-C into which one or more -OCO- groups are inserted 20 alkyl, mercapto-C8-C substituted by one or more hydroxyl groups 18 alkyl, C8-C 10 aryl or C6-C substituted by one or more substituents selected from the group consisting of the following 10 aryl: C1-C4 alkyl, 4-thienyl, 3-methyl-4-thienyl and C6-C 10 aryl-C1-C4 alkyl.

[0175] cation or cationic group B + is, for example, an alkali metal cation (such as sodium ion or potassium ion), ammonium ion, tri-C1-C4 alkylammonium ion (such as tetramethylammonium ion or tetraethylammonium ion), or choline base cation.

[0176] In a preferred embodiment, the thiol and dithiol are octadecyl mercaptan, pentaerythritol tetra(3-mercaptopropionate).

[0177] 15.2 Thiourane:

[0178] Examples of thiourane as a suitable activator have the following formula

[0179]

[0180] A is based on an organic isocyanate, wherein the group -S-R is introduced by reacting with an isocyanate group

[0181] R is a C2-C optionally substituted and / or inserted 40 alkyl, and

[0182] n is equal to or greater than 1.

[0183] A is preferably based on an organic isocyanate, each of which is an arylalkyl diisocyanate, aryl diisocyanate, isophorone diisocyanate or diarylalkane diisocyanate that is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino, or is a C4-C 20 alkyl diisocyanate, or an oligomeric or polymeric product obtained by reacting the above diisocyanates with themselves and / or with polyols.

[0184] The polyol is preferably a C1-C alkanol containing two or more hydroxyl groups, or a poly-C2-C 10 alkylene glycol. 10

[0185] ​The corresponding organic isocyanates are known or can be obtained according to known methods such as from WO 05 / 070987.

[0186] R can be inserted with, for example, -O-, -NH-, -S- and / or carbonyl. A possible substituent of R is -SH. The corresponding C8-C 40 alkyl, especially C8-C 20 alkyl is preferred.

[0187] In view of the above, the term "isocyanate functionalized with a sulfur compound" is related to the corresponding thiourethane.

[0188] In an embodiment, the additive is present in the polymer melt in an amount of 0.001 to 10 wt% based on the total weight of the polyethylene.

[0189] In a preferred embodiment, the additive is present in the polymer melt in an amount of 0.001 to 5 wt% based on the total weight of the polyethylene.

[0190] In an embodiment, a conventional filler or reinforcing agent can be present in the polymer melt in an amount of 0.1 to 10 wt% based on the total weight of the polyethylene.

[0191] In a preferred embodiment, a conventional filler or reinforcing agent can be present in an amount of 1 to 5 wt% based on the total weight of the polyethylene.

[0192] In another aspect, the invention claimed herein relates to a polyethylene composition comprising: 80 to 99.8 wt% of polyethylene based on the total weight of the composition; and a compound selected from: 0.1 to 10 wt% of polypropylene based on the total weight of the composition, 0.001 to 1 wt% of a hydroxylamine ester as defined above based on the total weight of the composition, or a combination thereof, wherein these hydroxylamine esters are selected from sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof.

[0193] The polyethylene composition further comprises an additive selected from: a light stabilizer, an antioxidant, a visbreaking agent other than the hydroxylamine ester having the formula (I), a metal deactivator, a phosphite and a phosphonite, a nitrone, a sulfur synergist, a peroxide scavenger, a basic co-stabilizer, a nucleating agent, a filler and a reinforcing agent, a benzofuranone, an indolinone, a slip additive, an acid scavenger, an anti-blocking additive, an anti-fogging additive, an activator, or a mixture of two or more thereof.

[0194] The polyethylene, polypropylene and additive are selected from the groups as defined above.

[0195] In yet another aspect, the present invention relates to the use of polypropylene and / or hydroxylamine esters, as defined above, for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, said hydroxylamine esters being selected from the hindered amines of formula (I), (IA), (IA’), (IA”), (IA”’) or mixtures of two or more thereof.

[0196] In an embodiment, the polyethylene is a polyethylene film or fiber.

[0197] Accordingly, another aspect of the present invention is an article comprising a polyethylene composition as defined above.

[0198] In an embodiment, the article is a polyethylene film or fiber.

[0199] The invention claimed herein provides one or more of the following advantages:

[0200] 1. A method for improving the processability of polyethylene.

[0201] 2. A method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene during processing, especially during extrusion of polyethylene.

[0202] Hereinafter, specific embodiments of the invention claimed herein are described:

[0203] 1. A method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, the method comprising the step of mixing the polyethylene with a compound selected from: 0.1 to 10 wt% of polypropylene, based on the total weight of the mixture, at least one hydroxylamine ester of formula (I), or a combination thereof

[0204]

[0205] wherein R a represents an acyl group;

[0206] R b and one of R c represents hydrogen, hydroxyl, or C1-C6 alkyl, and the other is C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 aryloxy, selected from -O-C(=O)-H, -O-C(=O)-C1-C 19 alkyl, -O-C(=O)-C1-C 54 alkenyl, -O-C(=O)-C6-C 10 aryl, -O-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl, -O-C(=O)-O-C1-C 19alkyl, -O-C(=O)-O-C6-C 10 aryl, -O-C(=O)-NH-C1-C6 alkyl, -O-C(=O)-NH-C6-C 10 acyloxy groups, C1-C6 alkylamino, di-C1-C6 alkylamino, C6-C 10 arylamino, selected from the group consisting of -NH-C(=O)-H, -NH-C(=O)-C1-C 19 alkyl, -NH-C(=O)-C1-C 54 alkenyl, -NH-C(=O)-C6-C 10 aryl, -NH-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl, -NH-C(=O)-O-C1-C 19 alkyl, -NH-C(=O)-O-C6-C 10 aryl, -NH-C(=O)-NH-C1-C6 alkyl, -NH-C(=O)-NH-C6-C 10 acylamino groups, selected from the group consisting of -NH-C(=O)-C1-C 19 alkyl]2 and -NH-C(=O)-C6-C 10 aryl]2, or N-acyl-N-C1-C6 alkylamino; or

[0207] R b and R c both represent hydrogen, hydroxy, or substituents the same as or different from those defined above; or

[0208] R b and R c are a 5- or 6-membered ring having the following general formula

[0209]

[0210] wherein, (*) indicates the attachment position,

[0211] R’ and R’’’ are C1-C4 alkyl, and

[0212] R” and R”” are C1-C4 alkylene-hydroxy, C4-C 32 acyloxy, or C4-C 32 acyloxy-C1-C4 alkylene;

[0213] R1-R4 each independently of one another represent C1-C6 alkyl; and

[0214] R5 and R6 each independently of one another represent hydrogen, C1-C6 alkyl or

[0215] C6-C 10 aryl; or

[0216] R5 and R6 together represent oxygen.

[0217] 2. The method according to embodiment 1, wherein increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with 0.1 to 10 wt% of polypropylene based on the total weight of the mixture.

[0218] 3. The method according to embodiment 1, wherein increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with at least one hydroxylamine ester having formula (I).

[0219] 4. The method according to embodiment 1, wherein increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with 0.001 to 1 wt% of at least one hydroxylamine ester having formula (I) based on the total weight of the mixture.

[0220] 5. The method according to embodiment 1, wherein increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with polypropylene and at least one hydroxylamine ester having formula (I).

[0221] 6. The method according to any one of embodiments 1, 3, 4 and 5, wherein the hydroxylamine ester having formula (I) is selected from the group consisting of sterically hindered amine derivatives having formula (IA)

[0222]

[0223] wherein, R a represents acyl, R1’, R2’ and R3’ are each independently of one another hydrogen or methyl, and ALK represents C2-C substituted with at least one substituent selected from the group consisting of 10 alkylene or C3-C 10 alkylene: C1-C4 alkylene-hydroxy, C4-C 32 acyloxy and C4-C 32 acyloxy-C1-C4 alkylene.

[0224] 7. The method according to any one of embodiments 1 to 6, wherein the hydroxylamine ester having formula (I) is selected from the group consisting of sterically hindered amine derivatives having formula (IA’)

[0225]

[0226] wherein R1’ and R2’ independently of one another represent hydrogen or methyl;

[0227] R a represents a C2-C8 acyl group; and

[0228] R a ’ represents a C8-C 22 acyl group.

[0229] 8. The method according to any one of embodiments 1 to 7, wherein the hydroxylamine ester having the formula (I) is selected from the sterically hindered amine derivatives having the formula (IA”).

[0230]

[0231] 9. The method according to any one of embodiments 1 to 8, wherein the hydroxylamine ester having the formula (I) is a compound having the formula (IA”’).

[0232]

[0233] 10. The method according to any one of embodiments 1 to 9, wherein increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with a compound selected from: polypropylene, a hydroxylamine ester as defined in embodiments 6 to 9 in an amount of 0.001 to 1 wt% based on the total weight of the mixture, or a combination thereof, and these hydroxylamine esters are selected from the sterically hindered amines having the formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof.

[0234] 11. The method according to any one of embodiments 1 to 10, wherein the mixing step comprises mixing the polypropylene and / or the hydroxylamine ester as defined in embodiments 6 to 9 with the polyethylene sequentially or simultaneously, and these hydroxylamine esters are selected from the sterically hindered amines having the formula (I), (IA), (IA’), (IA”) or (IA”’) or a mixture of two or more thereof.

[0235] 12. The method according to any one of embodiments 1 to 11, wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE or PE-WAX), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), high density crosslinked polyethylene (HDXLPE), crosslinked 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).

[0236] 13. The method according to any one of embodiments 1 to 12, wherein the polyethylene is linear low density polyethylene (LLDPE), or low density polyethylene (LDPE).

[0237] 14. The method according to any one of embodiments 1 to 13, wherein the polyethylene has a density of 0.910 to 0.960 g / cm 3 3.

[0238] 15. The method according to any one of embodiments 1 to 14, wherein the polyethylene is a recycled material.

[0239] 16. The method according to any one of embodiments 1 to 11, wherein the polypropylene is selected from the group consisting of: polypropylene homopolymer, or polypropylene copolymer.

[0240] 17. The method according to any one of embodiments 1 to 11 and 16, wherein the polypropylene has a melt flow index greater than or equal to 0.5 g / 10 min.

[0241] 18. The method according to any one of embodiments 1 to 17, wherein the weight ratio of the total amount of polypropylene to the total amount of polyethylene is in the range of 0.5:99.5 to 10:90.

[0242] 19. The method according to any one of embodiments 1 to 17, wherein the weight ratio of the total amount of polypropylene to the total amount of polyethylene is in the range of 1:99 to 5:95.

[0243] 20. The method according to any one of embodiments 1 to 15, wherein the weight ratio of the total amount of the hydroxylamine ester selected from the sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof as defined in embodiments 6 to 9 to the total amount of polyethylene is in the range of 0.001:99.999 to 0.05:99.95.

[0244] 21. The method according to any one of embodiments 1 to 15, wherein the weight ratio of the total amount of the hydroxylamine ester selected from the sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof as defined in embodiments 6 to 9 to the total amount of polyethylene is in the range of 0.01:99.99.

[0245] 22. The method according to any one of embodiments 1 to 21, wherein the mixing step further comprises an additive selected from the group consisting of: a light stabilizer, an antioxidant, a visbreaking agent other than those having the hydroxylamine ester of formula (I), a metal deactivator, a phosphite and a phosphonite, a nitrone, a sulfur synergist, a peroxide scavenger, a basic co-stabilizer, a nucleating agent, a filler and a reinforcing agent, a benzofuranone, an indolinone, a slip additive, an acid scavenger, an anti-blocking additive, an anti-fogging additive, an activator, or a mixture of two or more thereof.

[0246] 23. A polyethylene composition comprising

[0247] i. 80 to 99.8 wt% of polyethylene based on the total weight of the composition; and

[0248] ii. a compound selected from the group consisting of: 0.1 to 10 wt% of polypropylene based on the total weight of the composition, 0.001 to 1 wt% of a hydroxylamine ester as defined in embodiments 6 to 9 based on the total weight of the composition, or a combination thereof, the hydroxylamine esters being selected from sterically hindered amines having formula (I), (IA), (IA'), (IA"), (IA'''), or a mixture of two or more thereof.

[0249] 24. The polyethylene composition according to embodiment 23, wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE or PE-WAX), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), high density crosslinked polyethylene (HDXLPE), crosslinked 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).

[0250] 25. The polyethylene composition according to any one of embodiments 23 and 24, wherein the polyethylene is linear low density polyethylene (LLDPE), or low density polyethylene (LDPE).

[0251] 26. The polyethylene composition according to embodiment 23, wherein the polypropylene is a polypropylene homopolymer, or a polypropylene copolymer.

[0252] 27. The polyethylene composition according to any one of embodiments 23 to 26, further comprising an additive selected from the group consisting of: a light stabilizer, an antioxidant, a visbreaking agent other than the hydroxylamine ester having the formula (I), a metal deactivator, a phosphite and a phosphonite, a nitrone, a sulfur synergist, a peroxide scavenger, a basic co-stabilizer, a nucleating agent, a filler and a reinforcing agent, a benzofuranone, an indolinone, a slip additive, an acid scavenger, an anti-blocking additive, an anti-fogging additive, an activator, or a mixture of two or more thereof.

[0253] 28. Use of polypropylene and / or hydroxylamine ester according to any one of the preceding claims for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, said hydroxylamine esters being selected from the group consisting of sterically hindered amines having the formula (I), (IA), (IA'), (IA''), (IA''') or a mixture of two or more thereof.

[0254] 29. Use according to embodiment 28, wherein the polyethylene is a polyethylene film or fiber.

[0255] 30. An article comprising the polyethylene composition according to any one of embodiments 23 to 27.

[0256] 31. The article according to embodiment 30, wherein the articles are polyethylene films or fibers.

[0257] The following examples illustrate the invention in more detail. Unless otherwise stated, all percentages and parts are by weight.

[0258] Examples

[0259] Additives used:

[0260] 1. Polypropylene Evalene PHF0301 (PP1) from JG Summit Olefins Corporation: MFI 3 g / cm 3 ; density 0.900 g / cm 3

[0261] 2. Hydroxylamine ester: a compound having the formula (IA'''):

[0262] IUPAC name: 9-acetoxy-3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9-azaspiro [5,5] undec-3-yl-methyl stearate

[0263]

[0264] Example 1

[0265] Preparation:

[0266] In a high-speed mixer F35 MTU from MTI GmbH, Germany, the additives as indicated above and a 70 / 30 combination of PE-LD (ground Riblene FC 30) and PE-LLD (ground Dowlex SC 2108G) as the matrix are used to produce a mixture. The mixture is compounded at 230 °C using a twin-screw compounding unit 25 / 42D from Collin GmbH, Germany to obtain well-homogenized pellets.

[0267] Testing of drawability and melt strength:

[0268] The drawability and melt strength of these compounds are tested using a rheotense test device with a single-screw extruder from Göttfert GmbH, Germany connected thereto.

[0269] The test temperature is 190 °C. The sample is uniaxially drawn to a set of accelerating nips located 100 mm below the die, with an acceleration of 2.4 mm / s2. The tensile force (cN) is recorded as a function of the take-up speed of the nip rolls. The higher the value, the better the improvement in terms of melt strength.

[0270] The drawability is reported as the maximum ratio v / v0 of the draw to the initial extrusion rate before the occurrence of the draw resonance (as an indication of the draw perturbation and a limit to increasing throughput). The melt strength is the steady force before the strand breaks. The higher the ratio v / v0 (draw speed / initial extrusion speed at time zero) the better.

[0271] Results: The above results show that the drawability and melt strength of the polyethylene thus treated according to the invention are superior to the reference formulation.

[0272] Surprisingly, if polypropylene is present in the composition, the addition of the compound of formula (IA”’) does not result in the expected decrease in melt strength due to degradation, see Examples 1 and 2 of the invention compared to Comparative Example 4. Particularly surprisingly, in the presence of both polypropylene and the compound of formula (IA”’), the drawability increases significantly, see Examples 1 and 2 of the invention compared to Comparative Examples 1-4. This is even more surprising since the presence of the compound of formula (IA”’) was expected to cause degradation of the polypropylene.

Claims

1. A method for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, the method comprising the step of mixing the polyethylene with 0.1 to 10 wt% of polypropylene, based on the total weight of the mixture, and at least one hydroxylamine ester having the formula (I) wherein R a represents an acyl group; R b and R c one of which represents hydrogen, a hydroxyl group, or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group, a C1-C6 alkoxy group, a C6-C 10 aryloxy group, selected from the group consisting of -O-C(=O)-H, -O-C(=O)-C1-C 19 alkyl group, -O-C(=O)-C1-C 54 alkenyl group, -O-C(=O)-C6-C 10 aryl group, -O-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl group, -O-C(=O)-O-C1-C 19 alkyl group, -O-C(=O)-O-C6-C 10 aryl group, -O-C(=O)-NH-C1-C6 alkyl group, -O-C(=O)-NH-C6-C 10 aryl group and acyloxy groups of the group consisting of -O-C(=O)-N(C1-C6 alkyl)2, C1-C6 alkylamino groups, di-C1-C6 alkylamino groups, C6-C 10 arylamino groups, selected from the group consisting of -NH-C(=O)-H, -NH-C(=O)-C1-C 19 alkyl group, -NH-C(=O)-C1-C 54 alkenyl group, -NH-C(=O)-C6-C 10 aryl group, -NH-C(=O)-C1-C 36 alkenyl-C6-C 10 aryl group, -NH-C(=O)-O-C1-C 19 alkyl group, -NH-C(=O)-O-C6-C 10 aryl group, -NH-C(=O)-NH-C1-C6 alkyl group, -NH-C(=O)-NH-C6-C 10 aryl group and acylamino groups of the group consisting of -NH-C(=O)-N(C1-C6 alkyl)2, selected from the group consisting of -N[-C(=O)-C1-C 19 alkyl]2 and -N[-C(=O)-C6-C 10 aryl]2, or N-acyl-N-C1-C6 alkylamino groups; or R b and R c each represent hydrogen, a hydroxyl group, or a substituent the same as or different from those defined above; or R b and R c is a 5- or 6-membered ring having the following general formula Among them, (*) indicates the attachment position, R’ and R”’ are C1-C4 alkyl groups, and R” and R”” are C1-C4 alkylene-hydroxy, C4-C 32 acyloxy, or C4-C 32 acyloxy-C1-C4 alkylene; R1-R4 each independently represent a C1-C6 alkyl group; and R5 and R6 each independently represent hydrogen, a C1-C6 alkyl group or C6-C 10 aryl; or R5 and R6 together represent oxygen.

2. The method according to claim 1, wherein Increasing the drawability and / or melt strength and / or melt elasticity of polyethylene comprises the step of mixing the polyethylene with at least one hydroxylamine ester having the formula (I) in an amount of 0.001 to 1 wt% based on the total weight of the mixture.

3. The method according to claim 1 or 2, wherein The hydroxylamine ester having the formula (I) is selected from the group consisting of sterically hindered amine derivatives having the formula (IA) Wherein, R a represents an acyl group, R1’, R2’ and R3’ are each independently of one another hydrogen or methyl, and ALK represents a C2-C 10 alkylene or a C3-C 10 alkylene substituted with at least one substituent selected from the group consisting of: C1-C4 alkylene-hydroxy, C4-C 32 acyloxy and C4-C 32 acyloxy-C1-C4 alkylene.

4. The method according to any one of claims 1 to 3, wherein, The hydroxylamine ester having the formula (I) is selected from the group consisting of sterically hindered amine derivatives having the formula (IA’) wherein R1’ and R2’ independently of one another represent hydrogen or methyl; R a represents a C2-C8 acyl group; and R a ' represents C8-C 22 acyl group.

5. The method according to any one of claims 1 to 4, wherein The hydroxylamine ester having the formula (I) is selected from the group consisting of sterically hindered amine derivatives having the formula (IA”) 6. The method according to any one of claims 1 to 5, wherein, The hydroxylamine ester having the formula (I) is a compound having the formula (IA”’) 7. The method according to any one of claims 1 to 6, wherein Increasing the drawability and / or melt strength and / or melt elasticity of the polyethylene comprises the step of mixing the polyethylene with a compound selected from the following: polypropylene, hydroxylamine esters in an amount of 0.001 to 1 wt% based on the total weight of the mixture, said hydroxylamine esters being selected from sterically hindered amines having the formula (I), (IA), (IA’), (IA”), (IA”’) or a mixture of two or more thereof.

8. The method according to any one of claims 1 to 7, wherein The mixing step comprises mixing the polypropylene and / or these hydroxylamine esters with the polyethylene either sequentially or simultaneously, said hydroxylamine esters being selected from sterically hindered amines having the formula (I), (IA), (IA’), (IA”) or (IA”’) or a mixture of two or more thereof.

9. The method according to any one of claims 1 to 8, wherein The polyethylene is ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE or PE-WAX), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), high density crosslinked polyethylene (HDXLPE), crosslinked 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).

10. The method according to any one of claims 1 to 9, wherein, The polyethylene is linear low density polyethylene (LLDPE), or low density polyethylene (LDPE).

11. The method according to any one of claims 1 to 10, wherein This polyethylene has a density of 0.910 to 0.960 g / cm 3 .

12. The method according to any one of claims 1 to 11, wherein The polyethylene is a recycled material.

13. The method according to any one of claims 1 to 8, wherein The polypropylene is selected from the group consisting of: polypropylene homopolymer, or polypropylene copolymer.

14. The method according to any one of claims 1 to 8 and 13, wherein, The polypropylene has a melt flow index of greater than or equal to 0.5 g / 10 min.

15. The method according to any one of claims 1 to 14, wherein, The weight ratio of the total amount of polypropylene to the total amount of polyethylene is in the range of 0.5:99.5 to 10:

90.

16. The method according to any one of claims 1 to 12, wherein The weight ratio of the total amount of the hydroxylamine ester selected from the sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof to the total amount of polyethylene is in the range of 0.001:99.999 to 0.05:99.

95.

17. The method according to any one of claims 1 to 16, wherein The mixing step further comprises additives selected from: light stabilizers, antioxidants, visbreaking agents other than these hydroxylamine esters having the formula (I), metal deactivators, phosphites and phosphonites, nitrones, thio synergists, peroxide scavengers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones, indolinones, slip additives, acid scavengers, anti-blocking additives, anti-fogging additives, activators, or a mixture of two or more thereof.

18. A polyethylene composition comprising i. 80 to 99.8 wt% of polyethylene based on the total weight of the composition; and ii. Compounds selected from: 0.1 to 10 wt% of polypropylene based on the total weight of the composition, 0.001 to 1 wt% of hydroxylamine ester based on the total weight of the composition, or a combination thereof, these hydroxylamine esters being selected from the sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof.

19. The polyethylene composition according to claim 18, which further comprises additives selected from: light stabilizers, antioxidants, visbreaking agents other than the hydroxylamine esters having the formula (I), metal deactivators, phosphites and phosphonites, nitrones, thio synergists, peroxide scavengers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones, indolinones, slip additives, acid scavengers, anti-blocking additives, anti-fogging additives, activators, or a mixture of two or more thereof.

20. Use of polypropylene and / or hydroxylamine ester as defined in any of the preceding claims for increasing the drawability and / or melt strength and / or melt elasticity of polyethylene, these hydroxylamine esters being selected from the sterically hindered amines having the formula (I), (IA), (IA'), (IA"), (IA"') or a mixture of two or more thereof.

21. The use according to claim 20, wherein, The polyethylene is a polyethylene film or fiber.

22. An article comprising the polyethylene composition according to claim 18 or 19.

23. The article according to claim 22, wherein, These articles are polyethylene films or fibers.

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