Environmentally friendly processing aid based on modified polyacrylate polymer

Abstract

The present invention relates to a shaped polymeric article comprising a thermoplastic polymer; and a modified polyacrylate polymer obtainable by a process comprising i. polymerizing at least one methacrylate monomer and / or at least one acrylate monomer selected from substituted or unsubstituted C1-C22 alkyl acrylates, substituted or unsubstituted C4-C22 cycloalkyl acrylates, substituted or unsubstituted C1-C22 acrylamides, or esters of acrylic acid with polyalkylether alcohols, to obtain at least one polyacrylate polymer; and ii. modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one alcohol selected from unsubstituted C8-C36 alcohols (c1), or polyalkylether alcohols (c2). The present invention also relates to a process for improving the flow properties of a melt comprising a thermoplastic polymer, which comprises the step of incorporating the modified polyacrylate polymer into the thermoplastic polymer prior to or during melt processing. The present invention also relates to a use of the modified polyacrylate polymer to improve the flow properties of a melt comprising a thermoplastic polymer.

Description

[0001] 240584 wool

[0002] Environmentally friendly processing aid based on modified polyacrylate polymer

[0003] The present invention relates to a shaped polymeric article comprising a thermoplastic polymer; and a modified polyacrylate polymer obtainable by a process comprising i. polymerizing at least one methacrylate monomer, preferably selected from substituted or unsubstituted C1-C22 alkyl methacrylates, substituted or unsubstituted C1-C22 methacrylamides, or esters of methacrylic acid with polyalkylether alcohol, and / or at least one acrylate monomer selected from substituted or unsubstituted C1-C22 alkyl acrylates, substituted or unsubstituted C4-C22 cycloalkyl acrylates, substituted or unsubstituted C1-C22 acrylamides, or esters of acrylic acid with polyalkylether alcohols, to obtain at least one polyacrylate polymer; and ii. modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one alcohol selected from unsubstituted C8-C36 alcohols (d), or polyalkylether alcohols (c2). The present invention also relates to a process for improving the flow properties of a melt comprising a thermoplastic polymer, which comprises the step of incorporating the modified polyacrylate polymer into the thermoplastic polymer prior to or during melt processing. The present invention also relates to a use of the modified polyacrylate polymer to improve the flow properties of a melt comprising a thermoplastic polymer.

[0004] The flow characteristics of polymer melts have paramount significance for the design and operating conditions of industrial processing equipment and may tremendously affect the overall properties of manufactured polymer articles. Polymer melts typically exhibit a non-Newtonian behavior; i.e. their apparent viscosity is strongly dependent on the shear rate applied when processing polymers at temperatures well above their melt-ing points. High shear rates result typically from high levels of mechanical energy (pressure and shear) applied for the purpose of extruding, feeding or any sort of transporting polymer melts in the course of the shape-giving process. Furthermore, high shear rates may equally result from high flow rates or high flow velocities when polymer melts are forced to pass through narrow dies, nozzles, cylinder profiles and the like, which can be of round, rectangular, annular, slit-like, or any other irregular shape or low gapwidth cross sections.

[0005] If inadequate attention is paid to the peculiar rheological properties of polymer melts, this may eventually lead to several negative, and therefore undesired, consequences in the aesthetic or mechanical polymer properties, which are well known in extrusion processes, in particular in the manufacture of profiles, especially thin-walled profiles, cast or blown films. Various defects are commonly referred to as sharkskin, snake-skin or orange-peel. These terms are figurative and self-explanatory descriptions of melt fracture phenomena which become more and more apparent when high shear rates cause visible roughness or even cracks and 240584 wool crevices on the polymer surface, so that the optical and mechanical properties of the manufactured polymer article are heavily deteriorated.

[0006] A particular case concerns polyolefins, among them linear polyethylene, such as linear low-density polyethylene (LLDPE), a widely applied commodity polymer but known for its difficult melt processability. Several polyolefins, especially LLDPE, are prone to melt fracture (MF) due to their relatively narrow molecular weight distribution and to the specific entanglement features of their polymeric chains.

[0007] While there is consensus that fluorine-based polymers incorporated into LLDPE im-prove the appearance of extrudates at high output rates and reduce the polymer melt viscosity, these products are also known for several shortcomings, such as the long onset time until such processing aids perform as expected (i.e. until MF is eliminated or its occurrence postponed to significantly higher shear rates, and / or until the energy consumption for compounding at a given throughput gets significantly reduced). Purging, removing or cleaning after processing such polymers containing fluorine-based polymers is very time consuming, i.e. when passing from one production run to another one. In addition, such fluorine-based processing aids are often produced from the precursor perfluorooctaonic acid (PFOA) which appears to be very persistent in the environment and is suspected to be detrimental to the health.

[0008] Apart from fluorine-based polymer processing aids, the use of silicone-based polymers or of polyethylene glycol, waxes or various fatty acid esters, is also known in the art. Not only are the benefits of such products not always prominent, as the performance at given concentration can be inferior to fluorine-based polymer processing aids and because they may not display their efficiency on all equipment. Silicone-based polymers or those based on polyethylene glycol present further drawbacks such as the apparition of undesired streaks in the final product, for instance in films, the development of fumes, or plate out on calendring rolls.

[0009] The object was to overcome the above-mentioned drawbacks.

[0010] The object was solved by a shaped polymeric article comprising a) a thermoplastic polymer; and b) a modified polyacrylate polymer obtainable by a process comprising i. polymerizing at least one methacrylate monomer, preferably selected from substituted or unsubstituted C1-C22 alkyl methacrylates, substituted or unsubstituted C1-C22 methacrylamides, or esters of methacrylic acid with polyalkylether alcohol, and / or at least one acrylate monomer selected from substituted or unsubstituted C1-C22 alkyl acrylates, substituted or unsubstituted C4-C22 cycloalkyl acrylates, substituted or unsubstituted C1-C22 acrylamides, or esters of acrylic acid with polyalkylether alcohols, to obtain at least one polyacrylate polymer; and ii. modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one alcohol selected from unsubstituted C8-C36 alcohols (d), or polyalkylether alcohols (c2).

[0011] The object was also solved by a process for improving the flow properties of a melt comprising a thermoplastic polymer, which comprises the step of incorporating the modified polyacrylate polymer into the thermoplastic polymer prior to or during melt processing.

[0012] The object was also solved by a use of the modified polyacrylate polymer to improve the flow properties of the melt comprising the thermoplastic polymer.

[0013] The improved flow property is preferably a reduced melt fracture. The reduced melt fracture can be analyzed visually, e.g. by analyzing the time until a shark-skin disappears from the surface of the melt.

[0014] Within the context of the presently claimed invention, the term alkyl, as used herein, refers to an acylic saturated aliphatic groups, including linear alkyl saturated hydrocarbon radical denoted by a general formula CnH2n+i and wherein n is the number of carbon atoms 1 , 2, 3, 4 etc. Preferably, the alkyl refers to linear and branched unsubstituted C2 to C22 carbon atoms, selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, 1 -ethyl propyl, 1 -ethyl butyl, 2-ethyl butyl, 1 -ethyl pentyl, 2-ethyl pentyl, 3-ethyl pentyl, 1 -ethyl hexyl, 2-ethyl hexyl, 3-ethyl hexyl, 4-ethyl hexyl, 1 -ethyl heptyl, 2-ethyl heptyl, 3-ethyl heptyl, 4-ethyl heptyl, 5-ethyl heptyl, 1 -ethyl octyl, 2-ethyl octyl, 3-ethyl octyl, 4-ethyl octyl, 5-ethyl octyl, or 6-ethyl octyl. With other words, these carbon chains can be either linear or any kind of branched structure, unless otherwise specified. For example, C1-C22 alkyl can be any linear alkyl starting from a methyl-group up to an n-docosanyl-group. Alternatively, C1-C22 alkyl can also be any branched alkyl having at least 4 carbon atoms (iso-butyl) and having at maximum 22 carbon atoms (for example / so-docosanyl). This general rule regarding linear or branched alkyl groups applies unless specifically stated otherwise within the context of the invention. Within the context of the presently claimed invention, the term substituted alkyl as used herein, refers to a linear or branched alkyl group where at least one hydrogen atom of the alkyl is replaced by other atoms or functional groups (other than alkyl), preferably where only one hydrogen atom of the alkyl is replaced by other atoms or functional groups. Preferred substituents are hydroxyl, amino, amide, carboxyl, nitro, 240584 wool sulfhydryl, phenyl, cyano, alkoxy and / or halogen, like -Cl, -Br, -F, -I. This general rule regarding substituted alkyl groups applies unless specifically stated otherwise within the context of the invention.

[0015] Within the context of the presently claimed invention, the term cycloalkyl, as used herein, refers to a monocyclic and a bicyclic saturated cycloaliphatic group, including branched cycloalkyl saturated hydrocarbon. Preferably, the cycloalkyl refers to C4 to C22 carbon atoms, selected from cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cycloeodecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl, cycloicosyl, cyclohenicosyl, or cyclodocosyl.

[0016] Within the context of the presently claimed invention, when the term 'substituted' is used in conjunction with cycloalkyl, phenyl, alkenyl, aralkyl, or alkylene groups, it indicates that at least one hydrogen atom in these groups is replaced by other atoms or functional groups. Preferably, only one hydrogen atom is replaced. Preferred substituents include hydroxyl, amino, amide, carboxyl, nitro, phenyl, cycloalkyl, sulfhydryl, alkyl, cyano, alkoxy, and halogens such as chlorine, bromine, fluorine, and iodine. This general rule regarding substituted groups, other than alkyl, applies unless specifically stated otherwise within the context of the invention.

[0017] Within the context of the presently claimed invention, the term “alcohol” refers to a compound having one or more hydroxyl groups. Preferably, a C8-C36 alcohol refers to a linear or branched C8-C36 alkyl substituted with one hydroxyl group. In one embodiment, the at least one polyacrylate polymer is a homopolymer comprising substituted or unsubstituted alkyl acrylates; and step (i) involves polymerizing the acrylate monomer selected from substituted or unsubstituted alkyl acrylates. In an alternative embodiment, the at least one polyacrylate polymer is a homopolymer comprising substituted or unsubstituted alkyl methacrylates; and step (i) involves polymerizing the methacrylate monomer selected from substituted or unsubstituted alkyl methacrylates.

[0018] In one embodiment, the alkyl acrylate is selected from ethyl acrylate, propyl acrylate, n-butyl acrylate, 2- ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, linear or branched C12-C16 alkyl acrylate, n-octadecyl acrylate, or combinations thereof. In one embodiment, the alkyl acrylate is n-butyl acrylate or ethyl acrylate.

[0019] In one embodiment, the alkyl methacrylate is selected from ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, linear or branched C12-C16 alkyl methacrylate, n-octadecyl methacrylate, or combinations thereof. In one embodiment, the alkyl methacrylate is n-butyl methacrylate or ethyl methacrylate. In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight in the range of 1000 to 50000 g / mol; preferably in the range of 1000 to 25000 g / mol; and more preferably in the range of 1000 to 15000 g / mol determined according to DIN 55672-1. In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight of 5000 g / mol determined according to DIN 55672-1 . In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight of 9700 g / mol determined according to DIN 55672-1.

[0020] In one embodiment, the ester of acrylic acid with polyalkylether alcohol is selected from ethyldiglycol acrylate, polyethyleneglycol acrylate, polyethyleneglycol-polypropylenglycol acrylate, or combinations thereof.

[0021] In one embodiment, the at least one polyacrylate polymer is a copolymer comprising the acrylate monomer and at least one monomer selected from methacrylate monomers, or styrene monomers.

[0022] In one embodiment, the at least one polyacrylate polymer is a copolymer selected from random copolymers, or block copolymers, and step (i) involves polymerizing the acrylate monomer and the at least one monomer selected from methacrylate monomers, or styrene monomers to obtain the at least one polyacrylate polymer.

[0023] In one embodiment, the at least one polyacrylate polymer is a random copolymer, and step (i) involves polymerizing a monomer mixture comprising the acrylate monomer and the at least one monomer selected from methacrylate monomers, or styrene monomers.

[0024] In one embodiment, the at least one polyacrylate polymer is a block copolymer, and step (i) involves two or more sub-steps to prepare the block copolymer and comprises at least the sub-step of polymerizing the acrylate monomer, and at least the sub-step of polymerizing the at least one monomer selected from methacrylate monomers, or styrene monomers.

[0025] In one embodiment, the methacrylate monomer is selected from substituted or unsubstituted C1-C22 alkyl methacrylates, substituted or unsubstituted C1-C22 methacrylamides, or esters of methacrylic acid with polyalkylether alcohol. In one embodiment, the alkyl methacrylate is selected from ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, or combinations thereof.

[0026] Within the context of the presently claimed invention, the term Ci-C22 acrylamides and Ci-C22 methacrylamides as used herein, can refer to any kind of N-substituted acrylamide or methacrylamide, respectively, where the substituent having 1 to 22 carbons. Preferably, the term C1-C22 methacrylamides refers to substituted or unsubstituted C1-C22 alkyl methacrylamides or substituted or unsubstituted C1-C22 cycloalkyl methacrylamides. Likewise, the term C1-C22 acrylamides preferably refers to substituted or unsubstituted C1-C22 alkyl acrylamides or substituted or unsubstituted C1-C22 cycloalkyl acrylamides. More preferably, the term C1-C22 methacrylamides refers to substituted or unsubstituted C1-C22 alkyl methacrylamides and the term C1-C22 acrylamides refers to substituted or unsubstituted C1-C22 alkyl acrylamides. The methacrylamide or acrylamide can be substituted once or twice, resulting in either a secondary or tertiary amide.

[0027] In one embodiment, the ester of methacrylic acid with polyalkylether alcohol is selected from polyethyleneglycol-polypropyleneglycol-methacrylate, polyethyleneglycol-methacrylate, or combinations thereof.

[0028] In one embodiment, the at least one polyacrylate polymer comprises 1.0 to 20.0 wt.% of the methacrylate monomer based on the total weight of the polyacrylate polymer.

[0029] In one embodiment, the styrene monomer is selected from styrene, C1-C4 alkyl substituted styrene, or combinations thereof. In one embodiment, the at least one polyacrylate polymer comprises 1 .0 to 20.0 wt.% of the styrene monomer based on the total weight of the polyacrylate polymer.

[0030] Polymerization of monomers is carried out by a free radical polymerization process or by a controlled free radical polymerization process. In one embodiment, the at least one polyacrylate polymer obtained has a number average molecular weight in the range of 1000 to 50000 g / mol; preferably in the range of 1000 to 25000 g / mol; and more preferably in the range of 1000 to 15000 g / mol determined according to DIN 55672- 1.

[0031] In one embodiment, step (i) is carried out by a free radical polymerization process. The free radical polymerization process is carried out using at least one free radical initiator. In one embodiment, step (i) is carried out in the presence of at least one free radical initiator. In one embodiment, the at least one free radical initiator is selected from the group consisting of organic peroxides, and azo initiators.

[0032] In one embodiment, the at least one free radical initiator is selected from 2,4-dimethyl-2,5-dibenzyl peroxyhexane, tert-butyl peroxybenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl(peroxybutane), tert-butylperoxy isopropyl 240584 wool carbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peracetate, 2,4-pentadiene peroxide, ditert butyl peroxide, tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2- ethyl hexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, or 2,5-dimethyl-2,5-di(tertbutylperoxy) hexane. In one embodiment, the at least one free radical initiator is selected from tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2- ethyl hexanoate, azobisisobutyronitrile, or dibenzoyl peroxide. In one embodiment, the at least one free radical initiator is tert-butyl peroxy-2-ethyl hexanoate.

[0033] In one embodiment, step (i) is carried out at a temperature in the range of 60 to 160 °C; and preferably in the range of 80 to 140 °C.

[0034] In one embodiment, step (i) is carried out in the presence of a solvent selected from isopropanol, 2-butanol, butyl acetate, methoxypropyl acetate, methoxy propanol, xylene, or combinations thereof. In one embodiment, the solvent is 2-butanol.

[0035] In one embodiment, step (i) is carried out by controlled free radical polymerization process. A controlled free radical polymerization is often referred to as living polymerization, where the radicals are not present permanently as free radicals on the chain ends of the growing polymer chain, but instead are present in equilibrium with a non-radical form and are continually being formed anew under polymerization conditions. The CFRP process allows enhanced control over the polydispersity of the polymer and allows production of polymers within a narrow molecular weight distribution.

[0036] The controlled radical polymerization process by the NMP (nitroxide-mediated polymerization) method is preferred. Preferably, the CFRP process is carried out in the presence of at least one nitroxylether of general formula (B). In one embodiment, step (i) is carried out in the presence of at least one nitroxylether of general formula (B) wherein

[0037] R11and R12are independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted C7-C18 aralkyl; 240584 wool wherein the substituted alkyl bears a substituent selected from C1-C4 alkoxy, C1-C4 alkoxy-Ci-C4 alkoxy, or PO3RZ2, and Rzis C1-C4 alkyl; or

[0038] R11and R12together form a ring comprising substituted or unsubstituted C2-C10 alkylene or substituted or unsubstituted C2-C10 alkenylene; wherein the substituted C2-C10 alkylene or substituted C2-C10 alkenylene bear 1 , 2, 3, 4 or 5 substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-Ci-C4 alkoxy, COOH, or CONH2; and wherein the C2-C10 alkylene or C2-C10 alkenylene optionally have one or two CH2 groups independently of one another replaced by 0, C=0, C=NOH, CH-OCOCH3 or NRX, and Rxis C1-C4 alkyl or C1-C4 alkoxy;

[0039] R13is C1-C4 alkyl or H;

[0040] R14, R15, and R16independently of one another are C1-C4 alkyl;

[0041] X is selected from the group consisting of -CH2-phenyl, -CH(CH3)-phenyl, -C(CH3)2-phenyl, -0(05-06- cycloalkyl)2-CN, -C(CH3)2CN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(Ci-C4alkyl)CHR17-C(O)-phenyl, -(Ci- C4alkyl)-CHR17-C(O)-(Ci-C4alkoxy), -(Ci-C4alkyl)-CHR17-C(O)-(Ci-C4alkyl), -(Ci-C4alkyl)-CHR17-C(O)-N- di(Ci-C4alkyl), -(Ci-C4alkyl)-CHR17-C(O)-NH(Ci-C4alkyl), and -(Ci-C4alkyl)-CHR17-C(O)-NH2, wherein R17is hydrogen or Ci-C4alkyl.

[0042] In one embodiment, step (i) is carried out in the presence of at least one nitroxylether of general formula (B) wherein

[0043] R11and R12together form a ring comprising substituted or unsubstituted C2-C10 alkylene;

[0044] R13is C1-C4 alkyl or H;

[0045] R14, R15, and R16independently of one another are C1-C4 alkyl; and wherein the substituted C2-C10 alkylene preferably bear 1 , 2, 3, 4 or 5 substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-Ci-C4 alkoxy, COOH, or CONH2; and wherein the C2-C10 alkylene optionally have one or two CH2 groups independently of one another replaced by 0, 0=0, C=NOH, CH-OCOCH3 or NRX, and Rxis C1-C4 alkyl or C1-C4 alkoxy;

[0046] X as defined above. 240584 wool

[0047] In one embodiment, step (i) is carried out in the presence of at least one nitroxylether of general formula (B) wherein

[0048] R11and R12together form a ring comprising substituted or unsubstituted C2-C4 alkylene; wherein the substituted C2-C4 alkylene preferably bear 1 or 2 substituents independently selected from C1-

[0049] C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-Ci-C4 alkoxy, COOH, or CONH2; and wherein the C2-C4 alkylene optionally have one CH2 groups independently of one another replaced by 0, C=0, C=NOH, CH-OCOCH3 or NRX, and Rxis C1-C4 alkyl or C1-C4 alkoxy;

[0050] R14, R15, and R16independently of one another are C1-C4 alkyl; and

[0051] X is selected from the group consisting of -CF phenyl, -CHCHs-phenyl, -C(CH3)2-phenyl, -C(Cs-C6- cycloalkyl)2-CN.

[0052] In one embodiment, step (i) is carried out in the presence of nitroxylether (B-l)

[0053] In one embodiment, the amount of compound of the formula B is in the range from 0.01 to 20.0 wt.%; and preferably in the range from 0.1 to 10.0 wt.%, based on the total weight of the at least one acrylate monomer or at least one methacrylate monomer to be polymerized.

[0054] The at least one nitroxylether of general formula (B) decomposes under the action of heat with formation of a stable free nitroxyl radical. Alternatively, a free radical polymerization initiator is added to initiate the conversion of at least one nitroxylether of general formula (B) to corresponding stable free nitroxyl radical. In one embodiment, the at least one free radical initiator is selected from the group consisting of organic peroxides, and azo initiators.

[0055] In one embodiment, the at least one free radical initiator is selected from 2,4-dimethyl-2,5-dibenzyl peroxyhexane, tert-butyl peroxybenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl(peroxybutane), tertbutylperoxy isopropyl carbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peracetate, 2,4-pentadiene peroxide, ditert butyl peroxide, tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2- ethyl hexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, or 2,5-dimethyl-2,5-di(tertbutylperoxy) hexane.

[0056] In one embodiment, the at least one free radical initiator is selected from tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethyl hexanoate, azobisisobutyronitrile, or dibenzoyl peroxide. In one embodiment, the at least one free radical initiator is tert-butyl peroxy-2-ethyl hexanoate.

[0057] In one embodiment, the total amount of the at least one free radical initiator is in the range from 1 .5 to 7.0 wt.% based on the total weight of the monomer.

[0058] In one embodiment, step (i) is carried out in the presence of at least one stable free nitroxyl radical. In one embodiment, step (i) is carried out in the presence of at least one stable free nitroxyl radical selected from the group consisting of radicals of formulae Za, Zb, Zc, Zd, Ze, Zf, Zg and Zh,

[0059] In one embodiment, step (i) is carried out at a temperature in the range of 80 to 180°C; preferably in the range of 100 to 175 °C; more preferably in the range of 100 to 150°C; and even more preferably in the range of 110 to 130 °C.

[0060] In one embodiment, the polydispersity of the at least one polyacrylate polymer obtained by the controlled free radical polymerization process is in the range from 1.2 to 2.0; and preferably in the range from 1.2 to 1.8.

[0061] In one embodiment, the peak average molecular weight of the at least one modified polyacrylate polymer is in the range from 2000 to 100,000 g / mol. The polydispersity of the at least one modified polyacrylate polymer is in the range from 1 .2 to 2.0.

[0062] The at least one polyacrylate polymer obtained in step (i) is modified by transesterification with at least one alcohol selected from unsubstituted Cs-Cse alcohols (d), or polyalkylether alcohols (c2).

[0063] The transesterification can be catalysed by known transesterification catalysts, e.g., tetrabutoxytitanate, lithium tert-butoxide, or lithium methanolate. The transesterification can be achieved at elevated temperatures, such as at least 80 °C, 120 °C or 140 °C. The transesterification can be achieved under inert atmosphere, such as under nitrogen.

[0064] In one embodiment, the at least one polyacrylate polymer obtained in step (i) is modified by transesterification with the unsubstituted Cs-Cse alcohol (c1). In one embodiment, the unsubstituted Cs-C36 alcohol (d) is selected from 2-ethylhexanol, n-decanol, isodecanol, linear or branched C12-C16 alcohols, n-octadecanol, oleyl alcohol, or combinations thereof. In one embodiment, the unsubstituted Cs-Cse alcohol (d) is selected from linear or branched C12-C16 alcohols, oleyl alcohol, or combinations thereof; and preferably. In one embodiment, the unsubstituted Cs-Cse alcohol (d) is oleyl alcohol. 240584 wool

[0065] In one embodiment, the weight ratio of the at least one polyacrylate polymer to the unsubstituted Cs-Cse alcohol (d) is in the range of 25:1 to 5:1 ; preferably in the range of 20:1 to 8:1 ; and more preferably in the range of 15:1 to 10:1.

[0066] In one embodiment, the at least one polyacrylate polymer obtained in step (i) is modified by transesterification with the polyalkylether alcohol (c2). In one embodiment, the polyether alcohol (c2) is a compound of Formula A Formula A wherein, m is an integer in the range of >1 to < 10; n and p are independently integers in the range of >0 to < 2000, wherein n+p is an integer in the range of >1 to < 4000;

[0067] R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl; and

[0068] R2is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.

[0069] In one embodiment, the polyether alcohol (c2) is compound of Formula A Formula A wherein, m is an integer in the range of >1 to < 10; n and p are independently integers in the range of >0 to < 500, wherein n+p is an integer in the range of >1 to < 1000;

[0070] R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl; and

[0071] R2is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl. In one embodiment, the polyether alcohol (c2) is compound of Formula A Formula A wherein, m is an integer in the range of >1 to < 10; n and p are independently integers in the range of >0 to < 100, wherein n+p is an integer in the range of >1 to < 200;

[0072] R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl; and

[0073] R2is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.

[0074] In one embodiment, the polyether alcohol (c2) is compound of Formula A Formula A wherein, m is an integer in the range of >1 to < 10; n and p are independently integers in the range of >0 to < 100, wherein n+p is an integer in the range of >1 to < 200;

[0075] R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C3o alkenyl, or substituted or unsubstituted phenyl; and

[0076] R2is methyl.

[0077] In one embodiment, the polyether alcohol (c2) is R1-(O-CH2CH2)n-OH > Formula A1 wherein, n is an integer in the range of >1 to < 100;

[0078] R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C3o alkenyl, or substituted or unsubstituted phenyl. In one embodiment, the polyether alcohol (c2) is

[0079] R1-(O-CH2CH2)n-OH > Formula A1 wherein, n is an integer in the range of >1 to < 100;

[0080] R1is substituted or unsubstituted C1-C30 alkyl.

[0081] In one embodiment, the polyether alcohol (c2) is an ethoxylate of a mixture of C13-C15 oxo alcohols having 67.0 wt.% C13 oxo alcohol, and 33.0 wt.% C15 oxo alcohol.

[0082] In one embodiment, the polyether alcohol (c2) is a mixture of C13-C15 oxo alcohol ethoxylates with 3 moles of ethylene oxide. In one embodiment, the polyether alcohol (c2) is a mixture of C13-C15 oxo alcohol ethoxylates with 5 moles of ethylene oxide. In one embodiment, the polyether alcohol (c2) is a mixture of C13- C15 oxo alcohol ethoxylates with 7 moles of ethylene oxide. In one embodiment, the polyether alcohol (c2) is a mixture of C13-C15 oxo alcohol ethoxylates with 8 moles of ethylene oxide. In one embodiment, the polyether alcohol (c2) is Cio-Guerbet alcohol ethoxylate with 7 moles of ethylene oxide.

[0083] In one embodiment, the weight ratio of the at least one polyacrylate polymer to the polyether alcohol (c2) is in the range from 1 :6 to 6:1 ; and preferably in the range of 1 :4 to 4:1.

[0084] In one embodiment, the polyether alcohol (c2) is a mixture of (i) a mixture of C13-C15 oxo alcohol ethoxylates with 7 moles of ethylene oxide, and (ii) a mixture of C13-C15 oxo alcohol ethoxylates with 11 moles of ethylene oxide.

[0085] In one embodiment, the polyacrylate polymer obtained in step (i) is modified by transesterification with at least one alcohol comprising a combination of the unsubstituted Cs-Cse alcohol (d), and the polyalkylether alcohol (c2).

[0086] In one embodiment, the weight ratio of the unsubstituted Cs-Cse alcohol (d), and the polyalkylether alcohol (c2) is in the range from 1 :2 to 1 :80; and preferably in the range of 1 :5 to 1 :50; and more preferably in the range of 1 :5 to 1 :25.

[0087] In one embodiment, the at least one alcohol is a combination of a mixture of Ci2-Ci4 fatty alcohol ethoxylates with 7 moles of ethylene oxide (d), and oleyl alcohol (c2). In one embodiment, the at least one alcohol is a combination of branched tridecyl alcohol ethoxylate with 6 moles of ethylene oxide (d), and oleyl alcohol 240584 wool

[0088] (c2). In one embodiment, the at least one alcohol is a combination of iso-Ci3H27 alcohol ethoxylate with 5 moles of ethylene oxide (d), and oleyl alcohol (c2). In one embodiment, the at least one alcohol is a combination of Cio-Guerbet alcohol ethoxylate with 7 moles of ethylene oxide (d), and oleyl alcohol (c2). In one embodiment, the at least one alcohol is a combination of a mixture of linear C16-C18 alcohol ethoxylates with 11 moles of ethylene oxide (d), and oleyl alcohol (c2). In one embodiment, the at least one alcohol is a combination of Cio-Oxo alcohol ethoxylate with 7 moles of ethylene oxide (d), and oleyl alcohol (c2). In one embodiment, the at least one alcohol is a combination of a mixture of C13-C15 oxo alcohol ethoxylates with 7 moles of ethylene oxide (d), and oleyl alcohol (c2).

[0089] In one embodiment, the weight ratio of the at least one polyacrylate polymer to the at least one alcohol is in the range from 1 :6 to 6:1 ; and preferably in the range of 1 :4 to 4:1.

[0090] In one embodiment, the peak molecular weight of the modified polyacrylate polymer is in the range from 2000 to 100,000 g / mol; preferably in the range of 5000 to 60000 g / mol; and more preferably in the range of 10000 to 40000 g / mol according to DIN 55672-1.

[0091] In one embodiment, the modified polyacrylate polymer comprises

[0092] 1 . 20.0 to 70.0 wt.% of at least one polyacrylate polymer; and

[0093] 2. 30.0 to 80.0 wt.% of at least one alcohol selected from unsubstituted Cs-Cse alcohols (d), or at least one polyalkylether alcohols (c2), based on the total weight of the at least one modified polyacrylate polymer.

[0094] In one embodiment, the modified polyacrylate polymer comprises

[0095] 1 . 20.0 to 70.0 wt.% of at least one polyacrylate polymer; and

[0096] 2. 30.0 to 80.0 wt.% of at least one alcohol selected from polyalkylether alcohols (c2), based on the total weight of the at least one modified polyacrylate polymer.

[0097] In one embodiment, the modified polyacrylate polymer comprises

[0098] 1 . 20.0 to 70.0 wt.% of at least one polyacrylate polymer;

[0099] 2. 29.0 to 79.0 wt.% of at least one alcohol selected from polyalkylether alcohols (c2); and

[0100] 3. 1.0 to 10.0 wt.% of at least one alcohol selected from unsubstituted Cs-Cse alcohols (d), based on the total weight of the at least one modified polyacrylate polymer. The thermoplastic polymer may comprise 0.01 to 4 wt%, preferably 0.05 to 2 wt%, more preferably from 0.05 to 1 .0 wt% and in particular from 0.05 to 0.5 wt% of the modified polyacrylate polymer.

[0101] Preferably the thermoplastic polymer is free of fluorine-based polymers, such as per- and polyfluoroalkyl substances (also known as PFAS). Examples of fluorine-based polymers are elastomeric fluoropolymers (i. e. fluoroelastomers or amorphous fluoropolymers) and thermoplastic fluoropolymers (i. e. semi-crystalline fluoropolymers). Fluoroelastomers are fluoropolymers that are normally in the fluid state at room temperature and above, i. e. fluoropolymers which have Tg values below room temperature and which exhibit little or no crystallinity at room temperature. Fluorinated monomers which may be copolymerized to yield suitable fluoroelastomers include vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene and perfluoroalkyl perfluorovinyl ethers. Specific examples of the fluoroelastomers include copolymers of vinylidene fluoride and a comonomer selected from hexafluoropropylene, chlorotrifluoroethylene, 1 -hydropentafluoropropylene, and 2hydropentafluoropropylene ; copolymers of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene or 1 -or 2- hydropentafluoropropylene; and copolymers of tetrafluoroethylene, propylene and, optionally, vinylidene fluoride. Suitable semi-crystalline fluoropolymers are poly (vinylidene fluoride), homopolymers and copolymers of tetrafluoroethylene (such as Teflon FEP fluorocarbon resin, and copolymers of tetrafluoroethylene, propylene and, optionally, vinylidene fluoride).

[0102] Examples of suitable thermoplastic polymers are:

[0103] 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly- 4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE- HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0104] Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). 240584 wool b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls that may be either IT- or g- coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and / or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0105] 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

[0106] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / cycloolefin copolymers (e.g. ethylene / norbornene like COC), ethylene / 1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers orethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyal kylene / carbo n monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

[0107] 4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch. Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

[0108] 5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).

[0109] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, a- methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

[0110] 6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymers), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

[0111] 6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

[0112] 6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).

[0113] Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

[0114] 7. Graft copolymers of vinyl aromatic monomers such as styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0115] 8. Chlorine-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of chlorine-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, as well as copolymers thereof such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

[0116] 9. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

[0117] 10. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

[0118] 11. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

[0119] 12. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0120] 13. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

[0121] 14. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. 15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6 / 6, 6 / 10, 6 / 9, 6 / 12, 4 / 6, 12 / 12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or / and terephthalic acid and with or without an elastomer as modifier, for example poly-2, 4, 4, -trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

[0122] 16. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

[0123] 17. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1 , 4- dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

[0124] 18. Polycarbonates and polyester carbonates.

[0125] 19. Polyketones.

[0126] 20. Polysulfones, polyether sulfones and polyether ketones.

[0127] 21. Blends of the aforementioned polymers (polyblends), for example PP / EPDM, Polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0128] The thermoplastic polymer can be virgin or a recycled polymer, which may be obtainable from domestic, commercial and industrial waste or from useful material collections. The recycled polymer may originate from separation and sorting, or from specific industrial sectors and return obligations, for example from the automobile industry, electrical / electronic industry, construction, agriculture and the textile industry, or from households and commerce (for example supermarkets).

[0129] For example the thermoplastic polymer is polypropylene, polyethylene, any polypropylene copolymer or any polyethylene copolymer or any of their blends.

[0130] Preferably the thermoplastic polymer is a linear low density polyethylene (LLDPE).

[0131] The modified polyacrylate polymer may be added directly to the extruder together with the thermoplastic polymer or it may be premixed with the thermoplastic polymer and then added to the extruder.

[0132] Optionally, an interfacial agent can be incorporated in the composition. The role of a interfacial agent may be the reduction of the onset time or induction time until the polymer processing aid (PPA) effect is observable, or to further lower the melt viscosity or energy consumption required for compounding the polymer, or for enhanced processability. The interfacial agent often is a relatively low molecular weight ingredient which, for a particular system of PPA plus thermoplastic polymer, preferentially locates at the interface between these two polymers. The interfacial agent may be introduced to the polymer at any point up to and including the final melt shaping process. It is most desirable to combine the interfacial agent in a masterbatching step where both ingredients are present at high concentration (i. e. at a concentration greater than or equal to 0.5 wt. %, based on the total weight of masterbatch).

[0133] Possible interfacial agent are, among others, thermoplastic polymers which are characterized by 1) being in the liquid state (or molten) at the extrusion temperature, 2) having a lower melt viscosity than both the melt processable polymer and the comb or comb block copolymer process aid, and 3) freely wets the surface of the comb or comb block copolymer particles in the extrudable composition. Examples of such interfacial agent include, but are not limited to i) silicone-polyether copolymers ; ii) aliphatic polyesters such as poly (butylene adipate), poly (lactic acid) and polycaprolactone polyesters; iii) aromatic polyesters such as phthalic acid diisobutyl ester; iv) polyether polyols (preferably, not a polyalkylene oxide) such as poly (tetramethylene ether glycol) ; v) amine oxides such as octyldimethyl amine oxide; vi) carboxylic acids such as hydroxybutanedioic acid; vii) fatty acid esters such as sorbitan monolaurate and triglycerides; and vii) poly (oxyalkylene) polymers, including polyethylene glycols and their derivatives. Preferred aliphatic interfacial agent are polyethylene glycol or aliphatic polyester (preferably polycaprolactone) having a number average molecular weight in the range 500 to 32000, preferably 1000 to 15000, and most preferably 2000 to 12000. PEG as a further additive, e.g. interfacial agent, to the polymeric article according to the invention reduces melt viscosity, improving processability and minimizing extrusion defects like sharkskin. This combination offers a more cost efficient and eco-friendly alternative to traditional processing aids, enhancing the aesthetic and mechanical properties of polymeric articles.

[0134] The thermoplastic polymer may comprise a further additive such as antioxidant, UV absorber, light stabilizer, metal deactivator, peroxide scavenger, nucleating agent, filler, reinforcing agent, a partitioning agent, preferably an inorganic partitioning agent, such as calcium carbonate, silicon oxide, talc or any combination thereof.

[0135] In one form the thermoplastic polymer comprises a light stabilizer, preferably a hindered amine light stabilizer, and in particular oligomeric hindered amines.

[0136] The oligomeric hindered amine comprises usually a compound selected from a compound of the formula (I) wherein bi is a number from 1 to 20; the radicals Ri independently of one another are hydrogen, Ci-Csalkyl, O-, -OH, -CH2CN, Ci-Cisalkoxy, C5- Ci2cycloalkoxy, Cs-Cealkenyl, Cz-Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C4alkyl; or Ci-Csacyl;

[0137] R2 is C2-Cisalkylene, Cs-C / cycloalkylene or Ci-C4alkylenedi(C5-C7cycloalkylene);

[0138] R3 and R4 independently of one another are hydrogen, Ci-Ci2alkyl, C5-Ci2cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl; C7- Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C4alkyl; or a group of the formula (la) H3C C H3

[0139] — Q-R, H3C C H3 or

[0140] R3 and R4, together with the nitrogen atom to which they are linked, form a 5- to 10-membered heterocyclic ring; and / or a compound of the formula (II) wherein b2 is a number from 1 to 20; the radicals Xi independently of one another are hydrogen, Ci-Csalkyl, O-, -OH, -CH2CN, Ci-Cisalkoxy, Cs- Ci2cycloalkoxy, Cs-Cealkenyl, Cz-Cophenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C4alkyl; or Ci-Csacyl; the radicals Y1 independently of one another are hydrogen, Ci-Ci2alkyl, C5-Ci2cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl; C7- Cophenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C4alkyl; or a group of the formula (Ha); the radicals Z1 independently of one another are C2-Cisalkylene, Cs-C / cycloalkylene or Ci-C4alkylenedi(Cs- Czcycloalkylene). 240584 wool

[0141] Examples of alkyl having up to 12 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methyhpentyl, 1 .S-dimethybbutyl, n-hexyl, 1- methyhhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetra_|methy|-'butyl, l-methyhheptyl, 3-methyhheptyl, n-octyl, 2- ethylhexyl, 1 ,1 ,3-trimethyl-hexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1 -methylundecyl and dodecyl.

[0142] Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. A preferred radical is n-propoxy.

[0143] Examples of alkenyl having up to 6 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.

[0144] Examples of C5-Ci2cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl are cyclohexyl, methylcyclohexyl and dimethylcyclohexyl.

[0145] Examples of C5-Ci2cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Cyclohexoxy is preferred.

[0146] Examples of phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl are methylphenyl, dimethylphenyl, trimethylphenyl and tert-butylphenyl.

[0147] Examples of Cz-Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C4alkyl are methylbenzyl, dimethylbenzyl, trimethylbenzyl and tert-butyl benzyl.

[0148] Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl. Ci-CsAlkanoyl, Cs-Csalkenoyl and benzoyl are preferred.

[0149] Examples of alkylene having up to 18 carbon atoms are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene and octamethylene. C2- Cealkylene, in particular hexamethylene is preferred.

[0150] An example of Cs-C / cycloalkylene is cyclohexylene. An example of Ci-C4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.

[0151] A preferred example of a 5-to 7-membered heterocyclic ring is a morpholine group.

[0152] The radicals Ri and Xi are preferably hydrogen, methyl or propoxy, in particular n-propoxy.

[0153] Suitable compounds of component (I) and (II) are CHIMASSORB®944, CHIMASSORB®2020, CYASORB®UV 3346, CYASORB®UV 3529, DASTIB®1082, TINUVIN®NOR 371 , TINUVIN®NOR 356, UVASORB®HA88 and CHIMASSORB®119.

[0154] Examples of the compounds of the formulae (I) and (II) are: wherein bi is a number from 2 to 10, wherein bi is a number from 2 to 10, wherein bi is a number from 1 to 10, wherein b2 is a number from 2 to 10, and

[0155]

[0156] Particular preferred light stabilizers are the light stabilizer of the following formula:

[0157] For ease of processing, the modified polyacrylate polymers are often used in the form of a masterbatch, rather than neat, when they are added to the polymer. Within the scope of this invention, a masterbatch is usually a mixture of the modified polyacrylate polymer in a carrier polymer. The carrier polymer can be the same polymer that is to be extruded, or it can be a second polymer that does not deleteriously affect the extrusion behaviour of the thermoplastic polymer that is to be extruded.

[0158] Masterbatches typically contain 0.5-50 wt. %, preferably 1-30 wt. % of the modified polyacrylate polymer, based on the total weight of the masterbatch. Masterbatches can be made, for example, by mixing the appropriate amount of the modified polyacrylate polymer with carrier polymer in a mixer (e.g. Banbury mixer) or a co-rotating twin screw extruder, at a temperature above the melting point of the polymer.

[0159] Typically, such a masterbatch contains a) the carrier polymer, b) 0.5 to 50 weight percent of the modified polyacrylate polymer, and optionally c) an effective amount of an interfacial agent.

[0160] Preferably, the melt is processed by extrusion, such as film extrusion (cast film; blown film), fiber extrusion, pipe extrusion, profile extrusion, sheet extrusion; or tape extrusion.

[0161] The melt processing is preferably an extrusion, such as film extrusion (cast film; blown film), fiber extrusion, pipe extrusion, profile extrusion, sheet extrusion; or tape extrusion.

[0162] Examples

[0163] Weight average molecular weight (Mw): Mw was determined according to DIN55672-1 involving gel permeation chromatography using a refractometer as the detector. The mobile phase used was tetrahydrofuran (THF, 1mL / min, 35° C), the standard employed for determining the molecular weight being polystyrene (PS).

[0164] Number average molecular weight (Mn): Mn is determined according to DIN55672-1 involving gel permeation chromatography using a refractometer as the detector. The mobile phase used was tetrahydrofuran (THF, 1 mL / min, 35°C), the standard employed for determining the molecular weight being polystyrene (PS).

[0165] Peak molecular weight (Mp): The peak molecular weight (Mp) was determined from the retention time corresponding to the peak value of the obtained elution curve in gel permeation chromatography, based on standard polystyrene. The peak value of the elution curve is the point where the elution curve is at maximum. MPwas determined according to DIN55672- 1 involving gel permeation chromatography using a refractometer as the detector. The mobile phase used was tetrahydrofuran (THF, 1 mL / min, 35°C), the standard employed for determining the molecular weight being polystyrene (PS).

[0166] Polyethylene PE-1 : a high molecular weight linear low-density polyethylene (LLDPE), commercially available as ExxonMobil LL 1201 XV, ExxonMobil.

[0167] Additive PPA-1 : Dynamar® FX 5920A, from the company 3M, comprising a vinylidene fluoridehexafluoropropylene fluoroelastomer (25-35 wt%), an interfacial agent like PEG (60-70 wt%) and <5 wt% of partitioning agents like Talc and calcium.

[0168] Example 1 - General procedure for the synthesis of a polyacrylate polymer by free radical polymerization [FRP1

[0169] To a 5000 mL polymerization reactor equipped with an overhead stirrer, thermometer, distillation 30 line, vacuum pump and dosing devices, was charged 926.0 g of solvent. The reactor was maintained under nitrogen atmosphere and the content was heated to 100°C. A monomer feed of 1900.0 g methacrylate or acrylate (for example butylacrylate or ethylacrylate, in particular n-butylacrylate) and 45.2 g a feed of tert- butylperoxy-2-ethyl hexanoate were started, and these feeds were transferred to the reactor over a period of 300 minutes, while maintaining the temperature of the reaction mixture at 100 °C. After complete addition of the feeds, the solvent and volatiles were removed by distillation under reduced pressure at 100°C to obtain the polyacrylate polymer as a clear, colorless viscous liquid with a polymer content >99 wt.%.

[0170] Example 2 - General procedure for the transesterification of the polyacrylate polymer

[0171] To a reactor maintained under nitrogen atmosphere, were charged a poly acrylate polymer (20-70 wt.%) (for example charged a polyfbutyl acrylate) (20-70 wt.%) or a polyfethyl acrylate) (20-70 wt.%), in particular a poly(n-butyl acrylate) (20-70 wt.%)) and at least one alcohol (30-80 wt.%). The content of the reactor was heated under nitrogen atmosphere at 100 °C. 0.1-1.0 wt.% of a transesterification catalyst (e.g., tetrabutoxytitanate, lithium tert-butoxide, or lithium methanolate) was added to the reaction mixture and the resultant mixture was heated under reduced pressure (< 50mbar). The bath temperature was gradually 15 increased to 160 °C. After an expected amount of distillate was collected, the product was cooled to room temperature and was discharged from the reactor to obtain a modified polyacrylate polymer.

[0172] Example 3 - Modified poly (butyl acrylate) and modified poly (ethyl acrylate)

[0173] The following modified polyfethyl acrylate) and modified polyfbutyl acrylate) were prepared according to the general methods described in Example 1 and 2. A general formula for the modified polyfbutyl acrylate) is as follows: - PPA-2: Mp= 9614 Da; (Poly(butyl acrylate)= 40.5wt%, Mw 11.029 Da, Mn 3942 Da; R2= iso-C13H27 alcohol; n=7; alkoxylated polyether= 55.3wt%; R1 =oleyl alcohol= 4.3wt%).

[0174] - PPA-3: Mp= 37093 Da; (Poly(ethyl acrylate)= 43.9wt%, Mw 19838 Da, Mn 6598 Da; R2= iso-C13H27 alcohol; n=7; alkoxylated polyether= 51.4wt%; R1 =oleyl alcohol= 4.6wt%).

[0175] - PPA-4: Mp= 59418 Da; (Poly(ethyl acrylate)= 43.9wt%, Mw 23396 Da, Mn 7449 Da; R2= iso-C13H27 alcohol; n=7; alkoxylated polyether= 51.4wt%; R1 =oleyl alcohol= 4.6wt%).

[0176] - PPA-5: Mp= 12293 Da; (Poly(butyl acrylate)= 71.9wt%, Mw 11.646 Da, Mn 3942 Da; R1 = iso-C13H27 alcohol; n=7; alkoxylated polyether= 28.1wt%).

[0177] - PPA-6: Mp= 11380 Da; (Poly(butyl acrylate)= 29.9wt%, Mw 11.646 Da, Mn 3942 Da; R1= iso-C13H27 alcohol; n=7; alkoxylated polyether= 70.1wt%).

[0178] Example 4 - Production of Masterbatches

[0179] The Polyethylene PE-1 and processing aid components from PPA-1 to PPA-6 were blended in the amounts as indicated in Table 1 and then melt compounded into pellets on a 25 mm co-rotating twin-screw extruder Berstorff ZE25A x 47D, operating at 160 revolutions per minute (rpm) and at set temperatures of 190°C, and extruded into pellets to obtain the masterbatches MB-A to MB-F.

[0180] TABLE 1 : Concentrations of processing aid components in Masterbatches

[0181] Example 5 - Performance of formulation as Processing aid

[0182] Pelletized fully formulated masterbatch and Polyethylene PE-1 were dry blended in the amounts as indicated in Table 2 and melt processed into monofilament through a 1.5 mm die on a 20 mm single screw extrusion, Extrusionmeter 20D at set temperatures of 220 °C. Between each formulations the extruder was purged with Polyethylene PE-1 for 1 h and only after the subsequent formulation was tested. TABLE 2: Concentrations of added masterbatches in the LLDPE monofilaments

[0183] For each masterbatch composition tested, the time until melt fracture or shark-skin was eliminated from extruded monofilament was recorded in Table 3.

[0184] TABLE 3: Shark-skin Elimination * Rated "yes" if the shark-skin is eliminated during the test

[0185] ** Correspond to the time when the shark-skin is no longer visible

[0186] TABLE 3 (continued)

[0187] In Figure 1 a photograph of Monofilament Sample Ref.1 (comparative) after 5 min (A) and after 80 min (B) is shown. It showed that even after 80 min the shark skin was not eliminated.

[0188] In Figure 2 a photograph of Monofilament Sample INV.3 after 5 min (A), after 20 min (B) and after 40 min (C) is shown. It showed that already after 40 min the shark skin was no longer visible.

[0189] Inv. 3 to 12 improved significantly the processing performance of the composition in comparison to Comparative Compositions Ref. 1 and 2. The times until the shark-skin elimination were considerably lower for Inv. 3 to 12.

[0190] Example 6 - Production of Masterbatches including a light stabilizer

[0191] Polyethylene PE-1 and Light Stabilizers components LS-1 and LS-2 were blended in the amounts as indicated in Table 4 and then melt compounded into pellets on a 25 mm co-rotating twin-screw extruder Berstorff ZE25A x 47D, operating at 160 revolutions per minute (rpm) and at set temperatures of 190°C, and extruded into pellets. TABLE 4: Concentrations of Light Stabilizers components in Masterbatches

[0192] LS-1 : a high molecular weight (about 1600-1800 g / mol) hindered amine NOR light stabilizerof the following formula:

[0193] LS-2: a high molecular weight (about 3000 g / mol) hindered amine light stabilizer of the following formula:

[0194] Example 7 - Performance of formulation with light stabilizer as processing aid

[0195] Pelletized fully formulated masterbatch and Polyethylene PE-1 were dry blended in the amounts as indicated in Table 5 and melt processed into monofilament through a 1 .5 mm die on a 20 mm single screw extrusion, Extrusionmeter 20D at set temperatures of 220 °C. Between each formulations the extruder was purged with base PolyethyleneP E- 1 for 1 h and only after the subsequent formulation was tested.

[0196] TABLE 5: Concentrations of added masterbatches in monofilaments

[0197] For each masterbatch composition tested, the time until melt fracture or shark-skin was eliminated from extruded monofilament was recorded in Table 3.

[0198] TABLE 6: Shark-skin Elimination

[0199] * Rated "yes" if the shark-skin is eliminated during the test

[0200] ** Correspond to the time when the shark-skin is no longer visible

[0201] In Figure 3 a photograph of Monofilament Sample I NV.14 after 5 min (A), and after 20 min (B) is shown. It showed that already after 20 min the shark skin was no longer visible. Example 8 - Performance of formulation in Blown film

[0202] Pelletized fully formulated masterbatch and LLDPE (Petrothene® GA 1810, Lyondell Basell) were dry blended in the amounts as indicated in Table 6 and melt processed (5.2Kg / h, 100rpm) in single blown film with a nominal thickness of 70pm through a die (60mm diameter, 1.0mm gap) using a single screw extrusion (diameter: 30mm, length: 25D), at set temperatures of 200°C.

[0203] For each masterbatch composition tested, the time until shark-skin was eliminated from extruded film was recorded in Table 7.

[0204] Between each formulations the extruder was purged with Polyethylene (Petrothene® GA 1810) for 1 h and only after the subsequent formulation was tested.

[0205] TABLE 7: Concentrations of added masterbatches in the LLDPE Blown film

[0206] TABLE 8: Shark-skin Elimination

[0207] ** Correspond to the time when the shark-skin is no longer visible In Figure 4 a photograph of blown film Sample Ref.lA after 15 min (A), and after 60 min (B) is shown. It showed that even after 60 min the shark skin was not eliminated.

[0208] In Figure 5 a photograph of blown film Sample INV.3A after 5 min (A), and after 15 min (B) is shown. It showed that already after 15 min the shark skin was no longer visible.

[0209] In inventive samples from lnv.2A to lnv.5A a significant increase in the processing performance of these compositions was observed in comparison to reference composition Ref. 1 A without any type of processing aids.

[0210] Evaluation of optical properties after 60 minutes was measured for some formulations to show improved film optical properties when inventive compound is employed (Table 9).

[0211] TABLE 9: Optical properties of blown film after 60 minutes

Claims

Claims1 . A shaped polymeric article comprising a) a thermoplastic polymer; and b) a modified polyacrylate polymer obtainable by a process comprising i. polymerizing at least one methacrylate monomer, preferably selected from substituted or unsubstituted C1-C22 alkyl methacrylates, substituted or unsubstituted C1-C22 methacrylamides, or esters of methacrylic acid with polyalkylether alcohol, and / or at least one acrylate monomer selected from substituted or unsubstituted C1-C22 alkyl acrylates, substituted or unsubstituted C4-C22 cycloalkyl acrylates, substituted or unsubstituted C1-C22 acrylamides, or esters of acrylic acid with polyalkylether alcohols, to obtain at least one polyacrylate polymer; and ii. modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one alcohol selected from unsubstituted Cs-Cse alcohols (d), or polyalkylether alcohols (c2).

2. The article according to claim 1 , where the alkyl acrylate is selected from ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, linear or branched C12-C16 alkyl acrylates, n-octadecyl acrylate, or combinations thereof.

3. The article according to claim 1 or 2, where the polyacrylate polymer is a copolymer selected from random copolymers, or block copolymers, and wherein step (i) involves polymerizing the acrylate monomer and at least one monomer selected from methacrylate monomers, or styrene monomers to obtain the at least one polyacrylate polymer.

4. The article according to any of claims 1 to 3, where the unsubstituted Cs-Cse alcohol (C1) is selected from 2-ethylhexanol, n-decanol, isodecanol, linear or branched C12-C16 alcohols, n-octadecanol, oleyl alcohol, or combinations thereof.

5. The article according to any of claims 1 to 4, where the polyether alcohol (c2) is a compound of Formula A240584 woolFormula A wherein,- m is an integer in the range of >1 to < 10;- n and p are independently integers in the range of >0 to < 2000, wherein n+p is an integer in the range of >1 to < 4000;- R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl; and- R2is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.

6. The article according to any of claims 1 to 5, where the polyether alcohol (c2) is a compound of FormulaA1R1-(O-CH2CH2)n-OH Formula A1 wherein- n is an integer in the range of >1 to < 100; and- R1is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C3o alkenyl, or substituted or unsubstituted phenyl.

7. The article according to any of claims 1 to 6, where the peak molecular weight of the modified polyacrylate polymer is in the range from 2000 to 100,000 g / mol according to to DIN 55672-1.

8. The article according to any of claims 1 to 7, where the modified polyacrylate polymer comprises- 20.0 to 70.0 wt.% of at least one polyacrylate polymer; and- 30.0 to 80.0 wt.% of at least one alcohol selected from unsubstituted Cs-Cse alcohols (d), or polyalkylether alcohols (c2); and all weights are based on the total weight of the modified polyacrylate polymer.

9. The article according to any of claims 1 to 8, where the thermoplastic polymer is polypropylene, polyethylene, any polypropylene copolymer or any polyethylene copolymer or any of their blends.

10. The article according to any of claims 1 to 9, where the thermoplastic polymer comprises 0.01 to 4 wt%, preferably 0.05 to 2 wt%, more preferably from 0.1 to 1 .5 wt% and in particular from 0.2 to 1 .0 wt% of the modified polyacrylate polymer.

11. The article according to any of claims 1 to 10, where the thermoplastic polymer comprises a light stabilizer, preferebly a hindered amine light stabilizer.

12. The article according to any of claims 1 to 11 , further comprising an interfacial agent selected from the list of silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, polyether polyols, amine oxides, carboxylic acids, fatty acid esters and poly(oxyalkylene) polymers.

13. The article according to claim 12, where the interfacial agent is polyethylene glycol, preferably having a number average molecular weight in the range 500 to 32000, more preferably 1000 to 15000, and most preferably 2000 to 12000.

14. A process for improving the flow properties of a melt comprising a thermoplastic polymer, which comprises the step of incorporating a modified polyacrylate polymer as defined in any of claims 1 to 8 into the thermoplastic polymer prior to or during melt processing.

15. The process according to claim 14 where the thermoplastic polymer is free of a fluorine-based polymer.

16. The process according to claim 14 or 15 where the melt is processed by extrusion.

17. The process according to any of claims 14 to 16 where the improved flow property is a reduced melt fracture.

18. A use of a modified polyacrylate polymer as defined in any of claims 1 to 8 to improve the flow properties of a melt comprising a thermoplastic polymer.

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