WO2026037667A1 - Adjuvant respectueux de l'environnement à base de polymère de polyacrylate modifié - Google Patents

Adjuvant respectueux de l'environnement à base de polymère de polyacrylate modifié

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Publication number
WO2026037667A1
WO2026037667A1 PCT/EP2025/072429 EP2025072429W WO2026037667A1 WO 2026037667 A1 WO2026037667 A1 WO 2026037667A1 EP 2025072429 W EP2025072429 W EP 2025072429W WO 2026037667 A1 WO2026037667 A1 WO 2026037667A1
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WIPO (PCT)
Prior art keywords
unsubstituted
substituted
polymer
polyacrylate polymer
alcohol
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Pending
Application number
PCT/EP2025/072429
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English (en)
Inventor
Edoardo Menozzi
Andreas Gernandt
Frank Pirrung
Wiebke Wunderlich-Wippert
Daniel Müller
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BASF SE
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BASF SE
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Publication of WO2026037667A1 publication Critical patent/WO2026037667A1/fr
Pending legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • silicone-based polymers or of polyethylene glycol, waxes or various fatty acid esters are 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.
  • the object was to overcome the above-mentioned drawbacks.
  • 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
  • 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.
  • 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.
  • alkyl refers to an acylic saturated aliphatic groups, including linear alkyl saturated hydrocarbon radical denoted by a general formula C n H2n+i and wherein n is the number of carbon atoms 1 , 2, 3, 4 etc.
  • 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 pent
  • C1-C22 alkyl can be any linear alkyl starting from a methyl-group up to an n-docosanyl-group.
  • 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.
  • substituted alkyl 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.
  • substituted groups 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.
  • the term “alcohol” refers to a compound having one or more hydroxyl groups.
  • a C8-C36 alcohol refers to a linear or branched C8-C36 alkyl substituted with one hydroxyl group.
  • 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.
  • 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.
  • 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.
  • the alkyl acrylate is n-butyl acrylate or ethyl acrylate.
  • 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.
  • the alkyl methacrylate is n-butyl methacrylate or ethyl methacrylate.
  • 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.
  • the ester of acrylic acid with polyalkylether alcohol is selected from ethyldiglycol acrylate, polyethyleneglycol acrylate, polyethyleneglycol-polypropylenglycol acrylate, or combinations thereof.
  • 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.
  • 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.
  • the at least one polyacrylate polymer is a random copolymer
  • step (i) involves polymerizing a monomer mixture comprising the acrylate monomer and the at least one monomer selected from methacrylate monomers, or styrene monomers.
  • the at least one polyacrylate polymer is a block copolymer
  • 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.
  • 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.
  • the alkyl methacrylate is selected from ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, or combinations thereof.
  • 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.
  • C1-C22 methacrylamides refers to substituted or unsubstituted C1-C22 alkyl methacrylamides or substituted or unsubstituted C1-C22 cycloalkyl methacrylamides.
  • 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.
  • ester of methacrylic acid with polyalkylether alcohol is selected from polyethyleneglycol-polypropyleneglycol-methacrylate, polyethyleneglycol-methacrylate, or combinations thereof.
  • 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.
  • the styrene monomer is selected from styrene, C1-C4 alkyl substituted styrene, or combinations thereof.
  • 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.
  • 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.
  • 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.
  • step (i) is carried out in the presence of at least one free radical initiator.
  • the at least one free radical initiator is selected from the group consisting of organic peroxides, and azo initiators.
  • 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, azo
  • 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.
  • the at least one free radical initiator is tert-butyl peroxy-2-ethyl hexanoate.
  • 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.
  • 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.
  • a solvent selected from isopropanol, 2-butanol, butyl acetate, methoxypropyl acetate, methoxy propanol, xylene, or combinations thereof.
  • the solvent is 2-butanol.
  • 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.
  • the controlled radical polymerization process by the NMP (nitroxide-mediated polymerization) method is preferred.
  • the CFRP process is carried out in the presence of at least one nitroxylether of general formula (B).
  • step (i) is carried out in the presence of at least one nitroxylether of general formula (B) wherein
  • R 11 and R 12 are 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 PO3R Z 2, and R z is C1-C4 alkyl; or
  • R 13 is C1-C4 alkyl or H
  • R 14 , R 15 , and R 16 independently of one another are C1-C4 alkyl
  • R 11 and R 12 together form a ring comprising substituted or unsubstituted C2-C10 alkylene
  • step (i) is carried out in the presence of at least one nitroxylether of general formula (B) wherein
  • R 11 and R 12 together 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-
  • R 14 , R 15 , and R 16 independently of one another are C1-C4 alkyl
  • X is selected from the group consisting of -CF phenyl, -CHCHs-phenyl, -C(CH3)2-phenyl, -C(Cs-C6- cycloalkyl)2-CN.
  • step (i) is carried out in the presence of nitroxylether (B-l)
  • 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, azobisisobuty
  • 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.
  • the at least one free radical initiator is tert-butyl peroxy-2-ethyl hexanoate.
  • 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.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the at least one polyacrylate polymer obtained in step (i) is modified by transesterification with the unsubstituted Cs-Cse alcohol (c1).
  • 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.
  • the unsubstituted Cs-Cse alcohol (d) is selected from linear or branched C12-C16 alcohols, oleyl alcohol, or combinations thereof; and preferably.
  • the unsubstituted Cs-Cse alcohol (d) is oleyl alcohol. 240584 wool
  • 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.
  • the at least one polyacrylate polymer obtained in step (i) is modified by transesterification with the polyalkylether alcohol (c2).
  • 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;
  • R 1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl;
  • R 2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.
  • 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;
  • R 1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl;
  • R 2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.
  • 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;
  • R 1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, or substituted or unsubstituted phenyl;
  • R 1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C 2 -C3o alkenyl, or substituted or unsubstituted phenyl;
  • R 2 is methyl
  • the polyether alcohol (c2) is R 1 -(O-CH 2 CH 2 )n-OH > Formula A1 wherein, n is an integer in the range of >1 to ⁇ 100;
  • R 1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C 2 -C3o alkenyl, or substituted or unsubstituted phenyl.
  • the polyether alcohol (c2) is
  • R 1 -(O-CH 2 CH 2 )n-OH > Formula A1 wherein, n is an integer in the range of >1 to ⁇ 100;
  • R 1 is substituted or unsubstituted C1-C30 alkyl.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the at least one alcohol is a combination of a mixture of Ci 2 -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
  • 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).
  • 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).
  • 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.
  • 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.
  • the modified polyacrylate polymer comprises
  • the modified polyacrylate polymer comprises
  • the modified polyacrylate polymer comprises
  • 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.
  • thermoplastic polymer is free of fluorine-based polymers, such as per- and polyfluoroalkyl substances (also known as PFAS).
  • 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.
  • 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).
  • HDPE high density polyethylene
  • HDPE- HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density
  • 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.
  • 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).
  • 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 cop
  • 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.
  • Polystyrene poly(p-methylstyrene), poly(a-methylstyrene).
  • 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 sty
  • 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).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • 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; st
  • 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.
  • 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.
  • 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.
  • Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • 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
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • 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.
  • Blends of the aforementioned polymers 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.
  • 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
  • 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).
  • thermoplastic polymer is polypropylene, polyethylene, any polypropylene copolymer or any polyethylene copolymer or any of their blends.
  • thermoplastic polymer is a linear low density polyethylene (LLDPE).
  • LLDPE linear low density polyethylene
  • 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.
  • 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).
  • 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.
  • interfacial agent examples 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.
  • silicone-polyether copolymers examples include, but are not limited to i) silicone-polyether copolymers ; ii)
  • 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.
  • 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.
  • 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.
  • thermoplastic polymer comprises a light stabilizer, preferably a hindered amine light stabilizer, and in particular oligomeric hindered amines.
  • 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;
  • 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) H 3 C C H 3
  • 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-C
  • alkyl having up to 12 carbon atoms examples include 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 _
  • alkoxy having up to 18 carbon atoms examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
  • a preferred radical is n-propoxy.
  • alkenyl having up to 6 carbon atoms examples include allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred.
  • the carbon atom in position 1 is preferably saturated.
  • Ci-C4alkyl examples of C5-Ci2cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C4alkyl are cyclohexyl, methylcyclohexyl and dimethylcyclohexyl.
  • C5-Ci2cycloalkoxy examples are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Cyclohexoxy is preferred.
  • Ci-C4alkyl examples include methylphenyl, dimethylphenyl, trimethylphenyl and tert-butylphenyl.
  • Ci-C4alkyl 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.
  • 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.
  • alkylene having up to 18 carbon atoms examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene and octamethylene.
  • C2- Cealkylene, in particular hexamethylene is preferred.
  • Cs-C/cycloalkylene is cyclohexylene.
  • Ci-C4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.
  • a preferred example of a 5-to 7-membered heterocyclic ring is a morpholine group.
  • radicals Ri and Xi are preferably hydrogen, methyl or propoxy, in particular n-propoxy.
  • 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.
  • 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
  • Particular preferred light stabilizers are the light stabilizer of the following formula:
  • the modified polyacrylate polymers are often used in the form of a masterbatch, rather than neat, when they are added to the polymer.
  • 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.
  • 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.
  • a mixer e.g. Banbury mixer
  • co-rotating twin screw extruder at a temperature above the melting point of the polymer.
  • 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.
  • 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.
  • extrusion such as film extrusion (cast film; blown film), fiber extrusion, pipe extrusion, profile extrusion, sheet extrusion; or tape extrusion.
  • 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.
  • extrusion such as film extrusion (cast film; blown film), fiber extrusion, pipe extrusion, profile extrusion, sheet extrusion; or tape extrusion.
  • Mw Weight average molecular weight
  • Mn 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).
  • 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. M P was 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).
  • THF tetrahydrofuran
  • PS polystyrene
  • Polyethylene PE-1 a high molecular weight linear low-density polyethylene (LLDPE), commercially available as ExxonMobil LL 1201 XV, ExxonMobil.
  • LLDPE high molecular weight linear low-density polyethylene
  • 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.
  • 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.
  • a transesterification catalyst e.g., tetrabutoxytitanate, lithium tert-butoxide, or lithium methanolate
  • a transesterification catalyst e.g., tetrabutoxytitanate, lithium tert-butoxide, or lithium methanolate
  • 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.
  • Example 3 Modified poly (butyl acrylate) and modified poly (ethyl acrylate)
  • modified polyfethyl acrylate and modified polyfbutyl acrylate were prepared according to the general methods described in Example 1 and 2.
  • 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.
  • 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.
  • 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.
  • rpm revolutions per minute
  • LS-1 a high molecular weight (about 1600-1800 g/mol) hindered amine NOR light stabilizerof the following formula:
  • LS-2 a high molecular weight (about 3000 g/mol) hindered amine light stabilizer of the following formula:
  • 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.
  • 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.

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Abstract

La présente invention concerne un article polymère façonné comprenant un polymère thermoplastique ; et un polymère de polyacrylate modifié pouvant être obtenu par un procédé comprenant i) la polymérisation d'au moins un monomère de méthacrylate et/ou d'au moins un monomère d'acrylate choisi parmi les acrylates d'alkyle en C1-C22 substitués ou non substitués, les acrylates de cycloalkyle en C4-C22 substitués ou non substitués, les acrylamides en C1-C22 substitués ou non substitués, ou les esters d'acide acrylique avec des alcools polyalkyléther, afin d'obtenir au moins un polymère de polyacrylate ; et ii) la modification de l'au moins un polymère de polyacrylate obtenu à l'étape (i) par transestérification avec au moins un alcool choisi parmi les alcools C8-C36 (c1) non substitués, ou des alcools de polyalkyléther (c2). La présente invention se rapporte également à un procédé d'amélioration des propriétés d'écoulement d'une masse fondue comprenant un polymère thermoplastique, qui comprend l'étape consistant à incorporer le polymère de polyacrylate modifié dans le polymère thermoplastique avant ou pendant le traitement à l'état fondu. La présente invention se réfère également à une utilisation du polymère de polyacrylate modifié pour améliorer les propriétés d'écoulement d'une masse fondue comprenant un polymère thermoplastique.
PCT/EP2025/072429 2024-08-12 2025-08-05 Adjuvant respectueux de l'environnement à base de polymère de polyacrylate modifié Pending WO2026037667A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133898A (en) * 1989-03-03 1992-07-28 Th. Goldschmidt Ag Manufacturing polyacrylate esters with long-chain hydrocarbon and polyoxyalkylene groups
US20060036013A1 (en) * 2002-06-08 2006-02-16 Franz-Leo Heinrichs Side-chain-modified copolymer waxes
US20130144011A1 (en) * 2010-06-29 2013-06-06 Basf Se Process for improving the flow of properties of polymer melts

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133898A (en) * 1989-03-03 1992-07-28 Th. Goldschmidt Ag Manufacturing polyacrylate esters with long-chain hydrocarbon and polyoxyalkylene groups
US20060036013A1 (en) * 2002-06-08 2006-02-16 Franz-Leo Heinrichs Side-chain-modified copolymer waxes
US20130144011A1 (en) * 2010-06-29 2013-06-06 Basf Se Process for improving the flow of properties of polymer melts

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