Polymer processing aids for polymer extrusion

Abstract

The present invention relates to a thermoplastic polymer composition comprising a matrix polymer (A) and a polymer processing aid (B), wherein (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method), and the melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (where the melt viscosity is measured at 210°C and 100s). -1 This relates to thermoplastic polymer compositions (measured by capillary rheometry at shear rates).

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic polymer composition comprising a matrix polymer (A) and a polymer processing aid (B). The present invention also relates to a method for extruding a thermoplastic polymer composition using an extruder and to an extruded article. [Background technology]

[0002] In extrusion methods, typically in the melt extrusion method, a solid polymer (called a matrix polymer), usually in the form of pellets or powder, is fed into an extruder and heated to a temperature above its melting point to produce a polymer molten material. The polymer molten material is then conveyed through an extrusion die located at the end of the extruder and formed into a desired shape, such as a tube, sheet, or film.

[0003] During the extrusion process, the polymer molten material is subjected to shear stress that can partially cause quality defects on the surface of the product, the most common of which is "melt fracture." Melt fracture often manifests as surface haze, which is described as appearing matte in the finish, and under magnification, it visually appears as a rough surface with a sawtooth pattern.

[0004] As the polymer molten material exits the die, slower-moving polymers in direct contact with the die accelerate rapidly. This rapid acceleration often causes cohesive failure of the polymer surface, known as melt fracture. Melt fracture is generally considered an unacceptable quality issue that adversely affects the optical and visual properties of the final product (one example being an inflated film). Melt fracture can also adversely affect the physical and mechanical properties of the final product.

[0005] Melt fracture formation is most common when extruding high molecular weight polyolefin polymers, such as those with a melt index value of 1 g / 10 min or less. High molecular weight polymers are often chosen to obtain improved physical and mechanical properties of the manufactured film, such as higher tensile strength at break. In other cases, high molecular weight polymers are chosen for the desired processing properties, such as increased polymer melt strength. Methods such as blown film and pipe extrusion are common examples of methods that benefit from polymers with higher melt viscosity.

[0006] A quality problem that can result from melt fracture is the accumulation of polymer at the die exit, a problem often referred to as die rolls. When melt fracture occurs, small molten polymer particles can detach from the surface and accumulate on the tooling surface near the die exit. Over time, these small molten particles accumulate, forming die rolls. Because die rolls tend to remain on the die for extended periods, they can burn and form solid spots, which can eventually be released from the die, creating quality defects on the product (such as spots and drag marks). Such problems tend to limit overall production rates, in addition to increased scrap rates and labor costs. Additives such as mineral fillers (found in many polymer compounds) may further promote melt fracture and die roll formation.

[0007] Melt fractures and die roll formation often occur in conjunction with another phenomenon called die expansion. Die expansion is related to the rapid release of elastic stress in the molten material as it exits the die. The presence of excessive die expansion is known to contribute to quality problems.

[0008] Extrusion of polymers with low melt index often generates high melt pressures. In many cases, the manufacturing rate is limited by the maximum melt pressure rating of the system used.

[0009] To address and resolve these issues, polymer processing aids (PPAs) containing fluoropolymers are widely used. Polymer processing aids can function by depositing a “slippery” coating on the internal tooling surface that comes into direct contact with the polymer molten material. This creates a “wall slip” where the polymer slides at the interface with the die wall, thereby reducing the melt stress as the molten material exits the die. The polymer molten material can then flow through the die with less shear stress formation, eliminating melt fractures and lowering the melt pressure. Polymer processing aids can offer several benefits, including, but are not limited to, reduced or eliminated melt fractures (resulting in a visually clearer product), lower die expansion, lower die roll formation, lower melt pressure, faster line speeds, and improved product characteristics.

[0010] For melt-workable thermoplastic polymers (and compounds), there exists a shear rate below which processing produces only smooth (and often glossy) surfaces, and above which processing produces rough (and often dull) surfaces. The shear rate at which surface defects are first observed is called the critical shear rate (CSR). Below the CSR, the polymer surface is usually smooth, and just above the CSR, melt fractures begin to form. Generally, as the shear rate increases beyond the CSR, the size or strength of the melt fractures also increases. Examples of polymers with these properties are polyolefin polymers such as LLDPE resin (linear low-density polyethylene), which is used in the manufacture of inflation films. Other examples include LDPE (low-density polyethylene), MDPE (medium-density polyethylene), UHDPE (ultra-high-density polyethylene), or HDPE (high-density polyethylene).

[0011] LLDPE polymers with low melt index typically have a low critical shear rate and are prone to melt fracture. Generally, the lower the melt index of a polymer, the more likely it is to form melt fractures. Since LLDPE polymers with low melt index are commonly used to manufacture inflation films, the problem of melt fracture is, as expected, a common concern for such methods.

[0012] US5986005 describes compositions comprising a hydrocarbon polymer diluted with a fluoroelastomer and a thermoplastic polyamide for improving the conversion rate of the hydrocarbon polymer. A thermoplastic polyamide is defined as a polymer containing polyamide blocks and polyether blocks.

[0013] WO02 / 066544 describes an extrudeable composition comprising a non-fluorinated melt-processable polymer and a fluoropolymer processing aid.

[0014] US2013 / 093118 describes compositions comprising polyolefins and polymers that may be polyamides, copolyamides, second polyolefins different from the first polyolefin, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and vinyl alcohol (EVOH), polystyrene, polycarbonate, and polyvinyl chloride (PVC).

[0015] WO2023 / 017327 describes a polymer processing aid comprising a block copolymer having a polyamide block and a polyether block, which effectively reduces melt defects in thermoplastic polyolefins.

[0016] However, it was found that the PPA described above does not yield satisfactory results in reducing melting defects. [Prior art documents] [Patent Documents]

[0017]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0018] Therefore, there is a need for a PPA additive that is more effective than known fluorinated PPA or other types of PPA known in the art.

Means for Solving the Problems

[0019] The present invention is a thermoplastic polymer composition comprising a matrix polymer (A) and a polymer processing aid PPA (B), (δpolymer (B) - δmatrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is the solubility parameter calculated according to the Fedor method), The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (where the melt viscosity is measured by capillary rheometry at 210 °C and a shear rate of 100 s -1 of J), and provides a thermoplastic polymer composition.

[0020] The solubility parameter is determined according to the Fedor method (R.F. Fedors, Polymer engineering and science 142, 147-154, 1974; R.F. Fedors, Polym.Eng.Science, vol. 14, N°2, 147, 1974) according to the following formula.

[0021]

number

[0022] ΔE corresponds to the cohesive energy, and V corresponds to the molar volume.

[0023] Therefore, this method involves adding the energy contributions of the various groups that make up the polymer. The energy contributions of different groups are shown in the following study: Eric A. Grulke, Solubility Parameter Values, Polymer Handbook, 4th Edition, 1999, VII / 675-714.

[0024] According to the present invention, the amount of matrix polymer (A) in the thermoplastic polymer composition is at least 50% by weight, typically 55 to 99.9% by weight.

[0025] In some embodiments, the thermoplastic polymer composition comprises two or more polymer processing aids.

[0026] The present invention makes it possible to address the above-mentioned needs. More specifically, the present invention provides improved PPA additives for improving the processability of extruded polymers. For example, the PPA additives reduce or eliminate melt fractures, die buildup, and / or surface defects in the polymer composition during the extrusion method. This is achieved by using specific polymer processing aids, taking into account the matrix polymer used in the extrusion method.

[0027] Compared to conventional fluorinated PPA, this PPA is even more advantageous because it is cheaper and non-halogenated.

[0028] Therefore, the present invention provides a more effective PPA additive for improving the processability of extruded polymer materials, particularly for reducing melt fracture.

[0029] In some embodiments, the amount of polymer processing aid (B) in the thermoplastic polymer composition is 50 to 5000 ppm (parts per million), preferably 100 to 3000 ppm, and more preferably 200 to 3000 ppm, relative to the weight of the matrix polymer.

[0030] In some embodiments, the matrix polymer is a polyolefin composition, preferably the polyolefin composition comprises or consists of unfunctionalized polyolefins.

[0031] In some embodiments, the matrix polymer essentially consists of or comprises linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high-density polyethylene (UHDPE), or polypropylene (PP), or a combination thereof.

[0032] In some embodiments, polymer processing aids are selected from polyamides, PEBA, or mixtures thereof.

[0033] In some embodiments, the polymer processing aid is a polyamide.

[0034] In some embodiments, the polymer processing aid is a homopolyamide containing PA6, PA10, PA11 and / or PA12, and / or a copolyamide containing PA66, PA610, PA612, PA1012, PA1212 and / or PA6, 10, 12, preferably PA11, or a polyamide containing the same.

[0035] In some embodiments, the polymer processing aid is a copolyamide.

[0036] In some embodiments, the polymer processing aid is PEBA.

[0037] In some embodiments, the polymer processing aid (B) is greater than 20.0, preferably 21.0 (J1 / 2.cm) -3 A solubility parameter greater than / 2) (however, the solubility parameter is calculated according to the Fedor method), and 210°C and 100s -1 It has a melt viscosity of 10-500 Pa.s, preferably 20-400, and more preferably 20-350, as measured by capillary rheometry at a shear rate.

[0038] In some embodiments, the thermoplastic polymer composition comprises at least one adjuvant, preferably one or more selected from polyethers, aliphatic polyesters, poly(hydroxybutyrate), silicones, fatty acid esters, and fatty acid amides, preferably polyether copolymers, or comprising them.

[0039] In another aspect, the present invention relates to a method for extruding a thermoplastic polymer composition comprising a matrix polymer (A) using an extruder, comprising the step of supplying a polymer processing aid to the extruder. (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method), The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). -1 The method provides a way to measure the shear rate (measured by capillary rheometry).

[0040] In some embodiments, the method further includes the step of supplying at least one adjuvant to an extruder.

[0041] In some embodiments, the polymer processing aid and, if present, the adjuvant are supplied in the form of a masterbatch composition containing a carrier polymer (C).

[0042] In some embodiments, polymer processing aids and, if present, adjuvants are supplied directly to the extruder, separately, simultaneously, or as a blend.

[0043] In some embodiments, the matrix polymer is a polyolefin, and preferably the polyolefin composition comprises or consists of a non-functionalized polyolefin.

[0044] In some embodiments, the matrix polymer essentially consists of or comprises linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high-density polyethylene (UHDPE), or polypropylene (PP), or a combination thereof.

[0045] In some embodiments, the amount of polymer processing aid (B) is 50 to 5000 ppm, preferably 100 to 3000 ppm, and more preferably 200 to 3000 ppm, relative to the weight of the matrix polymer.

[0046] In some embodiments, polymer processing aids are selected from polyamides, PEBA, or mixtures thereof.

[0047] In some embodiments, the polymer processing aid (B) has a solubility parameter greater than 20 (J1 / 2.cm-3 / 2) (where the solubility parameter is calculated according to the Fedor method) and is processed at 210°C and 100 s. -1 It has a melt viscosity measured by capillary rheometry at a shear rate of 10 to 500 Pa.s, preferably 20 to 500, more preferably 20 to 400, and most preferably 30 to 100.

[0048] In some embodiments, the polymer processing aid is a polyamide, PEBA, or a mixture thereof.

[0049] Preferably, the polyamide is selected from PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamides PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or blends thereof of these polymers.

[0050] Preferably, the PEBA block polyamide is selected from PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamides PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or blends thereof of these polymers.

[0051] In some embodiments, one or more polymer processing aids are mixed with the matrix polymer (e.g., pre-mixed) or pre-blended (e.g., dry-blended or melt-blended) before the matrix polymer is extruded.

[0052] In some embodiments, one or more polymer processing aids are supplied simultaneously with the matrix polymer in the extruder.

[0053] In some embodiments, one or more polymer processing aids are added to a matrix polymer to prepare a masterbatch. The resulting masterbatch can then be used to introduce one or more polymer processing aids into the matrix polymer by any conventional method before extrusion of the matrix polymer (e.g., dry blending or melt blending) or during extrusion of the matrix polymer (e.g., simultaneous feeding with the matrix polymer to the extruder).

[0054] In another aspect, the present invention provides an extruded article comprising the polymer composition defined above, preferably a film, sheet, tube, pipe, wire, fiber, cable, wire coating, or cable jacket.

[0055] In another aspect, the present invention relates to the use of a polymer (B) as a processing aid for extruding a thermoplastic polymer composition comprising a matrix polymer (A), (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method), The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). -1 (Measured by capillary rheometry at shear rate), it provides a means of use. [Modes for carrying out the invention]

[0056] Herein, the present invention will be described in more detail without limiting it.

[0057] According to the present invention, PPA is used to improve the processability of extruded thermoplastic compositions containing a matrix polymer. Preferably, PPA is used as a polymer processing aid when extruding polyolefin compositions.

[0058] The term "polymer processing aid" or PPA, also known as "extruder," refers to additives used to improve the conversion rate of polymer materials, to improve the extrudeability of polymer materials, and / or to reduce quality defects such as melt fracture and die buildup that may occur during the extrusion process, and may also improve the mechanical and / or optical properties of the polymer materials.

[0059] Examples of improvements provided by the use of PPA according to the present invention include, but are not limited to, the elimination or reduction of melt fracture (sharkskin), improved film transparency, improved smoothness and surface properties, improved product appearance, improved mechanical properties, reduced gel, gauge control, reduced maintenance time, reduced die buildup, manufacturing consistency, smoother extrusion conditions, lower energy consumption, shorter cycle times and faster transitions, reduced potential negative interactions with other film additives such as antiblock and hindered amine light stabilizers (HALS), reduced extruder torque, and a decrease in the polymer critical shear rate.

[0060] A common method for evaluating PPA performance is to measure the time it takes to eliminate melt fractures after the PPA is introduced. A typical test involves setting up extrusion conditions favorable for melt fracture formation, including the appropriate selection of tooling, polymer, and process conditions. Once the correct conditions for melt fracture formation are obtained and the process is stable, the PPA can be added and the time it takes to eliminate the melt fractures can be recorded. A better performing PPA is one that requires less time to eliminate melt fractures. The elapsed time after the extruder is started that the extruded article exhibits a high degree of melt fracture before obtaining an extruded article with a smooth surface free of melt fractures is also called the conditioning time.

[0061] In general, PPAs that are found to be able to rapidly eliminate melt fractures are also found to offer better efficiency. For example, when manufacturing an inflation film, if one PPA can eliminate melt fractures in 30 minutes and another PPA can eliminate them in 40 minutes, the PPA that can eliminate melt fractures in 30 minutes is considered more efficient at eliminating melt fractures.

[0062] The present invention relates to a thermoplastic polymer composition comprising a matrix polymer (A) and a polymer processing aid PPA (B), (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method), The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). -1 The present invention provides a thermoplastic polymer composition (measured by capillary rheometry at shear rates).

[0063] In some embodiments, the difference between the solubility parameter of polymer (B) and the solubility parameter of matrix polymer (A) (δ polymer (B) - δ matrix polymer (A)) is greater than 3.2, preferably greater than 3.5, more preferably greater than 4.0, and even more preferably greater than 5.0 (J1 / 2.cm-3 / 2).

[0064] In some embodiments, the melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.15, preferably less than 0.10, and more preferably less than 0.05.

[0065] In some embodiments, the thermoplastic polymer composition comprises a matrix polymer (A) and a polymer processing aid PPA (B). (δ polymer (B) - δ matrix polymer (A)) > 3.2 (J1 / 2.cm-3 / 2), preferably > 3.5 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method), The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100s). -1 (Measured by capillary rheometry at shear rate).

[0066] In some embodiments, the thermoplastic polymer composition has a ratio of (δ polymer (B) - δ matrix polymer (A)) to (melt viscosity ratio of polymer (B) to matrix polymer (A)) greater than 13.1, preferably greater than 20.0, and more preferably greater than 30.0.

[0067] According to the present invention, the polymer processing aid is typically selected from polyamides, copolyether block amides (PEBAs), or mixtures thereof.

[0068] polyamide According to the present invention, the polymer processing aid is typically a homopolyamide, i.e., a polyamide obtained from one type of monomer, or a copolyamide, i.e., a polyamide obtained from several different types of monomers.

[0069] In some embodiments, the polymer processing aid is a homopolyamide.

[0070] In some embodiments, the polymer processing aid is a copolyamide.

[0071] The monomers (repeating units) that make up polyamides can be selected from units derived from amino acids, lactams, and units corresponding to the formula (Ca diamine) and (Cb diacid), where a represents the number of carbon atoms in the diamine and b represents the number of carbon atoms in the diacid, and a and b are in the range of 4 to 36, respectively.

[0072] When the unit represents a unit derived from an amino acid, it can be selected from 9-aminononanoic acid (A=9), 10-aminodecanoic acid (A=10), 12-aminododecanoic acid (A=12), and 11-aminoundecanoic acid (A=11), as well as their derivatives, particularly N-heptyl-11-aminoundecanoic acid.

[0073] When the unit represents a unit derived from lactam, it can be selected from pyrrolidinene, 2-piperidinone, caprolactam (A=6), enantractam, capryloractam, pelargolactam, decanolactam, undecanolactam, and lauryllactam (A=12).

[0074] When a unit represents a unit derived from a unit corresponding to the formula (Ca diamine).(Cb diacid), the (Ca diamine) unit is selected from linear or branched aliphatic diamines, alicyclic diamines, and alkyl aromatic diamines.

[0075] When the diamine is an aliphatic and linear compound of the formula H2N-(CH2)a-NH2, the (Ca diamine) monomer is preferentially selected from butanediamine (a=4), pentanediamine (a=5), hexanediamine (a=6), heptanediamine (a=7), octanediamine (a=8), nonanediamine (a=9), decanediamine (a=10), undecanediamine (a=11), dodecanediamine (a=12), tridecanediamine (a=13), tetradecanediamine (a=14), hexadecanediamine (a=16), octadecanediamine (a=18), octadecenediamine (a=18), eicosanediamine (a=20), docosanediamine (a=22), and diamines obtained from fatty acids.

[0076] If the diamine is aliphatic and branched, the diamine may contain one or more methyl or ethyl substituents on the main chain. For example, (Ca diamine) monomers can be advantageously selected from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-diaminopentane, 2-methyl-1,5-pentanediamine, and 2-methyl-1,8-octanediamine.

[0077] If the (Ca diamine) monomer is alicyclic, the (Ca diamine) monomer is preferentially selected from bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane (BMACM or MACM), p-bis(aminocyclohexyl)methane (PACM), and isopropylidene di(cyclohexylamine) (PACP). The (Ca diamine) monomer may also contain the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), and di(methylcyclohexyl)propane. A non-exclusive list of these alicyclic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0078] If the (Ca diamine) monomer is alkyl aromatic, the (Ca diamine) monomer is preferentially selected from 1,3-xylylenediamine and 1,4-xylylenediamine.

[0079] When the unit corresponds to the formula (Ca diamine).(Cb diacid), the (Cb diacid) unit is selected from linear or branched aliphatic diacids, alicyclic diacids, and aromatic diacids.

[0080] When the (Cb dioic acid) monomer is aliphatic and linear, the (Cb dioic acid) monomer is selected from succinic acid (b=4), pentanediic acid (b=5), adipic acid (b=6), heptanediic acid (b=7), octanedioic acid (b=8), azelaic acid (b=9), sebacic acid (b=10), undecanediic acid (b=11), dodecanediic acid (b=12), brassic acid (b=13), tetradecanediic acid (b=14), hexadecanedioic acid (b=16), octadecanediic acid (b=18), octadecenediic acid (b=18), eicosanedioic acid (b=20), docosanedioic acid (b=22), and fatty acid dimers containing 36 carbon atoms.

[0081] The above-mentioned fatty acid dimers are dimerized fatty acids obtained by oligomerization or polymerization of hydrocarbon long-chain unsaturated monobasic fatty acids (such as linoleic acid and oleic acid), as described in particular in reference EP0471566.

[0082] If the diacitor is alicyclic, it may include the following carbon-based skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), and di(methylcyclohexyl)propane.

[0083] If the diacid is aromatic, it is preferentially selected from terephthalic acid (indicated by T), isophthalic acid (indicated by I), and naphthalene diacid.

[0084] Polyamides may be crystalline or amorphous and transparent.

[0085] Preferably, the polyamide according to the present invention is selected from aliphatic polyamides, more specifically from aliphatic polyamides having a unit chain length in the range of 4 to 18, and more specifically from 4 to 12.

[0086] More preferably, the polyamide according to the present invention is selected from the polyamides PA6, PA10, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, and PA1212.

[0087] More preferably, the polyamide according to the present invention is selected from copolyamides PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or blends of these polymers.

[0088] As will be understood by those skilled in the art, the number molecular weight of polyamides can vary widely. In some embodiments, the number average molecular weight M n is from 300 to 50,000 g / mol, preferably from 500 to 30,000 g / mol, more preferably from 1,000 to 25,000 g / mol.

[0089] The number average molecular weight or number average molar mass M n is expressed as PMMA equivalent (used as a calibration standard) and can be measured by size exclusion chromatography (SEC) in accordance with the ISO16014-1:2019 standard. The polymer is dissolved in hexafluoroisopropanol stabilized with 0.05 M potassium trifluoroacetate at a concentration of 1 g / L, for example at a flow rate of 1 ml / min, at room temperature for 24 hours before passing through the column, and the molar mass is measured by refractive index. Size exclusion chromatography can be performed using columns of modified silica, for example, a set of two columns and a precolumn of modified silica including a 1000 Å column having dimensions of 300×8 mm and a particle size of 7 μm, a 100 Å column having dimensions of 300×8 mm and a particle size of 7 μm, and a precolumn having dimensions of 50×8 mm (for example, PGF columns and a precolumn from Polymer Standards Service), for example at a temperature of 40°C.

[0090] The polyamide or copolyamide can be obtained by melt condensation of one type of monomer or two different types of monomers as described above.

[0091] Several suitable polyamides or copolyamides are available from ARKEMA under the trademarks RILSAN® and Platamid®, from EVONIK under the trademarks VESTAMID® and VESTAMELT®, or from EMS under the trademarks GRILAMID® and GRILTEX®.

[0092] Suitable polyamides or copolyamides, such as PA12, according to the present invention can also be obtained by the anionic polymerization of lactams in a solvent or solution. Several suitable ones are commercially available from Arkema under the trademark ORGASOL®.

[0093] PEBA According to the present invention, the polymer processing aid comprises a polyamide block having a reactive end and a polyether block having a reactive end, in particular, 1) A polyamide block having a diamine chain terminus, and a polyoxyalkylene block having a dicarboxylic acid chain terminus, 2) A polyamide block having a dicarboxylic acid chain terminus, and a polyoxyalkylene block having a diamine chain terminus, obtained by cyanoethylation and hydrogenation of an α,ω-dihydroxylated aliphatic polyoxyalkylene block known as a polyetherdiol. 3) A polyamide block having a dicarboxylic acid chain terminus and a polyetherdiol (the resulting product is, in this particular case, a polyetheresteramide) It may also be a copolyether block amide (PEBA) resulting from polycondensation with [another substance].

[0094] Number-average molecular mass M of PEBA n The number-average molar mass of PEBA can vary from 500 to 30000 g / mol, preferably from 1000 to 25000 g / mol, more preferably from 1000 to 20000 g / mol, and even more preferably from 1000 to 15000 g / mol. The number-average molar mass of PEBA can be measured by gel permeation chromatography (GPC) before copolymerization of the block.

[0095] Polyamide blocks with dicarboxylic acid chain ends are derived, for example, from the condensation of polyamide precursors in the presence of a chain-restricting (also called a chain-restricting agent) dicarboxylic acid. Polyamide blocks with diamine chain ends are derived, for example, from the condensation of polyamide precursors in the presence of a chain-restricting (also called a chain-restricting agent) diamine.

[0096] Polymers containing polyamide blocks and polyether blocks may also contain randomly distributed units.

[0097] The types of polyamide blocks may be used in the same way as described above for polyamides. Typically, the polyamides constituting the polyamide block are selected from aliphatic polyamides, more specifically aliphatic polyamides with a unit chain length in the range of 4 to 18, and more specifically 4 to 12.

[0098] More preferably, the polyamides constituting the polyamide block are selected from PA6, PA10, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamides PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or blends of these polymers.

[0099] Polyether PE blocks are formed from alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide units, or tetrahydrofuran (resulting in a polytetramethylene glycol sequence). Therefore, PEG (polyethylene glycol) blocks, i.e., blocks formed from ethylene oxide units, PPG (propylene glycol) blocks, i.e., blocks formed from propylene oxide units, PO3G (polytrimethylene glycol) blocks, i.e., blocks formed from polytrimethylene glycol ether units (such copolymers with polytrimethylene ether blocks are described in US6590065), and PTMG blocks, i.e., blocks formed from tetramethylene glycol units, also known as polytetrahydrofuran. PEBA copolymers may contain several types of polyethers in their chains, and the copolyethers may be in block or statistical form.

[0100] A block obtained by oxyethylation of bisphenol, for example, bisphenol A, may also be used. The latter product is described in patent EP613919.

[0101] The polyether block may also be formed from an ethoxylated primary amine. An example of an ethoxylated primary amine is:

[0102] [ka] Examples of products include those in the formula (where m and n are between 1 and 20, and x is between 8 and 18). These products are marketed by CECA under the trade name Noramox® and by Clariant under the trade name Genamin®.

[0103] The flexible polyether block may include a polyoxyalkylene block having an NH2 chain terminus, such a block can be obtained by cyanoacetylation of an α,ω-dihydroxylated aliphatic polyoxyalkylene block called a polyetherdiol. More specifically, Jeffamine products (e.g., Jeffamine® D400, D2000, ED2003, XTJ542, commercially available products of Huntsman, as described in patents JP2004346274, JP2004352794 and EP1482011) may be used.

[0104] The polyetherdiol block is used in an unmodified form and co-condensed with a polyamide block having carboxylic acid-terminated groups, or they are aminated to a polyetherdiamine and then condensed with a polyamide block having carboxylic acid-terminated groups. A general method for the two-step preparation of a PEBA copolymer containing an ester bond between the PA block and the PE block is known, for example, described in French Patent FR2846332. A general method for the preparation of the PEBA copolymer of the present invention containing an amide bond between the PA block and the PE block is known, for example, described in European Patent EP1482011. The polyether block may be mixed with a polyamide precursor and a chain-restricting diacitor to produce a polymer containing a polyamide block and a polyether block having randomly distributed units (one-step process).

[0105] Needless to say, the term PEBA as used herein refers not only to the Pebax® products sold by Arkema, the Vestamid® products sold by Evonik®, and the Grilamid® products sold by EMS, but also to the Kellaflex® products sold by DSM or any other PEBA from other suppliers.

[0106] The number-average molar mass Mn of polyamide blocks in PEBA can typically be 400 to 20,000 g / mol, preferably 500 to 10,000 g / mol, and more preferably 600 to 5,000 g / mol.

[0107] The number-average molar mass of the polyether block can typically be 100 to 6000 g / mol, preferably 200 to 3000 g / mol, and more preferably 600 to 2500 g / mol.

[0108] The number-average molar mass is determined by the content of the chain-limiting agent. The number-average molar mass is calculated using the following formula: M n =n モノマー ×MW 繰返し単位 / n 鎖制限剤 +MW 鎖制限剤 It can be calculated according to [the formula].

[0109] In this formula, n モノマー n represents the number of moles of monomer, 鎖制限剤 represents the excess moles of the dioxide limiting agent, MW 繰返し単位 represents the molar mass of the repeating unit, MW 鎖制限剤 This represents the excess molar mass of the diacitor.

[0110] Adjuvant In some embodiments, the polymer processing aid is used in combination with at least one adjuvant. In other words, the polymer processing aid and at least one adjuvant are used together as a PPA when extruding the polymer composition. The adjuvant may be selected to further improve the stability and / or effectiveness of such a PPA. Examples of adjuvants include: i) Aliphatic polyesters, such as poly(caprolactone), poly(lactic acid), and poly(butylene adipate), ii) Poly(hydroxybutyrate), iii) Silicone, iv) Fatty acid esters, e.g., sorbitan monolaurate, v) Fatty acid amides, such as stearamide and erucamide These include, but are not limited to, the following:

[0111] Polymer processing aids and adjuvants may be provided as a blend before being included in the masterbatch or added directly to the polymer composition, as described later. The blend may be formed by methods including dry blending, melt blending, or compounding. The blend may be in the form of, for example, pellets or powder.

[0112] Matrix polymer (A) In some embodiments of the present invention, the matrix polymer (A) is a polyolefin composition, preferably the polyolefin composition comprises or consists of a non-functionalized polyolefin.

[0113] Examples of polyolefin compositions include, but are not limited to, linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high-density polyethylene (UHDPE), polypropylene (PP), or combinations thereof. Preferably, the polyolefin composition is essentially composed of or comprises LDPE or LLDPE.

[0114] The melt index of the matrix polymer is 0.01 g / 10 min to 100 g / 10 min, preferably 0.06 g / 10 min to 60 g / 10 min, more preferably 0.06 to 10 g / 10 min (2.16 kg weight, 300 s) -1 This may also be the collection shear rate and the melt index measured at a melting temperature of 190°C.

[0115] In one embodiment, these ranges apply to the matrix composition before / without PPA addition. In another embodiment, these ranges apply to the thermoplastic composition obtained after PPA addition.

[0116] The polydispersity of the matrix polymer composition may be 1.1 to 9.0, preferably 1.1 to 4.0, and more preferably 1.1 to 2.5. These ranges apply to the matrix composition without PPA addition / previously.

[0117] The polydispersity index (PDI) is a measure of chain length uniformity calculated from the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). These values ​​are defined by the following formulas.

[0118]

number

[0119] The polydispersibility of a matrix polymer can typically be determined by gel permeation chromatography (GPC)-viscositometry. The GPC-viscositometry technique is based on the ASTM D6474-99 method and analyzes the polymer sample using a dual refractometer / viscometer detector system.

[0120] In some embodiments, the polyolefin in the polyolefin composition is either a non-functionalized polyolefin or includes a non-functionalized polyolefin.

[0121] The polyolefin composition may also contain one or more other additives, such as fillers, pigments, dyes, antioxidants, UV absorbers and light stabilizers, nucleating agents and reinforcing agents.

[0122] The filler may include dispersed organic or inorganic particles. Examples of inorganic fillers include silica, alumina, zeolite, titanium dioxide, carbonate (e.g., sodium carbonate or potassium carbonate), hydrotalcite, talc, zinc oxide, magnesium oxide or calcium oxide, diatomaceous earth, and carbon black. The pigment may be inorganic or organic.

[0123] In some embodiments, the polyolefin composition is extruded as a film, tube, or sheet, for example, as an inflation film.

[0124] PPA and, if present, at least one adjuvant are added to the extruded thermoplastic polymer composition such that the total amount of PPA and at least one adjuvant (if present) is 10 to 200,000 ppm by weight, preferably 25 to 100,000 ppm by weight, and more preferably 50 to 2,000 ppm by weight, relative to the total weight of the thermoplastic composition obtained after extrusion.

[0125] When PPA is used together with at least one adjuvant, the weight ratio of PPA to at least one adjuvant in the resulting polymer composition may be in the range of 90:10 to 20:80, preferably 70:30 to 30:70, more preferably 60:40 to 40:60, for example, about 50:50.

[0126] Masterbatch In some embodiments, PPA(B) and, if present, an adjuvant are added together in the form of a masterbatch to a thermoplastic polymer composition comprising a matrix polymer (A).

[0127] In this application, the term “masterbatch” refers to a composition containing a polymer processing aid pre-dispersed in a carrier polymer. The terms “carrier polymer” or “diluted polymer” refer to the main component of the masterbatch used to contain the polymer processing aid composition. The carrier polymer may be, or may contain, the same polymer composition being extruded. Alternatively, the carrier polymer may be, or may contain, a different polymer composition that does not adversely affect the extrusion behavior of the extruded polymer composition. In this application, the extruded polymer composition, i.e., the host resin or matrix polymer, is a polyolefin composition.

[0128] The masterbatch may be provided in the form of a powder, granules, or pellets. The preparation of the masterbatch can be carried out using any method or process known in the art, such as the method described in US8501862.

[0129] Masterbatches are typically manufactured by extrusion compounding to produce products in pellet form, but other embodiments may also be included.

[0130] The carrier polymer may be a polyolefin, whether functionalized, unfunctionalized, or a mixture thereof. For example, it may be polyethylene such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or ultra-high-density polyethylene (UHDPE), or a combination thereof. It may be polyethylene obtained using a metallocene-type catalyst, or more generally, a "single-site" catalyst, a Phillips-type catalyst, or a Ziegler-Natta-type catalyst. Polypropylene, particularly isotactic polypropylene or syndiotactic polypropylene, biaxially oriented polypropylene, polybutene (obtained from 1-butene), poly(3-methylbutene) or poly(4-methylpentene), or a blend of two or more polyolefins, such as a blend of LLDPE and LDPE, can be used as carriers.

[0131] The carrier polymer may be a copolymer, for example, ethylene acrylate (which can be seen under the Lotryl® trademark from SK Functional Polymer) or ethylene vinyl acetate.

[0132] The selection of a suitable polyolefin carrier polymer for a masterbatch typically addresses several concerns, including miscibility within the polyolefin polymer used and its ability to disperse well without gel formation. Masterbatches prepared with carrier polymers having a low melt index (high melt viscosity) are expected to form a gel, or have the potential to form a gel, when introduced into polyolefin polymers with a higher melt index. Specifically, the formed gel contains large undispersed aggregates of the masterbatch. Typically, the carrier polymer is selected to have a melt index equal to or higher than that of the matrix polymer used. The typical melt index range for carrier polymers is 0.06 to 20, and masterbatches prepared using this polyethylene carrier polymer are best suited for polyolefin polymers with a melt index of 2 or less.

[0133] In some embodiments, PPA and, if present, an adjuvant are added to a thermoplastic polymer composition comprising a matrix polymer in the form of a masterbatch containing a polyolefin.

[0134] In some embodiments, the masterbatch contains PPA and, if present, adjuvants at a level ranging from 1 to 30% by weight, preferably 2 to 15% by weight, and more preferably 5 to 10% by weight, relative to the total weight of the masterbatch. For example, the amount of PPA and, if present, adjuvants in the masterbatch is about 7.5% by weight.

[0135] The masterbatch can be used in any manner known in the art, and is typically pre-blended with a thermoplastic polymer composition containing a matrix polymer in pellet or powder form, or supplied separately using suitable equipment such as a loss and weight feeder, or pre-formulated to produce an extrudeable compound. For example, the masterbatch may be added by dry blending during the extrusion of the polymer composition.

[0136] Masterbatches are particularly advantageous when used as PPA for thermoplastic polymers such as polyethylene that exhibit high molecular weight and / or a narrow molecular weight distribution (typically such that the polydispersity index is less than 3, rather less than 2.5, and better even less than 2.2). Masterbatches are especially useful for extruding polyolefins, particularly polyethylene, in film form.

[0137] In addition to the masterbatch form, in some embodiments, PPA and, if present, adjuvants are added directly to the polymer composition. PPA and, if present, adjuvants may be added separately, simultaneously, or as a blend (particularly a dry blend) to the extruded thermoplastic polymer composition.

[0138] PPA and, if present, adjuvants may be added to the thermoplastic polymer composition by dry blending in powder form, or by melt blending or compounding. Melt blending may be carried out in an extruder or co-kneader, more preferably a twin-screw extruder or co-kneader.

[0139] method The present invention also relates to a method for extruding a thermoplastic polymer composition containing a matrix polymer using an extruder, comprising the step of supplying a polymer processing aid to the extruder.

[0140] The extrusion method of the present invention is typically a melt extrusion method.

[0141] In some embodiments, the method further includes the step of supplying at least one adjuvant to an extruder. The PPA, at least one adjuvant, and thermoplastic polymer composition are those defined above.

[0142] In some embodiments, the polymer processing aid and, if present, the adjuvant are supplied in the form of a masterbatch composition containing a carrier polymer (C).

[0143] In some embodiments, polymer processing aids and, if present, adjuvants are supplied directly to the extruder, separately, simultaneously, or as a blend.

[0144] This method may include a further step of supplying one or more other additives, such as fillers, pigments, dyes, and antioxidants, to the extruder.

[0145] In some embodiments, the method is carried out at a shear rate that produces a thermoplastic composition extruded with melt fracture defects when the method is carried out using a thermoplastic composition consisting essentially of a matrix polymer.

[0146] Goods The present invention also relates to an article comprising a thermoplastic polymer composition extruded by a method according to the present invention, or an article manufactured from said thermoplastic polymer composition.

[0147] In some embodiments, the article is selected from films, tubes, pipes, wires, fibers, cables, wire coatings, and cable jackets. [Examples]

[0148] The following examples will be described without limiting the present invention.

[0149] Synthesis of polyamides [Example 1] 308 g of caprolactam, 111.6 g of hexamethylenediamine, 140.6 g of adipic acid, 840 g of lauryl lactam, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 280°C under stirring and autocompensation. The mixture is maintained at 280°C for 4 hours, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set, and a torque meter is used to allow the reaction medium to thicken, stopping the polymerization at the desired torque. The reactor is drained into a water bath, and the polymer then forms a cooling rod, which is granulated.

[0150] [Example 2] 630 g of caprolactam, 217 g of hexamethylenediamine, 273 g of adipic acid, 280 g of lauryl lactam, and 7 g of water are added to a 4 L autoclave. The synthesis is carried out in the same manner as in Example 1, except that the target material temperature is 260 °C and the holding time is 3 hours.

[0151] [Example 3] 343 g of caprolactam, 98.1 g of hexamethylenediamine, 289.6 g of dodecanedioic acid, 421.4 g of amino-11-undecanoic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 260°C under stirring and autocompacting pressure. The mixture is maintained at 260°C for 1 hour, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set for 30 minutes, then the autoclave is placed under vacuum (<20 mbar). 247.9 g of PEG with a molar mass of 600, followed by 2.8 g of zirconium acetate, are introduced into the reactor. The reactor is returned to vacuum and polymerization is stopped at the desired torque. The reactor is drained into a water bath, and the polymer is cooled to form rods, which are then granulated.

[0152] [Example 4] 655.1 g of caprolactam, 73.4 g of adipic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 230°C under stirring and autocompensation. The mixture is maintained at 260°C for 1 hour, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set for 10 minutes, and then 671.5 g of PEG1500 is introduced into the reactor. The reactor is placed under vacuum (<10 mbar) for 1 hour, and then 4.2 g of zirconium butoxide is added. Polymerization is continued under vacuum until the desired torque is reached. The reactor is drained into a water bath, and the polymer is cooled to form rods, which are then granulated.

[0153] [Example 5] 659.9 g of lauryl lactam, 70.6 g of adipic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 280°C under stirring and autocompensation. The mixture is maintained at 280°C for 4 hours, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set for 10 minutes, and then 669.5 g of PEG1500 is introduced into the reactor. The reactor is placed under vacuum (<10 mbar) for 1 hour, and then 3 g of zirconium butoxide is added. Polymerization is continued under vacuum until the desired torque is reached. The reactor is drained into a water bath, and the polymer is cooled to form rods, which are then granulated.

[0154] [Example 6 (Comparative Example)] The synthesis was carried out in the same manner as in Example 5, except that 235.2 g of lauryl lactam, 37.3 g of adipic acid, 7 g of water, 576.7 g of PEG1500, and 1.7 g of zirconium butoxide were used.

[0155] [Example 7] 259.8 g of lauryl lactam, 78.8 g of adipic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 280°C under stirring and autocompensation. The mixture is maintained at 280°C for 4 hours, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set for 10 minutes, and then 1061.3 g of PTMG2000 is introduced into the reactor. The reactor is placed under vacuum (<10 mbar) for 1 hour, and then 4.2 g of zirconium butoxide is added. Polymerization is continued under vacuum until the desired torque is reached. The reactor is drained into a water bath, and the polymer is cooled to form rods, which are then granulated.

[0156] [Example 8] 648.1 g of amino-11-undecanoic acid, 72.0 g of adipic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 250°C under stirring and autocompact pressure. The mixture is maintained at 250°C for 1 hour, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set for 10 minutes, and then 679.8 g of PTMG1000 is introduced into the reactor. The reactor is placed under vacuum (<10 mbar) for 1 hour, and then 2 g of zirconium butoxide is added. Polymerization is continued under vacuum until the desired torque is reached. The reactor is drained into a water bath, and the polymer is cooled to form rods, which are then granulated.

[0157] [Example 9] The synthesis was carried out in the same manner as in Example 5, except that 652 g of lauryl lactam, 56.5 g of adipic acid, 7 g of water, 691.5 g of PTMG2000, and 2.2 g of zirconium butoxide were used.

[0158] [Example 10] 7.4 g of adipic acid, 1392.6 g of lauryl lactam, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 280°C under stirring and autocompact pressure. The mixture is maintained at 280°C for 4 hours, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set, and a torque meter is used to allow the reaction medium to thicken, stopping the polymerization at the desired torque. The reactor is drained into a water bath, and the polymer is then cooled to form rods, which are granulated.

[0159] [Example 11] 9.3 g of adipic acid, 1390.7 g of amino-11-undecanoic acid, and 7 g of water are introduced into a 4 L autoclave. After inactivation under nitrogen, the mixture is heated to 250°C under stirring and autocompact pressure. The mixture is maintained at 250°C for 1 hour, then expanded to atmospheric pressure over 2 hours to reach 230°C. A nitrogen sweep is set, and a torque meter is used to allow the reaction medium to thicken, stopping the polymerization at the desired torque. The reactor is drained into a water bath, and the polymer then forms a cooling rod, which is granulated.

[0160] Solubility parameters As an example, the calculation of the solubility parameters for Example 1 is described below (Table 1). It is a random copolymer of PA6, PA66, and PA12.

[0161] PA6 consists of 5 CH2 groups and 1 amide, PA66 consists of 10 CH2 groups and 2 amides, and PA12 consists of 11 CH2 groups and 1 amide.

[0162] The cohesive energy E is the sum of the squares of the energies of each group.

[0163] The molar volume V is the sum of the squares of the molar volumes of each group.

[0164] The solubility parameter is the square root of the sum of mole fractions of E relative to the sum of mole fractions of V.

[0165] [Table 1]

[0166] Melt Fracture Test If we consider the degree of melt fracture of LLDPE alone without additives to be 100%, then for Examples 1 to 14, a time was obtained in which melt fracture was reduced by 100%.

[0167] The results are shown in Table 2 below.

[0168] The term "melt fracture" is well known to those skilled in the art and generally refers to a film having obvious signs of surface defects that appear as die lines, haze bands, or small bands of soft melt fracture (orange peeling) or hard melt fracture (sharkskin). The phrase "melt fracture clear" means that the film has a clear and defect-free surface.

[0169] The polymers (2000 ppm) from Examples 1-14 were added to the LLDPE (PE)-based matrix polymer during extrusion. The LLDPE was melted at a melting temperature of 190°C for 300 seconds. -1 Under the conditions of the collection shear rate, the MVR (molten volume flow rate) is 8 g / 10 min for a weight of 2.16 kg.

[0170] [Table 2]

[0171] As can be seen in the results of the examples in Table 2, melt fracture of LLDPE during extrusion was effectively reduced by using the polymers of Examples 1-5 and 8-13 as additives.

[0172] The improvement in melt fracture reduction was particularly significant in Examples 1-5, 10, and 11.

Claims

1. A thermoplastic polymer composition comprising a matrix polymer (A) and a polymer processing aid (B), (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method). The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). －１ A thermoplastic polymer composition (measured by capillary rheometry at shear rate).

2. The thermoplastic polymer composition according to claim 1, wherein the amount of polymer processing aid (B) is 50 to 5000 ppm, preferably 100 to 3000 ppm, and more preferably 200 to 3000 ppm, relative to the weight of the matrix polymer (A).

3. The thermoplastic polymer composition according to claim 1 or 2, wherein the matrix polymer is a polyolefin composition, preferably the polyolefin composition comprises or consists of a non-functionalized polyolefin.

4. A thermoplastic polymer composition according to any one of claims 1 to 3, wherein the matrix polymer essentially comprises or consists of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high-density polyethylene (UHDPE), or polypropylene (PP), or a combination thereof.

5. The thermoplastic polymer composition according to any one of claims 1 to 4, wherein the polymer processing aid is selected from polyamide, PEBA, or a mixture thereof.

6. The thermoplastic polymer composition according to claim 5, wherein the polyamide or PEBA block polyamide is PA6, PA10, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamide PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or a blend of these polymers.

7. The polymer processing aid (B) is greater than 20.0, preferably 21.0 (J1 / 2.cm). －３ / 2) A solubility parameter greater than (where the solubility parameter is calculated according to the Fedor method), 210°C and 100s －１ A thermoplastic polymer composition according to any one of claims 1 to 6, having a melt viscosity of 10 to 500 Pa.s, preferably 20 to 400, more preferably 20 to 350, as measured by capillary rheometry at a shear rate.

8. A thermoplastic polymer composition according to any one of claims 1 to 7, comprising at least one adjuvant, preferably one or more selected from polyethers, aliphatic polyesters, poly(hydroxybutyrate), silicones, fatty acid esters, and fatty acid amides, preferably polyether copolymers.

9. A method for melt extrusion of a thermoplastic polymer composition comprising a matrix polymer (A), comprising the step of supplying the matrix polymer (A) and a polymer processing aid (B) together or separately to an extruder, (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method). The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). －１ The method involves measuring the shear rate by capillary rheometry.

10. The method according to claim 9, further comprising the step of supplying at least one adjuvant to an extruder.

11. The method according to claim 9 or 10, wherein the polymer processing aid and, if present, the adjuvant are supplied in the form of a masterbatch composition containing a carrier polymer (C).

12. The method according to any one of claims 9 to 11, wherein polymer processing aids and, if present, adjuvants are supplied directly to the extruder separately, simultaneously, or as a blend.

13. The method according to any one of claims 9 to 12, wherein the matrix polymer is a polyolefin, and preferably the polyolefin composition comprises or comprises a non-functionalized polyolefin.

14. The method according to any one of claims 9 to 13, wherein the matrix polymer essentially comprises or consists of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high-density polyethylene (UHDPE), or polypropylene (PP), or a combination thereof.

15. The method according to any one of claims 9 to 14, wherein the amount of polymer processing aid (B) is 50 to 5000 ppm, preferably 100 to 3000 ppm, more preferably 200 to 3000 ppm, relative to the weight of the matrix polymer (A).

16. The polymer processing aid (B) is greater than 20.0, preferably 21.0 (J1 / 2.cm). －３ / 2) A solubility parameter greater than (where the solubility parameter is calculated according to the Fedor method), and 210°C and 100 s －１ The method according to any one of claims 9 to 15, wherein the melt viscosity is measured by capillary rheometry at a shear rate of 10 to 500 Pa.s, preferably 20 to 400, more preferably 20 to 350.

17. The method according to any one of claims 9 to 16, wherein the polymer processing aid is selected from polyamide, PEBA, or a mixture thereof.

18. The method according to claim 17, wherein the polyamide or PEBA block polyamide is PA6, PA10, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212, or copolyamide PA6 / 12, PA6 / 11, PA6 / 1010, PA6 / 66, PA6 / 66 / 12, PA6 / 66 / 11, PA6 / 66 / 610, PA6 / 612 / 11, or a blend of these polymers.

19. An extruded article comprising a polymer composition according to any one of claims 1 to 8, preferably a film, sheet, tube, pipe, wire, fiber, cable, wire coating, or cable jacket.

20. The use of polymer (B) as a processing aid for extruding a thermoplastic polymer composition containing a matrix polymer (A), (δ polymer (B) - δ matrix polymer (A)) >= 2.0 (J1 / 2.cm-3 / 2), preferably > 3.0 (J1 / 2.cm-3 / 2) (where δ is a solubility parameter calculated according to the Fedor method). The melt viscosity ratio of polymer (B) to matrix polymer (A) is less than 0.30, preferably less than 0.20 (wherein the melt viscosity is measured at 210°C and 100 s). －１ (Measured by capillary rheometry at shear rate), used.

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