Polyolefin composition

Abstract

This disclosure relates to polyolefin compositions comprising polyamide condensation polymers of C32-C44 dimer dioic acids and C2-C44 aliphatic diamines. The polyamide condensation polymers may be used in a range of concentrations with additional additives. The use of the condensation polymers described herein in polyolefin compositions helps prevent surface defects when the polyolefin compositions are processed into final products.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 502,741, filed on 17 May 2023, which is incorporated herein by reference in its entirety.

[0002] (Field of invention) This application relates to a specific polyolefin composition designed to facilitate the manufacture of finished products such as films. [Background technology]

[0003] Polyolefins have the general formula (CH2CHR) n Polyolefins are a type of polymer having the formula R being an alkyl group or hydrogen. They are usually derived from a small set of simple olefins (alkenes). In a commercial sense, polyethylene and polypropylene are dominant. More specialized polyolefins include polyisobutylene and polymethylpentene. They are all colorless or white oils and solids. Many copolymers are known, for example, polybutenes derived from mixtures of different butene isomers. The name of each polyolefin indicates the olefin from which it is prepared. For example, polyethylene is derived from ethylene, and polymethylpentene is derived from 4-methyl-1-pentene. Polyolefins may be homopolymers, copolymers, random, or block copolymers.

[0004] To produce finished products, polyolefin compositions are often heated to a molten state and extruded through a die to produce finished products such as films. One such example is linear low-density polyethylene (LLDPE). As a poor system, the polymer molten material does not flow easily or uniformly through the die. Rather, the material flowing near the surface of the die flows more slowly than the material closer to the center of the die opening. As the flow rate through the die increases, this imbalance increases until surface defects become detectable at the die exit. The surface changes from a smooth, glossy state to a matte state and eventually becomes rough. Finally, the surface of the extruded material is deformed to what is called the "sharkskin" effect in the art. This is produced by the flow transitioning to irregular flows of slower and faster movements. Extrusion can be described as abrupt movements or pulsations from the die.

[0005] The sharkskin effect occurs at the die exit when the shear rate increases to a level where the center of the molten material moves very quickly and the material adhering to the wall exhibits a stick-slip phenomenon. Sharkskin tends to be promoted by lower extrusion temperatures, narrower die gaps, high molecular weight (low MFI) polymers, lack of long-chain branching, and a narrow molecular weight distribution. This is particularly common in linear low-density polyethylene (LLDPE) grades. LLDPE is a copolymer of ethylene and short α-olefins such as 1-butene, 1-hexene, methylpentene, or 1-octene.

[0006] To avoid this effect, manufacturers must make certain choices. They can operate the extrusion more slowly, or they can operate it at higher temperatures. However, both solutions increase processing costs, which is undesirable. Alternatively, fluoropolymers have commonly been added to polyolefin compositions to improve this difficulty. Used as processing aids, fluoropolymers deposit on the die surface, smoothing the transition from adhesion to sliding and delaying the occurrence of surface defects at higher shear rates.

[0007] Unfortunately, the use of fluoropolymers has very significant drawbacks. The manufacture and use of these substances are associated with significant environmental impacts on human populations. Furthermore, fluoropolymers are extremely durable materials and are resistant to biodegradation. When they enter terrestrial, lake, and marine ecosystems, they persist for their lifespan. These materials are highly undesirable and are increasingly regulated.

[0008] Polyolefin manufacturers are eager to replace fluoropolymer additives with solutions that are sustainably supplied and avoid these serious environmental drawbacks. SUMMARY OF THE INVENTION

[0009] The present disclosure provides alternative additives to polyolefin compositions that are bio-based, more sustainable, and have less environmental impact than existing solutions. The polyolefin compositions containing polyamides described herein have the advantages of reduced haze, improved gloss, and improved transparency compared to control compositions, and have little or no impact on production speed. In particular, the materials described herein can be used to replace the functionality of fluoropolymers in polyolefin processing.

[0010] The present disclosure provides a polyolefin composition comprising a polyamide condensation polymer of a C32 - C44 dimer diacid and a C2 - C44 diamine in an amount greater than 100 ppm. ​​​​​​​​​​​​​​​​​R1 is hydroxyl, -OR3, -NHXNH2, or -NHXNHCOR3, R2 is hydrogen, -COR3, or -COYCOR4, R3 is C12 - C22 alkyl, R4 is hydroxyl or C12 - C22 alkoxy, n is a positive integer such that the average molecular weight (Mw) of the condensed polymer is 3,000 - 100,000.

[0013] The polyolefin composition without the polyamide additive disclosed herein requires a higher processing temperature and may have reduced flow characteristics. This reduction in the smooth flow through the processing equipment results in a non-uniform residence time and local overheating of the polymer composition. This overheating can lead to undesirable cross-linking and gel formation of the polymer, contributing to surface defects in the manufactured articles.

Brief Description of the Drawings

[0014] [Figure 1] It is a depiction of the extrusion equipment utilized in the examples to prepare test samples for evaluation. [Figure 2] It is an enlarged view of the equipment of Figure 1 explaining the size of the die of the equipment and the characteristics of monitoring.

Modes for Carrying Out the Invention

[0015] Next, specific aspects of the disclosed subject matter are referred to in detail. It will be understood that the disclosed subject matter is described with the recited claims, but the exemplified subject matter is not intended to limit the disclosed subject matter to the claims. One aspect described with a particular aspect is not necessarily limited to that aspect and can be implemented with any other aspect.

[0016] Throughout this specification, values ​​expressed in range form should be interpreted flexibly to include not only the numerical values ​​explicitly listed as limits to the range, but also all individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly listed. For example, the range "approximately 0.1% to approximately 5%" or "approximately 0.1% to approximately 5%" should be interpreted to include not only approximately 0.1% to approximately 5%, but also the individual values ​​within the indicated range (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). The statement "approximately X to Y" has the same meaning as "approximately X to about Y" unless otherwise indicated. Similarly, the phrase "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise specified.

[0017] As used herein, the singular forms “a,” “an,” and “the,” as well as similar referents in contexts describing elements (particularly in the context of the following claims), include multiple referents unless the context explicitly indicates otherwise. For example, a reference to “a substituent” includes a single substituent as well as two or more substituents. Unless otherwise indicated herein or unless explicitly contradicted by the context, any singular term may include its plural counterpart and vice versa.

[0018] The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The statement "at least one of A and B" has the same meaning as "A, B, or A and B".

[0019] Furthermore, it should be understood that any expressions or terms used herein, unless otherwise defined, are for illustrative purposes only and not intended to be restrictive. The use of any section headings is intended to aid in the reading of this document and should not be interpreted as restrictive. Information related to a section heading may be located within or outside that particular section. Any publications, patents, and patent documents referenced herein are incorporated herein in whole by reference as if they were incorporated individually by reference. Where there is inconsistency in use between this document and the documents thus incorporated by reference, the use in the incorporated references should be interpreted as supplementing the use in this document. In the event of irreconcilable conflict, the use in this document shall prevail.

[0020] As used herein, the terms “for example,” “for instance,” “such as,” or “including” are intended to introduce examples that further clarify a more general issue. Unless otherwise noted, these examples are provided solely to aid in understanding the uses illustrated in this disclosure and are not intended to limit them in any way.

[0021] In the methods described herein, the actions may be performed in any order without departing from the principles of this disclosure, unless a temporal or operational order is explicitly enumerated. Furthermore, certain actions may be performed in parallel unless explicitly stated to be performed separately by the wording of the claims. For example, the claimed action of performing X and the claimed action of performing Y may be performed simultaneously within a single operation, but the resulting process falls within the literal scope of the claimed process.

[0022] As used herein, the term “substantially” means at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or a majority or most of the portion, such as 100%. In some aspects, “substantially” means more than 90% or 90% to 100%.

[0023] As used herein, the following terms have the following meanings unless expressly stated otherwise:

[0024] The term "esterification or esterified" refers to the following: 1) a dehydration reaction between an alcohol and an acid; 2) transesterification, a reaction between an alcohol and an ester to form a new ester; or 3) the formation of an ester bond, including transesterification.

[0025] The term "polydispersity index" (also known as the molecular weight distribution), as used herein, is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). Polydispersity data are collected according to the following procedure.

[0026] The molecular weights of the materials disclosed herein were determined by methods well known in the art for polymer analysis. GPC is a typical method for evaluating experimental samples against a standard curve created by a reference polystyrene benchmark.

[0027] The sample for GPC was prepared as follows. Approximately + / -7.5 mg of the sample was weighed in a 2 mL LC vial. 750 μl of THF was added and the vial was capped. If the sample needed to be dissolved, the sample was gently heated. The vial was opened and 100 μl of pyridine and 100 μl of acetic anhydride were added. The vial was capped and stirred for 10 - 20 seconds. The mixture was reacted at 80 °C for 30 minutes. The vial was opened and the solvent was evaporated at 80 °C under a N2 stream. The residue was redissolved in + / -750 μl of THF to a concentration of 10 mg / mL, and this sample was used for GPC analysis.

[0028] The standards were prepared as follows. Polystyrene low mix MW 570, 970, 2450, 5050, 11600, 28500, 660000. Polystyrene high mix MW 108000, 176000, 320000, 475000. For both standards, 2 - 3 mg per standard were combined and dissolved in 10 mL of mobile phase (THF). The sample solution was filtered through a 0.45 μm PTFE filter and stored refrigerated at 4 °C in a transparent vial capped with a PTFE - lined crimp cap.

[0029] The GPC sample was run under the following conditions.

[0030]

Table 1

[0031] The molecular weight data was determined by comparison with a set of polystyrene standards.

[0032] As used herein, the term "weight average molecular weight" is ΣM i 2 n i / ΣM i n i (where n i is the number of molecules of molecular weight M i ) equal to M wThis refers to the weight-average molecular weight in various examples. In various examples, the weight-average molecular weight may be determined by the tests described herein, or by using size exclusion chromatography, light scattering, small-angle neutron scattering, X-ray scattering, and sedimentation velocity.

[0033] The term "number average molecular weight" is used herein by reference to M n This refers to the total weight of the sample divided by the number of molecules in the sample. n is, equation ΣM i n i / n i It can be expressed by, but in the formula, n i M is the molecular weight i This is the number of numerators.

[0034] The term "Acid Value" (AV), as used herein, is defined as the weight (mg) of KOH required to neutralize the organic acid present in 1 g of a test sample, and is a measure of the free fatty acids present in the composition. AV can be determined by AOCS Official Method Cd 3d-63.

[0035] The term "amine value" (AmV), as used herein, is defined as the weight (mg) of KOH required to neutralize the free amine present in 1 g of a test sample, and is a measure of the amine present in a composition. The amine value is defined as the number of mg of potassium hydroxide required to neutralize the free fatty acid in 1 g of sample and was measured by direct titration with standard hydrochloric acid. AmV can be determined by AOCS Official Method Cd 5a-40.

[0036] C2~C 44 Alkyl, C2~C 36 Alkyl, C2~C 12 ;C4~C8;C6~C 12 , and C1~C 10The term alkyl refers to alkyl groups containing 1 to 36, 2 to 12, 4 to 8, and 1 to 10 carbon atoms. Any similar numerical range should be considered as well. In some embodiments, alkyl groups may be branched. In other embodiments, alkyl groups may be unbranched or linear. In other embodiments, alkyl groups may be a mixture of branched and unbranched. In other embodiments, alkyl groups may be cyclic, aromatic, or unbranched. One or more alkyl groups may be saturated, unsaturated, or a mixture thereof. In other embodiments, alkyl groups may be substituted, unsubstituted, or a mixture thereof.

[0037] Polyethylene can be a homopolymer of ethylene or a random copolymer of ethylene and α-olefin. Changing the amount of α-olefin alters the amount of branching, which affects the density. For typical products, the density is approximately 0.88–0.97 g / cm³. 3 There is a continuum between them. Pes < 0.91 g / cm³ 3 It is common to call this VLLDPE (Very Low LLDPE), sometimes "plastomer," with 0.91-0.93 being called LLDPE (Low LLDPE), 0.93-0.945 being called LMDPE (Medium LLDPE), and >0.945 being called HDPE (High Density Polyethylene).

[0038] Polycondensation composition The polyolefin compositions described are C 36 ~C 44 Dimer dioic acid and C2~C 44 It contains polycondensation products with diamines.

[0039] Diamines are any C2-C2 compounds such as ethylenediamine, propylenediamine, and hexamethylenediamine. 44 They may be branched, cyclic, aromatic, or linear diamines. In some embodiments, the diamine is C2-C 12 It is an aliphatic diamine. In some embodiments, the diamine is a C4-C8 aliphatic diamine. In some embodiments, the diamine is a hexamethylenediamine. In some embodiments, the diamine may be a mixture of diamines.

[0040] Dimer acids (also referred to herein as dimer acids) are well known in the art and are produced by the bipolymerization of unsaturated fatty acids such as oleic acid or linoleic acid, drying oil fatty acids or semi-drying oil fatty acids, or lower monoalcohol esters of these fatty acids, with or without a catalyst. Dimer fatty acids are described in TEBreuer, 'Dimer Acids', JIKroschwitz (ed.), Kirk-Othmer Encyclopaedia of Chemical Technology, 4th Ed., Wily, New York, 1993, Vol.8, pp.223-237. Typically, dimer acids are obtained as a mixture of unreacted monomers, the main component dimer, and other higher-order polymers. If necessary, the dimer acid components may be highly concentrated by appropriate fractionation methods such as vacuum distillation or solvent extraction. Furthermore, to reduce the degree of unsaturation, saturated dimer acids can be produced and used by hydrogenating the polymerized fatty acids before or after fractionation. Dimer acids may be aliphatic, cyclic, aromatic, or mixtures thereof.

[0041] Depending on the dimerization conditions and starting materials, one or more of the following structures are typically present in the dimer acid composition. In these structures, R and R' are alkyl groups.

[0042] [ka]

[0043] Commercially available dimer acids can be used, such as Cargill's Prepol 1017, Prepol 1022, Prepol 1029, Prepol 1012, Prepol 1013, Prepol 1014, Prepol 1025, Prepol 1027, Prepol 1006, Prepol 1009, Prepol 1010, and Tsuno Dime 216 and Tsuno Dime 395. Dimer acids may be used individually or in combination of two or more. In one embodiment, these one or more combinations are selected from Prepol 1012, Prepol 1013, Prepol 1014, Prepol 1006, Prepol 1010, and Tsuno Dime 395.

[0044] In some embodiments, dimer dioic acid is represented by the formula HO2CYCO2H, where Y is C 30 ~C 42 It is an aliphatic or aromatic carbon group.

[0045] In some embodiments, dimer dioic acid is represented by the formula HO2CYCO2H, where Y is C 34 It is an aliphatic or aromatic carbon group.

[0046] In some embodiments, the dimer acid is C36 dimer acid. In some embodiments, the dimer acid is pre-pol 1006.

[0047] In some embodiments, the diacid comprises a dimer acid and additional diacids. Other dibasic acid components besides the dimer acid include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid, tridecamethylenedicarboxylic acid, tetradecamethylenedicarboxylic acid, pentadecamethylenedicarboxylic acid, hexadecamethylenedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, and mixtures thereof. These additional diacids can be used individually or in combination of two or more.

[0048] In some embodiments, the additional diacid is selected from the group consisting of adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures thereof.

[0049] In another embodiment, the polyolefin composition comprises a condensed polymer or polymer of formula 1:

[0050] [ka] During the ceremony, X is a branched or linear aliphatic or aromatic group containing 2 to 44 carbon atoms. Y is a branched or linear aliphatic or aromatic group containing 30 to 44 carbon atoms. R1 is hydroxyl, -OR3, -NHXNH2, or -NHXNHCOR3. R2 is hydrogen, -COR3, or -COYCOR4. R3 is a C12-C22 alkyl group. R4 is a hydroxyl or C12-C22 alkoxy compound. n is a positive integer such that the average molecular weight (Mw) of the condensed polymer is between 3,000 and 100,000.

[0051] In some embodiments, X is an aliphatic group containing 2 to 8 carbon atoms.

[0052] In some embodiments, X is an aliphatic group containing six carbon atoms.

[0053] In some embodiments, Y contains 32 to 40 carbon atoms, or 34 carbon atoms.

[0054] In some embodiments, Y contains 34 carbon atoms.

[0055] In some embodiments, R1 is a hydroxyl group.

[0056] In some embodiments, R1 is -NHXNH2.

[0057] In some embodiments, R2 is hydrogen.

[0058] In some embodiments, R1 is -NHXNH2 and R2 is hydrogen.

[0059] In some embodiments, R1 is hydroxyl and R2 is hydrogen.

[0060] In some embodiments, R2 is hydrogen or -COR3.

[0061] In some embodiments, R1 is hydroxyl and R2 is hydrogen or -COR3.

[0062] In some embodiments, the average molecular weight (Mw) of the condensed polymer is between 30,000 and 75,000.

[0063] In some embodiments, the polyamide polymer is melted or substantially softened at 65°C to 120°C.

[0064] In some embodiments, the polyamide polymer or compound of Formula 1 has an amine value of at least 2 mg KOH / g.

[0065] In some embodiments, the polyamide polymer or compound of Formula 1 has an amine value of 2 mg KOH / g to 10 mg KOH / g.

[0066] In some embodiments, the polyamide product or compound of formula 1 has an acid value of <1 mg KOH / g and / or an amine value greater than 2 mg KOH / g. In some embodiments, the polyamide product or compound of formula 1 has an acid value of 0.1 to 1 mg KOH / g and / or an amine value of 1 to 10 mg KOH / g. In some embodiments, the polyamide product or compound of formula 1 has an acid value of 0.1 to 1 mg KOH / g and / or an amine value of 2 to 10 mg KOH / g. In some embodiments, the polyamide product or compound of formula 1 has an acid value of 0.1 to 1 mg KOH / g and / or an amine value of 3 to 7 mg KOH / g.

[0067] Method for preparing polyamide compositions Typically, dimer dioic acid (and other dioic acid, if used) and diamine are mixed together at high temperature, with water removed optionally in the presence of a catalyst. This reaction is well known in the art. The dimer acid is heated to about 60°C under an inert atmosphere (optionally in the presence of 0.05–0.5 w / w% of a catalyst, e.g., sodium hypophosphite, phosphoric acid, phosphorous acid, triphenyl phosphite, TBT, stannous oxide, etc.), and the diamine is slowly added in a controlled manner. The reactants are then slowly heated to a temperature of about 220–250°C until the desired endpoints of the acid value and / or amine value are reached. The reactants are cooled, and the polyamide product is isolated.

[0068] Those skilled in the art will understand that the polycondensation described herein yields a mixture of products. Molecules of various chain lengths exist, as well as chains terminated by i) an amine group and an acid group, ii) two amine groups, or iii) two acid groups. Depending on the stoichiometry of the dimer acid and diamine, the resulting products may have more of one type of terminal group than others. In some embodiments, the diamine is used in a molar excess of 3-10% primarily to obtain amine-terminated capped products. Furthermore, the degree of polymerization can be varied depending on time, temperature, and catalyst to achieve different molecular weights.

[0069] In some embodiments, the ratio of dimer dioic acid to diamine is 1.5 / 1.0 to 1.0 / 1.5. In other embodiments, the ratio of dimer dioic acid to diamine is 1.3 / 1.0 to 1.0 / 1.3. In other embodiments, the ratio of dimer dioic acid to diamine is 1 / 1 to 1.0 / 1.3.

[0070] These terminal groups can be further reacted or "capped". Amine terminal groups may be capped by the addition of a monoacid such as a fatty acid. Acid terminal groups may be monoamines, diamines, or C 12 ~C 22 The end capping can be performed by reaction with an aliphatic alcohol. These end capping reactions may be carried out after the completion of the polycondensation reaction, or in situ by adding a monoacid, monoamine, or alcohol to the polycondensation reaction mixture. In some embodiments, the polyamide is C8-C 22 The ends may be capped with fatty acids. In some embodiments, the polyamide is C2-C 22 It can be terminally capped with an aliphatic amine. In some embodiments, the polyamide is C8-C 22 Fatty acids or C2-C 12 The ends may be capped with an aliphatic amine.

[0071] In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mn) of at least 3,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mn) of at least 5,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mn) of 3,000 to 100,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mn) of 4,000 to 15,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mw) of at least 20,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mw) of 5,000 to 80,000 daltons. In some embodiments, the polyamide polymer or compound of formula 1 has a molecular weight average (Mw) of 30,000 to 70,000 daltons.

[0072] Any combination of two or more features disclosed herein for natural oil-based petrolatum has been specifically conceived and envisioned by the inventors. Accordingly, the inventors have conceived and disclosed any combination of single points and ranges disclosed for the parameters described herein.

[0073] Polyolefins Polyolefins have the general formula (CH2CHR) nPolyolefins are a type of polymer having a double bond, where R is an alkyl group or hydrogen. They are usually derived from a small set of simple olefins (alkenes). In a commercial sense, polyethylene and polypropylene are dominant. More specialized polyolefins include polyisobutylene and polymethylpentene. The name of each polyolefin indicates the olefin from which it is prepared. For example, polyethylene is derived from ethylene, and polymethylpentene is derived from 4-methyl-1-pentene. Polyolefins are not olefins in themselves, as the double bonds of each olefin monomer are ring-opened to form a polymer. Monomers with more than one double bond, such as butadiene and isoprene, give rise to double-bond-containing polymers (polybutadiene and polyisoprene), which are considered polyolefins for the purposes of this disclosure. They can be purchased from a wide variety of industrial producers. For example, LLDPE can be purchased from Versalis under the Clearflex® brand.

[0074] Examples of polyolefins include, but are not limited to, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), very low-density polyethylene (ULDPE), medium-density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), ethylene-octene copolymer, stereoblock PP, olefin block copolymer, and propylene butane copolymer.

[0075] Method for preparing polyolefin compositions The polyolefin compositions of this disclosure can be prepared by any method known in the art for combining polymer additives with an extruded resin composition. For example, but not limited to, the following methods may be used: the polyamide may be blended with the polyolefin, coated onto the polyolefin, co-injected into an extruder in an appropriate dose, or prepared in a masterbatch. The method of preparing the polyolefin is not important, and those skilled in the art using additives similar to the polyamides of this disclosure will select from these and other methods depending on the specific circumstances.

[0076] The polyolefin composition may further contain any additional additives desired by the end user, including UV protectants, antioxidants, colorants, plasticizers, anti-tack agents, and slip agents.

[0077] In some embodiments, the polyolefin is polyethylene or polypropylene.

[0078] In some embodiments, the polyolefin is polyethylene or low-density polyethylene.

[0079] In some embodiments, the polyolefin is linear low-density polyethylene.

[0080] In some embodiments, the polyolefin comprises more than 100 ppm of a polyamide condensation product or a product of Formula 1 disclosed herein.

[0081] In some embodiments, the polyolefin comprises 200 ppm to 3000 ppm of the polyamide condensation product disclosed herein or the product of Formula 1. In some embodiments, the polyolefin comprises 200 ppm to 1500 ppm of the polyamide condensation product disclosed herein or the product of Formula 1.

[0082] In some embodiments, the polyolefin composition is a masterbatch containing 5% to 25% by weight of a polyamide condensation product disclosed herein or a product of Formula 1. [Examples]

[0083] [Table 2]

[0084] Examples 1A-F A 500 mL four-necked round-bottom flask equipped with a magnetic stirrer with a metal propeller stirrer, a temperature feedback probe, a nitrogen spur inlet, and a condenser with a receiving flask was filled with Prepol 1006 (213.72 g, 0.375 mol; 0.75 equivalents), and the contents were heated to 60°C under atmospheric pressure while stirring (150-200 rpm) and purging with N2 through the mixture.

[0085] At 60°C, hexamethylenediamine (HMDA) (46.28 g, 0.40 mol; 0.80 equivalents) was slowly added over 30 minutes to raise the temperature. Before administering HMDA, the nitrogen spurge inlet was removed from the liquid and nitrogen was spurged into the headspace.

[0086] Next, the mixture was heated to between 160 and 170°C, at which point significant foaming occurred and the distillation of water as a byproduct began. At this stage, the heat input was reduced to control the temperature, and the stirring speed was slowed to 50 rpm. At 190°C, the foaming disappeared, nitrogen was sprayed through the liquid, and the mixture was heated to approximately 230°C, with the stirring speed increased to 150 to 200 rpm.

[0087] The reaction conditions were maintained at the reaction temperature for approximately 3-4 hours until the desired specifications (acid value < 1 mg KOH / g, amine value < 10 mg KOH / g) were reached. The mixture was cooled to 200°C, 0.1 w / w% Irganox 1010 and Irgafos 168 were added, and the mixture was mixed for 15 minutes. Finally, the mixture was poured into an uncoated metal pan at 200°C and allowed to cool.

[0088] Example 1B was a repeated experiment in which stearic acid was added at the start of the reaction to cap the end of the polyamide.

[0089] Example 1C is a repeated experiment, but different stoichiometry was used to obtain acid-terminated polyamides with lower amine values ​​and higher acid values.

[0090] Example 1D is a repetition of 1A using a different stoichiometry to obtain a (more) short-chain amine-terminated polyamide.

[0091] Example 1E is a repetition of 1B using a different stoichiometry to obtain an amine-terminated polyamide with a higher amine value.

[0092] Example 1F is a repeat of 1C using a different stoichiometry, resulting in an even higher acid value and a shorter chain length.

[0093] Examples 1G and 1H are a repetition of incorporating stearic acid to produce polyamides that are terminally capped with short (or more) stearyl or partially stearyl.

[0094] [Table 3]

[0095] [Table 4]

[0096] Example 2: Sharkskin and melt fracture in cast films can be evaluated using small-scale processing equipment, provided that an appropriate shear rate can be generated. The Haake Rheocord system was utilized, which is essentially a highly instrumented polymer processing system. This system consists of an extrusion mode using a small single-screw extruder, fed into a slit capillary die equipped with temperature and pressure transducers that allow for measurement of pressure drop along the die length. This enables evaluation of the rheological properties of the polymer, along with measurement of the output rate.

[0097] In this process, visual inspection of the transparency and smoothness of the extruded strips was sufficient for screening polymer processing aids. However, for completeness, torque, motor power consumption, output speed, and die pressure drop can also be recorded. Using the output and die pressure, the apparent shear rate, shear stress, and apparent viscosity can be calculated.

[0098] Example 2A was prepared by dissolving 1.1 g of the polyamide from Example 1A in 500 mL of solvent (industrial denatured alcohol, cyclohexane, or a blend of the two as needed) in a 1 L Duran bottle, stirring and heating as needed. 125 mL of this solution was added to 250 g of LLDPE in a 1 L round-bottom flask. The solvent was removed using a rotary evaporator until no further evaporation was observed. The flask was removed from the rotary evaporator, and the pellet was discharged into an aluminum foil tray with stirring. This was repeated three more times to obtain 1 kg of sample. An additional 0.1 g was used to account for surface losses on the apparatus, and a polyolefin composition containing approximately 1000 ppm of polyamide processing aid was obtained.

[0099] Example 2B was prepared in the same manner as Example 2A, except that the processing aid was Crystasense LP3, which is commercially available from Croda. Crystasense LP3 is a polyamide composition derived from the polycondensation of a C36 dimer acid and ethylenediamine, and further terminally capped with stearic acid.

[0100] Examples 2A and 2B were compared with LLDPE samples containing fluoropolymer processing additives (300 ppm to 1000 ppm) under the same extrusion conditions. The resulting polymer + additive blends and controls were extruded using a Haake Rheocord [QC equipped with a 19 / 25 QC-B uniscrew extruder and a slit capillary die (L 150 mm x W 18 mm x H 1.2 mm)] as shown in Figures 1 and 2, using the parameters listed in Table 4.

[0101] [Table 5]

[0102] Each run was performed as follows: The extruded material was fed onto a cooling roller (15°C) running at a speed setting of 100. The control material was run until stable torque, pressure, and temperature were achieved. The polymer level in the feed port was allowed to flow out until the top of the screw was visible. A test sample (1 kg) was added to the feed hopper. The sample was collected when the conditions stabilized again (torque and pressure may change to new stable levels and were recorded). When approximately two-thirds of the polymer had been consumed (750 g), the strip was observed for evidence of changes in appearance.

[0103] The samples could be visually evaluated by their degree of cloudiness, clarity, and the presence of surface defects. The control sample without additives produced a poor film with a high degree of cloudiness and surface defects. The control sample containing fluoropolymer processing additive (FPPA) showed improvement over the base control, but still exhibited a considerable degree of cloudiness and defects. Both Examples 2A and 2B showed dramatically better performance than the control and FPPA materials. The clarity and surface quality of the samples were both remarkably good.

[0104] Similar results were obtained by repeating the analysis using a laboratory-scale inflated film apparatus. Examples 2A and 2B produced films with significantly better clarity and fewer surface defects than either the base control or the control containing FPPA.

[0105] Example 3 Various diamines (shown in Table 5) were used to prepare polyamides using dimer acid according to the procedure of Example 1. The diamines were added to the reactants (1,8-octanediamine was a 50 wt% aqueous solution). Foaming was controlled by carefully managing stirring and heating. Stoichiometric and analytical data are shown in Table 6 below. The evaluation protocol of Example 2 was repeated with samples 3A-G formulated in LLDPE (Versalis Clearflex FF106A) at a 500 ppm inclusion level through the use of a masterbatch. All samples showed significant improvement in clarity and sharkskin texture compared to the control.

[0106] [Table 6]

[0107] [Table 7] * As a 50% by weight solution

[0108] Example 4 The evaluation of Example 2 was repeated with samples 1A-H formulated in LLDPE (Clearflex FF106A from Versalis) at an inclusion level of 500 ppm through the use of a masterbatch. These were prepared and pelletized by a standard method by extrusion at 210°C in a Prism twin-screw extruder. The output speed was measured and clarity was observed. Samples were evaluated after 60 minutes of extrusion. Some samples showed improved clarity in the early stages of the run, but the comparison was made at 60 minutes. From Table 7, it is clear that compositions with higher amine values ​​may be preferred. Furthermore, acid-terminated caps may be unfavorable in certain situations.

[0109] [Table 8]

[0110] Example 5

[0111] [ka]

[0112] Example 1A (the above reaction) was scaled up to a 25 kg scale and repeated as described in Table 8 below. The monomers (HMDA and Pripol 1006) were melted by heating in an oven at 60°C for 6-8 hours. The reactor was heated to 60°C before loading the dimer acid. The dimer was stirred at 100-150 rpm while nitrogen was sprayed through the headspace. Molten HMDA was added in a controlled manner and the exothermic reaction was monitored. After the foaming decreased and the distillation rate slowed, the temperature was increased to an internal temperature of 230°C-250°C, preferably continuing nitrogen spraying through the mixture (to allow for better removal of water). The reaction was monitored by AV and amine value until AV was <1 mg KOH / g and the amine value was approximately 7 mg KOH / g. The reactor was cooled to 200°C-220°C and discharged into a water bath through the bottom valve to obtain polymer strands. The strands were pulled along with the help of a conveyor belt and eventually transported to a strand pelletizer, where they were cut into pellets. Finally, the resulting pellets were dried in an air-circulating oven to remove any residual moisture from the water bath and then bagged in aluminum foil bags.

[0113] [Table 9] * HMDA is included with a purity of (98% or 99.5%). ** Example 5C experienced some difficulties during the addition of HMDA and during the reaction, which resulted in atypical results.

Claims

1. A polyolefin composition containing a polyamide condensation polymer of C32-C44 dimer dioic acid and C2-C44 diamine in a concentration exceeding 100 ppm.

2. The polyolefin composition according to claim 1, wherein the polyamide condensed polymer is an acid-terminated, amine-terminated, terminal capped, or a mixture thereof.

3. The polyolefin composition according to claim 1, wherein the molar ratio of dimer dioic acid to diamine is 1 / 1 to 1.0 / 1.

5.

4. The polyolefin composition according to claim 1, comprising 200 ppm to 2000 ppm of the polyamide condensation polymer.

5. The polyolefin composition according to claim 1, comprising 5% to 25% by weight of the polyamide condensation polymer.

6. The polyolefin composition according to claim 1, wherein the dimer dioic acid is a C36 dimer dioic acid and the diamine is a C2 to C8 diamine.

7. The polyolefin composition according to claim 5, wherein the diamine is 1,6-hexamethylenediamine.

8. The polyolefin composition according to any one of claims 1 to 7, wherein the polyamide condensed polymer has an Mw of at least 5,000 Daltons, or 5,000 to 80,000 Daltons, or 30,000 to 70,000 Daltons.

9. The polyolefin composition according to any one of claims 1 to 7, wherein the polyamide condensed polymer has an amine value greater than 2.

10. The polyolefin composition according to any one of claims 1 to 7, wherein the polyamide condensed polymer has an amine value of 3 to 7.

11. The polyolefin composition according to any one of claims 1 to 7, wherein the polyamide condensation polymer has an amine value of 3 to 7 and an acid value of less than 1.

12. The polyolefin composition according to any one of claims 1 to 7, wherein the polyolefin comprises polyethylene.

13. A polyolefin composition comprising the condensation polymer of formula 1, 【Chemistry 1】 During the ceremony, X is a group containing 2 to 44 carbon atoms. Y is a branched or linear aliphatic or aromatic group containing 30 to 44 carbon atoms. R １ is hydroxyl, -OR ３ , -NHXNH ２ , or -NHXNHCOR ３ And, R ２ is hydrogen, -COR ３ , or -COYCOR ４ And, R ３ is C １２ to C ２２ alkyl, and R ４ is hydroxyl or C １２ ~C ２２ It is an alkoxy, A polyolefin composition in which n is a positive integer such that the Mw of the condensed polymer is between 3,000 and 100,000.

14. The polyolefin composition according to claim 13, wherein X is a group containing 2 to 12 carbon atoms.

15. The polyolefin composition according to claim 14, wherein X is a group containing 4 to 8 carbon atoms.

16. The polyolefin composition according to claim 15, wherein X is a group containing six carbon atoms.

17. The polyolefin composition according to any one of claims 13 to 16, wherein Y is a group containing 36 carbon atoms.

18. R ２ is hydrogen, R １ NHXNH ２ The polyolefin composition according to any one of claims 13 to 17.

19. A polyolefin composition according to any one of claims 13 to 18, comprising 200 ppm to 2000 ppm of the polyamide condensation polymer.

20. A polyolefin composition according to any one of claims 13 to 18, comprising 5% to 25% by weight of the polyamide condensation polymer.

21. The polyolefin composition according to any one of claims 13 to 20, wherein the polyamide condensed polymer has an Mw of at least 5,000 daltons or 5,000 to 80,000 daltons.

22. The polyolefin composition according to any one of claims 13 to 21, wherein the polyamide condensed polymer has a Mw of 30,000 to 70,000 Daltons.

23. The polyolefin composition according to any one of claims 13 to 22, wherein the polyamide condensed polymer has an amine value greater than 2.

24. The polyolefin composition according to any one of claims 13 to 23, wherein the polyamide condensed polymer has an amine value of 3 to 7.

25. The polyolefin composition according to any one of claims 13 to 24, wherein the polyamide condensed polymer has an amine value of 3 to 7 and an acid value of less than 1.

26. The polyolefin composition according to any one of claims 13 to 25, wherein the polyolefin comprises polyethylene.

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