Recovery of polyolefin waste by addition of amide fining agents

Abstract

The present invention relates to a process for recovering clarified polyolefin waste comprising the steps of collecting clarified polyolefin waste containing a sorbitol fining agent and adding an amide fining agent to the clarified polyolefin waste to form a regenerated polyolefin. The invention also relates to a regenerated polyolefin comprising an amide fining agent and a clarified polyolefin waste comprising a sorbitol fining agent; and to the use of an amide fining agent to reduce the haze of clarified polyolefin waste containing a sorbitol fining agent after recovery of the clarified polyolefin waste.

Description

[0001] This invention relates to a method for recycling clarified polyolefin waste, comprising collecting clarified polyolefin waste containing sorbitol clarifying agent and adding an amide clarifying agent to the clarified polyolefin waste to form recycled polyolefin. The invention also relates to recycled polyolefin containing an amide clarifying agent and clarified polyolefin waste containing sorbitol clarifying agent; and to a method for reducing the haze of clarified polyolefin waste containing sorbitol clarifying agent after recycling the clarified polyolefin waste using an amide clarifying agent.

[0002] Recycled polyolefins are expected to become a growing market and an important part of natural resource recycling management. Recycled polyolefins are typically designed to replace virgin polyolefins with the same or at least equivalent performance characteristics.

[0003] Polyolefins such as polyethylene, polypropylene, or poly(propylene-co-ethylene) have applications in various industrial sectors, such as consumer product packaging. In some of these applications, such as injection-molded thermoformed polypropylene food and storage containers, cups, plates, lids, or blow-molded bottles, good transparency is desired. Therefore, several types of clarifying agents have been developed to achieve good transparency. Maintaining this good transparency in recycled polyolefin products is also desirable.

[0004] In the recycling of polyolefins containing sorbitol clarifying agents, an undesirable increase in haze often occurs, for example, during multi-extrusion processes. Therefore, polyolefins containing sorbitol clarifying agents are generally unusable in recycling because this recycled polyolefin material loses its initial transparency. The goal is to overcome this problem and produce recycled polyolefins with good transparency, low haze, and low color.

[0005] This objective is achieved by a method for recycling clarified polyolefin waste, the method comprising the following steps: a) Collect clarified polyolefin waste containing sorbitol clarifying agent, and b) Add an amide clarifying agent to the clarified polyolefin waste to form recycled polyolefin.

[0006] This objective is achieved through recycled polyolefins from clarified polyolefin waste containing amide clarifying agents and sorbitol clarifying agents.

[0007] This objective is achieved by using an amide clarifying agent to reduce the haze of clarified polyolefin waste containing sorbitol clarifying agent after recycling the clarified polyolefin waste.

[0008] The clarified polyolefin waste can be - Pre-consumption waste, such as production waste collected from manufacturers or processors; - Post-consumer waste, such as household packaging collected via curbside collection or designated recycling systems, or discarded products returned by consumers; or - Demolition waste, such as waste from the demolition of civil buildings.

[0009] Materials collected and reused in the same manufacturing process are generally not considered clarified polyolefin waste.

[0010] Polyolefins in clarified polyolefin waste typically exhibit pre-damage, for example, the formation of new chemical groups (such as carbonyl groups) on the polymer chains through oxidation or photo-oxidation methods. Typically, polyolefins in clarified polyolefin waste contain carbonyl groups that are not present in virgin polyolefins. The concentration of carbonyl groups is often a measure of the pre-damage to the polyolefin. The concentration of carbonyl groups can be measured by infrared spectroscopy, for example, by measuring at 1720 cm⁻¹. -1 It is determined by the absorption of carbonyl vibrations within the range.

[0011] Clarified polyolefin waste may further include plastic additives added during the production of virgin polyolefins, such as antioxidants, UV absorbers, light stabilizers, metal deactivators, phosphites, phosphonates, hydroxylamine and amine N-oxides, nitrones, sulfur synergists, rheology modifiers, peroxide scavengers, acid scavengers, alkali co-stabilizers, nucleating agents, benzofuranones and indolineones, and flame retardants.

[0012] The collection of clarified polyolefin waste can be carried out in various ways, and generally depends on its source. Post-consumer waste can be collected through: curbside collection of specific waste categories; designated recycling systems where users deposit used products into containers; or returning discarded products (such as electronic devices or vehicles) to suppliers, who then send them to specialized companies for dismantling and final recycling of the plastic components. Pre-consumer waste can be collected from production waste from manufacturers and processors, which can be granulated or otherwise centrally processed through distributors. Demolition waste, typically generated from the demolition of residential buildings, can be collected by separating the plastic-containing components and sending them to specialized companies for further sorting.

[0013] Clarified polyolefin waste can take the form of flakes, powders, granules, fragments, films, bottles, bags, fiber scraps, and mixtures thereof.

[0014] Clarified polyolefin waste can be washed, for example, with a solvent such as water. This washing can be performed before, after, or both before and after the collection of the clarified waste. Preferably, the clarified polyolefin waste is washed after collection.

[0015] Clarified polyolefin waste can be pulverized, for example, by grinding, crushing, slicing, granulating, or micronizing. Pulverization can be performed before, after, or both before and after collection of the clarified waste. Preferably, the clarified polyolefin waste is pulverized after collection.

[0016] Clarified polyolefin waste can be sorted, for example, manually or by machine. During sorting, unwanted material can be removed. Sorting can be performed before, after, or both before and after the collection of clarified waste. Preferably, the clarified polyolefin waste is sorted after collection.

[0017] The concentration of the sorbitol clarifying agent can vary in different batches, for example, batches collected from different sources or on different days. Clarified polyolefin waste from different batches can be mixed to adjust the concentration of the sorbitol clarifying agent in the clarified polyolefin waste.

[0018] The clarified polyolefin waste may contain at least 0.01 wt%, preferably at least 0.05 wt%, and particularly at least 0.1 wt% of sorbitol clarifying agent.

[0019] Clarified polyolefin waste may contain up to 1.5 wt%, preferably up to 0.8 wt%, and particularly up to 0.5 wt% of sorbitol clarifying agent.

[0020] The clarified polyolefin waste may contain 0.01 to 3 wt%, preferably 0.05 to 1.0 wt%, and particularly 0.1 to 0.6 wt% of sorbitol clarifying agent.

[0021] When used in step b), the clarified polyolefin waste typically contains at least 80, 85, 90, 95, 96, 97, 98, or 99 wt% polyolefin, preferably poly(propylene-co-ethylene). The polyolefin concentration in the clarified polyolefin waste may be low when collected in step a), and it can then be washed and / or sorted.

[0022] Suitable polyolefins are polymers of monoolefins and dienes, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, polyhexene, polyoctene, and polymers of cyclic olefins (e.g., cyclopentene, cyclohexene, cyclooctene, or norbornene), (optionally crosslinked) polyethylene, such as high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE), and (ULDPE), or polypropylene, such as isotactic, syndiotactic, and atactic polypropylene.

[0023] Suitable polyolefins are also copolymers of monoolefins and dienes, such as ethylene / propylene copolymers (also known as poly(propylene-co-ethylene)), linear low-density polyethylene (LLDPE) and its mixtures with low-density polyethylene (LDPE), very low-density polyethylene, propylene / but-1-ene copolymers, propylene / isobutene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / cyclic olefin copolymers (e.g., ethylene / norbornene, like COC), ethylene / 1-olefin copolymers (where the 1-olefin is generated in situ), propylene / butadiene copolymers, and isobutene / isoprene copolymers.

[0024] Suitable polyolefins are also mixtures of polyolefins, such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), and mixtures of different types of polyethylene (e.g., LDPE / HDPE).

[0025] The preferred polyolefin is polypropylene or a polypropylene copolymer (e.g., poly(propylene-co-ethylene)). Preferably, the clarified polyolefin waste is clarified poly(propylene-co-ethylene) waste.

[0026] A suitable sorbitol clarifying agent is the sorbitol clarifying agent of formula (I). (I) Where R 1 R 2 and R 3 It is independently selected from H or C1-C6 alkyl groups. A mixture of sorbitol clarifying agents may also be used.

[0027] Suitable R 1 Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, or hexyl, it can be straight-chain or branched, with straight-chain being preferred. Preferred R 1 It is independently selected from H, methyl, ethyl or n-propyl.

[0028] Suitable R 2 Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, or hexyl, it can be straight-chain or branched, with straight-chain being preferred. Preferred R 2 It is H or methyl.

[0029] Suitable R 3 Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, or hexyl, it can be straight-chain or branched, with straight-chain being preferred. Preferred R 3 It is H or n-propyl.

[0030] Preferably, the sorbitol clarifying agent is a compound of formula (I), wherein R 1 Independently selected from H, methyl, ethyl, or propyl, R 2 It is independently selected from H or methyl, and R3 is H or propyl.

[0031] In a preferred form of equation (I), R 1 R 2 and R 3 It's H.

[0032] In another preferred form of equation (I), R 1 It is a methyl group, and R 2 and R 3 It's H.

[0033] In another preferred form of equation (I), R 1 It is ethyl, and R 2 and R 3 It's H.

[0034] In another preferred form of equation (I), R 1 and R 2 It is methyl, and R 3 It's H.

[0035] In another preferred form of equation (I), R 1 It is n-propyl, R 2 It is H, and R 3 It's n-propyl.

[0036] The clarified polyolefin waste may contain only one type of sorbitol clarifying agent of formula (I) (e.g., where R...). 1 It is a methyl group, and R 2 and R 3 It is H; or as another instance where R 1 It is n-propyl, R 2 It is H, and R 3 It is a mixture of sorbitol clarifying agents of different types of formula (I), such as n-propyl sorbitol.

[0037] Step b) includes adding the amide clarifying agent to the clarified polyolefin waste to form recycled polyolefin.

[0038] The amide clarifying agent can be added to the clarified polyolefin waste at a concentration of less than 500 ppm, preferably less than 250 ppm, and especially less than 200 ppm.

[0039] The amide clarifying agent can be added to the clarified polyolefin waste at a concentration of at least 1 ppm, preferably at least 10 ppm, and particularly at least 25 ppm.

[0040] The amide clarifying agent can be added to the clarified polyolefin waste at a concentration of 0.0001-0.1 wt%, preferably 0.001-0.025 wt%, and particularly 0.003-0.018 wt%.

[0041] In another form, the amide clarifying agent is added to the clarified polyolefin waste at a weight ratio of amide clarifying agent to sorbitol clarifying agent of 1:4 to 1:80, preferably 1:7 to 1:50, and particularly 1:10 to 1:40.

[0042] The amount of sorbitol clarifying agent in clarified polyolefin waste can be analyzed by high-performance liquid chromatography (HPLC).

[0043] Preferably, in the recycling method of the present invention, for example in step a) or step b), no further sorbitol clarifying agent is added to the clarified polyolefin waste. The term "no further addition of sorbitol clarifying agent" generally means neither adding an additional amount of the same sorbitol clarifying agent already contained in the clarified polyolefin waste, nor adding any sorbitol clarifying agent different from that already contained in the clarified polyolefin waste.

[0044] The amide clarifying agent can be added to the clarified polyolefin waste by melting it and by mixing it with the amide clarifying agent. The melting of the clarified polyolefin waste and the mixing of the clarified polyolefin waste with the amide clarifying agent can be carried out simultaneously or continuously in any order.

[0045] In a preferred embodiment, the amide clarifying agent can be added to the clarified polyolefin waste by melting the clarified polyolefin waste and by mixing the clarified polyolefin waste with an amide clarifying agent, for example, by a side feeder on an extruder.

[0046] In another form, the amide clarifying agent can be added to the clarified polyolefin waste by first mixing the clarified polyolefin waste with the amide clarifying agent and then melting the clarified polyolefin waste.

[0047] Amide clarifying agents can be added to clarify polyolefin waste in the following forms.

[0048] -In pure form, preferably in pure powder form. - In masterbatch form, it contains an amide clarifying agent incorporated into a carrier polymer; or - A compounded polymer form containing an amide clarifying agent incorporated into a polymer matrix.

[0049] In one form, the amide clarifying agent is added to the clarified polyolefin waste in the form of a masterbatch containing the amide clarifying agent incorporated in a carrier polymer. The masterbatch can be in powder or granular form, preferably granular. The carrier polymer can be a polyolefin, such as polyethylene or polypropylene. The carrier polymer can be a virgin polymer or a recycled polymer. The masterbatch typically contains 0.1-5 wt%, preferably 0.25-2 wt%, of the amide clarifying agent. The masterbatch can contain other plastic additives or pigments, such as those listed below. The masterbatch can be added to the clarified polyolefin waste by first melting the clarified polyolefin waste and then mixing it with the clarified polyolefin waste via, for example, a side feeder on an extruder.

[0050] In another form, the amide clarifying agent is added to the clarified polyolefin waste in the form of a compounded polymer, said compounded polymer comprising the amide clarifying agent incorporated into a polymer matrix.

[0051] The polymer matrix can be a polyolefin, such as polyethylene or polypropylene. The polymer matrix can be a virgin polymer or a recycled material. The compounded polymer typically contains 0.0001 to 0.1 wt%, preferably 0.001 to 0.025 wt%, and particularly 0.003 to 0.018 wt% of an amide clarifying agent. The compounded polymer may contain other plastic additives or pigments, such as those listed below. The compounded polymer can be added to the clarified polyolefin waste by first premixing the compounded polymer with the clarified polyolefin waste, and then melting the premix containing the compounded polymer and the clarified polyolefin waste in, for example, an extruder.

[0052] The melting of clarified polyolefin waste can be achieved at a temperature of at least 80, 90, 100, 110 or 150°C. The melting of clarified polyolefin waste in step b) can be achieved at a temperature of 800 to 300°C, preferably 100 to 250°C.

[0053] The amide clarifying agent can be added to the clarified polyolefin waste via a mixer, kneader, or extruder, with an extruder being preferred. Suitable extruders are single-screw extruders, twin-screw extruders, planetary gear extruders, or ring extruders. The addition of the amide clarifying agent can be carried out under air or an inert gas condition, such as nitrogen. The addition of the amide clarifying agent can be carried out under atmospheric pressure or vacuum.

[0054] Suitable amide clarifying agents can be any bisamide, triamide, or tetraamide of the formula (IA), (IB), and (IC).

[0055] in x and y are 2, 3, or 4; z' and z" are independently 1, 2, or 3, provided that the sum of z' and z" is 2, 3, or 4; X0 is a residue formed by eliminating x carboxyl groups from a saturated or unsaturated aliphatic polycarboxylic acid having 3-25 carbon atoms, a residue formed by eliminating x carboxyl groups from a saturated or unsaturated alicyclic polycarboxylic acid having 7-25 carbon atoms, or a residue formed by eliminating x carboxyl groups from an aromatic polycarboxylic acid having 8-25 carbon atoms; any of the polycarboxylic acids optionally contains other heteroatoms in its skeleton. The groups X1 are independent of each other: C1-C 20 Alkyl groups, which are unsubstituted or substituted with one or more hydroxyl, amino, and / or nitro groups; C2-C 20 Alkenyl groups, which are unsubstituted or substituted with one or more hydroxyl, amino, and / or nitro groups; C2-C interrupted by oxygen or sulfur 20 alkyl; C3-C 12 Cycloalkyl groups, which are unsubstituted or substituted by one or more C1-C2 groups. 20 Alkyl-substituted; Double [C3-C] 12 [cycloalkyl]-C1-C 10 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; A bicyclic or tricyclic hydrocarbon group having 5-20 carbon atoms, which is unsubstituted or surrounded by one or more C1-C2 groups. 20 Alkyl-substituted; Phenyl, which is unsubstituted or substituted with one or more compounds selected from C1-C2. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylamino, di(C1-C) 20 Substituted with alkyl, amino, hydroxyl, and nitro groups; Phenyl-C1-C 20 Alkyl groups, which are unsubstituted or composed of one or more compounds selected from C1-C2. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylamino, di-(C1-C) 20 Substituted with alkyl, amino, hydroxyl, and nitro groups; Phenyl vinyl groups, which are unsubstituted or converted by one or more C1-C2 groups. 20 Alkyl-substituted; Biphenyl-(C1-C)10 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthyl group, which is unsubstituted or surrounded by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthyl-C1-C 20 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthoxymethyl, which is unsubstituted or converted by one or more C1-C2 groups. 20 Alkyl-substituted; Biphenylene, fluorenyl, anthracene; 5- to 6-membered heterocyclic groups, which are unsubstituted or surrounded by one or more C1-C1 groups. 20 Alkyl-substituted; C1-C containing one or more halogens or pseudohalogens 20 hydrocarbon group; Three (C1-C) 10 alkyl)silyl; or Three (C1-C) 10 Alkyl)silyl (C1-C) 10 alkyl); Y0 is formed by eliminating y amino groups of a saturated or unsaturated aliphatic polyamine having 3-25 carbon atoms, by eliminating y amino groups of a saturated or unsaturated alicyclic polyamine having 6-25 carbon atoms, or by eliminating y amino groups of an aromatic polyamine having 6-25 carbon atoms; any of the polyamines optionally contains other heteroatoms in its backbone. Z0 is formed by eliminating z' amino groups and z” carboxyl groups of an unsaturated or saturated aliphatic aminocarboxylic acid having 2-25 carbon atoms, by eliminating z' amino groups and z” carboxyl groups of a saturated or unsaturated alicyclic aminocarboxylic acid having 7-25 carbon atoms, or by eliminating z' amino groups and z” carboxyl groups of an aromatic aminocarboxylic acid having 7-25 carbon atoms; any of the aminocarboxylic acids optionally contains other heteroatoms in its skeleton. Groups Z1 and Z2 independently have the same definition as X1.

[0056] Examples of saturated or unsaturated aliphatic polycarboxylic acids having 3 to 25, preferably 3 to 16, particularly 4 to 12 carbon atoms and x carboxyl groups, and optionally containing other heteroatoms in their skeleton, are malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanoic acid, 1,18-octadecanoic acid, citric acid, and solanine. Alkanetricarboxylic acid, propanetricarboxylic acid, propylenetricarboxylic acid, pentanetricarboxylic acid, ethanetetracarboxylic acid, propanetricarboxylic acid (especially 1,2,3-propanetricarboxylic acid), propanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid (especially 1,2,3,4-butanetetracarboxylic acid), dodecanetetracarboxylic acid, ethylenediaminetetraacetic acid, ethylenediaminotriacetic acid, ethylene glycol bis[β-aminoethyl ether]N,N,N',N'-tetraacetic acid, N-hydroxyethylethylenediamine-N,N',N'-triacetic acid, 1,3-diaminoprop-2-ol-N,N,N',N'-tetraacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, ethylenediaminotripropionic acid, 1,6-hexamethylenediaminetetraacetic acid, N-(2-carboxyethyl)iminodiacetic acid, etc.

[0057] Examples of saturated or unsaturated alicyclic polycarboxylic acids having 7-25, preferably 8-16, carbon atoms and x carboxyl groups, and optionally containing other heteroatoms in their skeleton, are 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, 5-(succinic acid)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, and 5,6,9,10-tetracarboxylic tricyclic[6.2.2.0] which may have lower alkyl groups as substituents. 2,7 [4.2.0] Dodecane-2,11-diene (e.g., with a methyl group at the 3-, 8-, 11-, or 12-position), 1,2-cyclohexanediaminetetraacetic acid, 2,3,5-tricarboxycyclopentylacetic acid, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid, 3,5,6-tricarboxynorbornene-2-acetic acid, thiobis(norbornene-2,3-dicarboxylic acid), bicyclo[4.2.0]octane-3,4,7,8-tetracarboxylic acid, 1,1'-bicyclopropane-2,2',3,3'-tetracarboxylic acid, 1,2-bis(2,3-dimethyl-2,3-dicarboxycyclobutyl)ethane, pyrazine-2,3,5,6-tetracarboxylic acid, tricyclo[4.2.2.0] 2,5Dec-9-en-3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthosuccinic acid (e.g., with a methyl group at the 1-, 5-, 6-, or 7-position), 2,3,4,5,6,7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid, etc.

[0058] Examples of aromatic polycarboxylic acids having 8 to 25, preferably 8 to 22, particularly 8 to 17 carbon atoms and x carboxyl groups, and optionally containing other heteroatoms in their skeleton, include p-phenylene diacetic acid, p-phenylene diacetic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2, 6-Naphthalenedicarboxylic acid, 2,7-Naphthalenedicarboxylic acid, biphenylic acid, 3,3′-biphenylenedicarboxylic acid, 4,4′-biphenylenedicarboxylic acid, 4,4′-binaphthalenedicarboxylic acid, bis(3-carboxyphenyl)methane, bis(4-carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)propane, 3,3′-sulfonyldibenzoic acid, 4,4-sulfonyldibenzoic acid, 3 3′-Oxybenzoic acid, 4,4′-Oxybenzoic acid, 3,3′-Carbonylbenzoic acid, 4,4′-Carbonylbenzoic acid, 3,3′-Thiobenzoic acid, 4,4′-Thiobenzoic acid, 4,4′-(Phenylidenedioxy)benzoic acid, 4,4′-Isophthaloylbenzoic acid, 4,4′-Terephthaloylbenzoic acid, Dithiosalicylic acid, Tribenzoic acid (such as pyromellitic acid) Formic acid, benzoyl tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, diphenylmethane tetracarboxylic acid, pyrene tetracarboxylic acid, naphthalene tetracarboxylic acid, 4,4′-dinaphthalenedicarboxylic acid, benzidine-3,3′-dicarboxy-N,N'-tetraacetic acid, diphenylpropane tetracarboxylic acid, anthracene tetracarboxylic acid, phthalocyanine tetracarboxylic acid, ethylene glycol trimellitic acid diester, benzohexacarboxylic acid, glyceryl trimellitic acid diester, etc.

[0059] Examples of straight-chain or branched alkyl groups having up to 20 carbon atoms and optionally substituted with one or more hydroxyl, amino, and / or nitro groups are ethyl, n-propyl, 1-methylethyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-ethylpropyl, tert-butylmethyl, hexyl, 1-methylpentyl, heptyl, isoheptyl, 1-ethylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, isononyl, neononyl, 2,4,4-trimethylpentyl, undecyl, tridecyl, pentadecyl, heptadecanyl, hydroxymethyl, 1-hydroxyethyl, and 1-aminoethyl. Branched C3-C 10Alkyl groups are particularly preferred. One preferred meaning of groups X1, Y1, Z1, and Z2 is a branched C3-C chain with a quaternary C atom at position 1. 10 Alkyl groups, especially -C(CH3)2-H or -C(CH3)2-(C1-C7 alkyl groups).

[0060] C2-C interrupted by oxygen or sulfur 20 Examples of alkyl groups are tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, tert-butoxybutyl, (H3C)3C-S-CH2-, (H3C)3C-S-C2H4-, (H3C)3C-S-C3H5- ​​and (H3C)3C-S-C4H8-.

[0061] Examples of C1-C8 alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, and octoxy. Methoxy is particularly preferred.

[0062] Examples of C1-C8 alkylthio groups are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, and octylthio.

[0063] Examples of C1-C8 alkyl sulfinyl groups are methyl sulfinyl, ethyl sulfinyl, propyl sulfinyl, butyl sulfinyl, pentyl sulfinyl, hexyl sulfinyl, heptyl sulfinyl, and octyl sulfinyl.

[0064] Unsubstituted or substituted C1-C groups with one or more hydroxyl, amino, and / or nitro groups 20 Examples of alkenyl groups are 9-decenyl, 8-heptadecenyl, 11-hydroxy-8-heptadecenyl, and 11-amino-8-heptadecenyl.

[0065] Unreplaced or by one or more C1-C 20 Alkyl groups, such as 1, 2, 3, or 4 C1-C4 alkyl-substituted C3-C4 alkyl groups. 12 Examples of cycloalkyl groups are cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, and cycloheptyl.

[0066] Unreplaced or by one or more C1-C 20 Alkyl groups, such as 1, 2, or 3 C1-C4 alkyl-substituted bis[C3-C] 12 cycloalkyl]-C1C 10 An example of an alkyl group is dicyclohexylmethyl.

[0067] Unreplaced or by one or more C1-C 20Examples of alkyl groups, such as 1, 2, or 3 C1-C4 alkyl-substituted bicyclic or tricyclic hydrocarbon groups having 5-20 carbon atoms, are: as well as .

[0068] Unsubstituted or selected from one or more of C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylamino, di(C1-C) 20 Examples of phenyl groups substituted with alkyl, amino, hydroxyl, and nitro groups, preferably C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, di(C1-C4 alkyl)amino, hydroxyl, and nitro groups, are phenyl, 3-methylphenyl, 3-methoxyphenyl, 4-methylphenyl, 4-ethylphenyl, propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 2,3-dimethoxyphenyl, 2-nitrophenyl, 3-methyl-6-nitrophenyl, 4-dimethylaminophenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-ditert-butylphenyl, 2,4,6-trimethylphenyl, and 3,5-ditert-butyl-4-hydroxyphenyl.

[0069] Unsubstituted or selected from one or more of C1-C 20 Alkyl, C3-C 12 cycloalkyl, phenyl, C1-C 20 Alkoxy, amino, hydroxyl, and nitro groups, preferably C1-C4 alkyl, C3-C5 cycloalkyl, phenyl, C1-C4 alkoxy, and hydroxyl groups substituted with phenyl-C1-C... 20 Examples of alkyl groups are benzyl, α-cyclohexylbenzyl, diphenylmethyl, 1-phenylethyl, α-hydroxybenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 3-methylbenzyl, 3,4-dimethoxybenzyl, and 2-(3,4-dimethoxyphenyl)ethyl.

[0070] Unreplaced or by one or more C1-C 20 An example of an alkyl-substituted phenyl vinyl group, such as 1, 2 or 3 C1-C4 alkyl-substituted phenyl vinyl groups, is 2-(4-methylphenyl)vinyl.

[0071] Unreplaced or by one or more C1-C 20 Alkyl groups, such as biphenyls with 1, 2, or 3 C1-C4 alkyl substituted groups - (C1-C4) 10 An example of alkyl is 4-biphenylmethyl.

[0072] Unreplaced or by one or more C1-C 20 Examples of alkyl groups, such as 1-naphthyl and 2-naphthyl groups substituted with 1, 2 or 3 C1-C4 alkyl groups, are 1-naphthyl and 2-naphthyl.

[0073] Unreplaced or by one or more C1-C 20 Alkyl groups, such as naphthyl-C1-C4 substituted with 1, 2, or 3 C1-C4 alkyl groups. 20 Examples of alkyl groups are 1-naphthylmethyl and 2-naphthylmethyl.

[0074] Unreplaced or by one or more C1-C 20 An example of an alkyl group, such as a naphthoxymethyl group substituted with 1, 2, or 3 C1-C4 alkyl groups, is 1-naphthoxymethyl.

[0075] Examples of biphenylene, fluorenyl, or anthracene are 2-biphenylene, 9-fluorenyl, 1-fluorenyl, or 9-anthrayl, respectively.

[0076] Unreplaced or by one or more C1-C 20 Examples of alkyl groups, such as 5- to 6-membered heterocyclic groups substituted with 1, 2, or 3 C1-C4 alkyl groups, are 3-pyridyl, 4-pyridyl, 2-hydroxypyridin-3-yl, 3-quinolinyl, 4-quinolinyl, 2-furanyl, 3-furanyl, and 1-methyl-2-pyrroleyl.

[0077] C1-C containing one or more halogens or pseudohalogens such as 1, 2, 3, 4, 5, or 6-F, -Cl, or -I. 20 Examples of hydrocarbon groups are 1-bromo-2-methylpropyl, dichloromethyl, pentafluoroethyl, 3,5-bis[trifluoromethyl]phenyl, 2,3,5,6-tetrafluoro-p-tolyl, 2,3-dichlorophenyl, 3,4-dichlorophenyl and 2,4-bis[trifluoromethyl]phenyl.

[0078] Three (C1-C) 10 An example of alkyl(silyl) is (H3C)3Si-.

[0079] Three (C1-C) 10 Alkyl)silyl (C1-C) 10 An example of an alkyl group is (H3C)3Si-(CH2)2-.

[0080] Examples of saturated or unsaturated aliphatic polyamines having 3 to 25 carbon atoms and y amino groups and optionally containing other heteroatoms in their skeleton are 1,3-diaminopropane, 1,4-diaminobutane and 1,5-diaminopentane.

[0081] Examples of saturated or unsaturated alicyclic polyamines having 6 to 25, preferably 6 to 13, carbon atoms and y amino groups, and optionally containing other heteroatoms in their skeleton, are 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexyl, 4,4′-diamino-3,3′-dimethyldicyclohexyl, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophorone diamine, menthyl diamine, melamine, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,4,5-tetraaminocyclohexane, etc.

[0082] Examples of aromatic polyamines having 6 to 25, preferably 6 to 17, particularly 6 to 13 carbon atoms and y amino groups, and optionally containing other heteroatoms in their skeleton, include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 2,4-diaminotrimethylbenzene, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 1,5-diaminonaphthalene, etc. 1,8-Diaminonaphthalene, 2,3-Diaminonaphthalene, 2,7-Diaminonaphthalene, 9,10-Diaminophenanthrene, 3,3',5,5'-Tetramethylbenzidine, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethoxy-4,4'-Diaminobiphenyl, 4,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 4,4'-Methylenedi-o-toluidine, 4,4'-Methylenedi-2,6-dimethyltoluidine, 4,4'-Methylenedi-2,6-diethylaniline, 4,4'-Diamino-1,2-diphenylaniline Alkane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminostilbene, 3,4'-diamino-2,2-diphenylpropane, 4,4'-diamino-2,2-diphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-thiodiphenylamine, 2,2'-dithiodiphenylamine, 4,4'-dithiodiphenylamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzoylaniline, o-toluidine sulfone, 2 ,7-Diaminofluorene, 3,7-Diamino-2-methoxyfluorene, bis(p-aminophenylaniline), 1,3-bis(4-aminophenylpropyl)benzene, 1,4-bis(4-aminophenylpropyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene-1,2,4,5-tetraaminobenzene, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, Para Rosaniline, 2,4,6-triaminophenol, 3,3'-diaminobenzidine, tris(4-aminophenyl)methane, 2,4,6-triaminopyrimidine, etc.

[0083] Examples of unsaturated or saturated aliphatic aminocarboxylic acids having 2 to 25, preferably 2 to 12, particularly 2 to 5 carbon atoms, z' amino groups and z” carboxyl groups, and optionally containing other heteroatoms in their skeleton, are glycine, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid, β-aminobutyric acid, γ-aminobutyric acid, α-amino-α-methylbutyric acid, γ-amino-α-methylbutyric acid, α-aminoisobutyric acid, β-aminoisobutyric acid, α-aminopentanoic acid, δ-Aminovaleric acid, β-aminocrotonic acid, α-amino-β-methylvaleric acid, α-aminoisovaleric acid, 2-amino-4-pentenoic acid, α-aminohexanoic acid, 6-aminohexanoic acid, α-aminoisohexanoic acid, 7-aminoheptanoic acid, α-aminooctanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 2-aminoadipic acid, arginine, asparagine, aspartic acid, cystine, glutamic acid, glutamine, ornithine, creatine, aminomalonic acid, etc.

[0084] Examples of saturated or unsaturated alicyclic aminocarboxylic acids having 7 to 25, preferably 7 to 9, carbon atoms, z' amino groups and z” carboxyl groups, and optionally containing other heteroatoms in their skeleton, are 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, 1-amino-1,3-cyclohexanedicarboxylic acid, etc.

[0085] Examples of aromatic aminocarboxylic acids having 7 to 25, preferably 7 to 15, particularly 7 to 11 carbon atoms, z' amino groups and z” carboxyl groups, and optionally containing other heteroatoms in their skeleton, are α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-aminocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic acid, meta-aminobenzoic acid, etc. Aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3 -Methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4-(4-aminophenyl)butyric acid, 4-aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid, p-aminohippuric acid, 2-amino-1-naphthoic acid, 3-amino-1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6- Amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid, 8-amino-2-naphthoic acid, 3,5-diaminobenzoic acid, 3,5-dicarboxyaniline, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, etc.

[0086] Examples of halogens or pseudohalogens are -F, -Cl, -Br, -I, -CN, -CNO, -OCN, -SCN, and -CNS.

[0087] In a preferred embodiment, the amide clarifying agent is a triamide or tetraamide according to formula (IA). In this preferred embodiment, x is an integer of 3 or 4; X0 is a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid; and X1 is represented by formula (ID). (ID) Furthermore, the three or four X2s are the same or different, and each independently represents a hydrogen atom or a C1-C atom. 10 Straight-chain or branched alkyl groups. Straight-chain or branched C1-C... 10Examples of alkyl groups include methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-ethylpropyl, tert-butylmethyl, hexyl, 1-methylpentyl, heptyl, isoheptyl, 1-ethylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, isononyl, neononyl, and 2,4,4-trimethylpentyl.

[0088] Preferably, the amide clarifying agent is an aromatic diamide, an aromatic triamide, or an aromatic tetraamide.

[0089] In a preferred embodiment, the amide clarifying agent is a bisamide, triamide, or tetraamide according to any one of formulas (IA), (IB), and (IC). In such a preferred embodiment, x, y, or the sum of z′ and z′ is 2, and X0, Y0, and Z0 are groups of formulas (II), (III), (IVA), or (IVB). Where R represents a hydrogen atom, an optionally substituted or branched C1-C4 alkyl group, or an optionally substituted C3-C4 alkyl group. 12 cycloalkyl or optionally substituted C6-C 20 Aryl.

[0090] Examples of C1-C4 alkyl groups include methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 2-methylpropyl, 1-methylpropyl, and tert-butyl. Optional substitutions are also possible for C3-C4 alkyl groups. 12 Examples of cycloalkyl groups include cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, and cycloheptyl. Optional substitutions are available for C6-C... 20Examples of aryl groups include phenyl, 3-methylphenyl, 3-methoxyphenyl, 4-methylphenyl, 4-ethylphenyl, propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 2,3-dimethoxyphenyl, 2-nitrophenyl, 3-methyl-6-nitrophenyl, 4-dimethylaminophenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, and 3,5-di-tert-butylphenyl. -4-hydroxyphenyl, benzyl, α-cyclohexylbenzyl, diphenylmethyl, 1-phenylethyl, α-hydroxybenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 3-methylbenzyl, 3,4-dimethoxybenzyl and 2-(3,4-dimethoxyphenyl)ethyl, 2-(4-methylphenyl)vinyl, 4-biphenylmethyl, naphthyl, 1-naphthyl, 2-naphthyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthoxymethyl, 2-biphenylenyl, 9-fluorenyl, 1-fluorenyl and 9-anthrayl.

[0091] A particularly suitable group of amide clarifying agents are aromatic bisamides based on formula (VI): (VI) R1 and R2 are each independently selected from C1-C5 straight-chain or branched alkyl groups or substituted or unsubstituted C3-C6 cycloalkyl groups, preferably both R1 and R2 are tert-butyl. In this case, R1 and R2 represent each Y1 of formula (IB).

[0092] A preferred compound of formula (II) is a compound of formula (XI).

[0093] (XI) A preferred compound of formula (VI) is a compound of formula (XII).

[0094] (XII) A preferred compound of formula (IV A) is a compound of formula (XIII).

[0095] (XIII) Another preferred compound according to formula (IV A) is a compound of formula (XIV).

[0096] (XIV) In a preferred embodiment, the amide clarifying agent is a triamide according to any one of formulas (IA), (IB), and (IC). In such a preferred embodiment, x, y, or the sum of z′ and z′ is 3, and X0, Y0, and Z0 are groups of formula (V). (V) A more preferred embodiment of formula (V) includes a compound according to structure (VA), (VB), (VC), or (VD).

[0097] Each X1, each Y1, each Z1, and each Z2 has the same meaning as previously provided, independently of each other.

[0098] Preferably, the amide clarifying agent is a diamide or triamide of formula (IB), wherein when the amide clarifying agent is a diamide, Y0 is represented by formula (III) or formula (II), and when the amide clarifying agent is a triamide, Y0 is represented by formula (V).

[0099] More preferably, the amide clarifying agent is a triamide of formula (IB), wherein Y0 is represented by formula (V). Particularly preferred is an aromatic triamide of formula (VII). (VII) R1, R2, and R3 are each independently selected from C1-C5 straight-chain or branched alkyl groups or substituted or unsubstituted C3-C6 cycloalkyl groups, preferably R1, R2, and R3 are all tert-butyl. In this case, R1, R2, and R3 represent each Y1 of formula (IB).

[0100] In a desired implementation, R1 is a substituted cyclohexyl group. Suitably, R1 has the structure shown in formula (VII A): (VII A) Where W can be selected from C1-C 10 The substituted or unsubstituted alkyl group, whether straight-chain or branched, can be at any substitution position of the cyclohexyl group, preferably at the para position. In this case, R2 and R3 will have the same definitions given for the structure of formula (VII). Preferably, W is at the para position and in the cis position relative to the bond of the carbonyl carbon attached to the cyclohexane diester ring. Preferably, W is at the para position and in the trans position relative to the bond of the carbonyl carbon attached to the cyclohexane diester ring.

[0101] In another preferred embodiment, R2 has the same definition as R1 as represented by equation (VII A), independent of R1.

[0102] In another preferred embodiment, R2 and R3 are independent of each other, and R1 has the same definition as R1 represented by equation (VII A).

[0103] Therefore, according to another preferred embodiment, the amide clarifying agent is an aromatic triamide having formula (VII B): (VII B) Each V group is independently selected from C1-C5 straight-chain or branched alkyl groups, preferably C3 or C4 branched alkyl groups, and more preferably all V groups are tert-butyl groups.

[0104] A specific suitable compound according to formula (VII B) is 1,3,5-tris[cis-4-tert-butylcyclohexylcarbonylamino]benzene, as shown in formula (XV): (XV) Another specific suitable compound according to formula (VII B) is trans-4-tert-butylcyclohexylcarbonylamino-3,5-bis[cis-4-tert-butylcyclohexylcarbonylamino]benzene, as shown in formula (XVI): (XVI) Another suitable compound according to formula (VII B) is cis-4-tert-butylcyclohexylcarbonylamino-3,5-bis[trans-4-tert-butylcyclohexylcarbonylamino]benzene, as shown in formula (XVII): (XVII) Another specific suitable compound according to formula (VII B) is 1,3,5-tris[trans-4-tert-butylcyclohexylcarbonylamino]benzene, as shown in formula (XVIII): (XVIII) Other specific suitable compounds according to formula (VII B) are 1,3,5-tris[cis-4-isopropylcyclohexylcarbonylamino]benzene, trans-4-isopropylcyclohexylcarbonylamino-3,5-bis[cis-4-isopropylcyclohexylcarbonylamino]benzene, trans-4-isopropylcyclohexylcarbonylamino-3,5-bis[cis-4-isopropylcyclohexylcarbonylamino]benzene and 1,3,5-tris[trans-4-isopropylcyclohexylcarbonylamino]benzene.

[0105] As described above, a preferred embodiment of the compound of formula (VII) is wherein R1, R2, and R3 are all tert-butyl groups. A particularly preferred amide clarifying agent of this type is N,N',N''-1,3,5-phenyltriyltris(2,2-dimethylpropionamide), which may have the structure according to formula (XIX): (XIX) In addition to amide clarifying agents, other plastic additives may be added to the clarified polyolefin waste in step b). Suitable other plastic additives include antioxidants, UV absorbers, light stabilizers, metal deactivators, phosphites, phosphonates, hydroxylamine and amine N-oxides, nitrones, thiosynergists, rheology modifiers, acid scavengers, basic co-stabilizers, nucleating agents, benzofuranones and indolones, and flame retardants.

[0106] The present invention also relates to recycled polyolefins containing amide clarifying agents and clarified polyolefin waste containing sorbitol clarifying agents.

[0107] Recycled polyolefins can often replace virgin polyolefins with the same or at least equivalent properties. Recycled polyolefins exhibit pre-damage, such as the formation of new chemical groups (e.g., carbonyl groups) on the polymer chain through oxidation or photo-oxidation processes. Typically, recycled polyolefins contain carbonyl groups not present in virgin polyolefins. The concentration of carbonyl groups is often a measure of the pre-damage in recycled polyolefins. The concentration of carbonyl groups can be determined by infrared spectroscopy, for example, by measuring at 1720 cm⁻¹. -1 Absorption of carbonyl vibrations within the range.

[0108] Recycled polyolefins can typically be obtained through a method for recovering clarified polyolefin waste that includes the following steps: a) Collect clarified polyolefin waste containing sorbitol clarifying agent, and b) Add an amide clarifying agent to the clarified polyolefin waste to form recycled polyolefin.

[0109] The present invention also relates to the use of amide clarifying agents for reducing the haze of clarified polyolefin waste containing sorbitol clarifying agents after recycling.

[0110] A reduction in haze can be determined when sorbitol clarifying agent (e.g., bis(4-propylbenzylene)propylsorbitol, which may be added in an amount of 100 ppm to 5000 ppm, preferably 150 ppm to 4000 ppm, more preferably 200 ppm to 2500 ppm, for example 300 ppm) instead of amide clarifying agent is added to the clarified polyolefin waste.

[0111] Haze can be measured on a plate according to ASTM standard D1003, for example, on a haze testing instrument from BYK Gardner GmbH, Germany. In this test, haze is typically defined as the portion of visible light scattered over a wide angle (2.5° < θ < 90°). Haze is generally a measure of the turbidity of a sample.

[0112] Example Sorbitol A: Millad® 3998, purchased from Millicken, 1,3:2,4-bis(3,4-dimethylbenzyl)sorbitol.

[0113] Sorbitol B: Millad® NX8000, purchased from Milliken, bis(4-propylbenzylene)propyl sorbitol.

[0114] Triamide A: N,N',N''-1,3,5-benzenetriyltri[2,2-dimethylpropionamide].

[0115] Polyolefin A: a random copolymer of poly(propylene-co-ethylene), free of antiblocking agents, slip agents, and calcium stearate, with a melting point of about 150°C (ISO 11357-3), a Vicat softening temperature of about 140°C (ISO 306), and a flexural modulus of 1100 mPa (ISO 178). It is a powder and can be purchased from Borealis AG, Austria, RD204CF.

[0116] Example 1 a) Sorbitol clarifying agent for clarifying polyolefin waste The clarified polyolefin waste model system was prepared as follows: Polyolefin A powder was mixed with 1800 ppm sorbitol A (“Waste 1”) or 1800 ppm sorbitol B (“Waste 2”) in a high-speed mixer and compounded into granules using a twin-screw extruder at 230°C. The granules were then injection molded into 2 mm thick sheets at 230°C using an injection molding machine. The haze of the sheets was analyzed using a haze meter according to ASTM standard D1003. Haze is defined as the portion of visible light scattered over a wide angle (2.5° < θ < 90°) and is a measure of the turbidity of the sample. The results are listed in Table 1 or 2.

[0117] b) Regenerated polyolefins containing sorbitol A and triamide A A model system of recycled polyolefin waste containing 1800 ppm sorbitol A and added triamide A was prepared as follows: Powdered polyolefin A was mixed with 1800 ppm sorbitol A and an additional 50 or 150 ppm triamide A (sample "Recycled 1 or 2") used in Waste 1 in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C. For comparison, random copolymer polypropylene was mixed with 1800 ppm sorbitol A and 300 ppm sorbitol B (sample "Recycled Comparison A") used in Waste 1 in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C.

[0118] The granules were molded into 2 mm thick plates at 230°C using an injection molding machine. The haze of the plates was analyzed as described in Example 1a). The results are listed in Table 1.

[0119] Table 1: Haze of 2mm plate

[0120] Data from this model system used for recycled polyolefins indicate that the clarified polyolefin waste model containing only sorbitol A (“Waste 1”) showed increased haze when attempts were made to clarify it by adding another sorbitol clarifying agent (“Recycled Comparison A”). However, the haze remained at a similar level to “Waste 1” in “Recycled 1”, or even decreased by adding triamide A (“Recycled 2”).

[0121] c) Regenerated polyolefins containing sorbitol B and triamide A A model system of recycled polyolefin waste containing 1800 ppm sorbitol B and added triamide A was prepared as follows: Powdered polyolefin A was mixed with 1800 ppm sorbitol B and an additional 50 or 150 ppm triamide A (samples "Recycled 3 or 4") used in Waste 1 in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C. For comparison, random copolymer polypropylene was mixed with 1800 ppm sorbitol B and 300 ppm sorbitol A (sample "Recycled Comparison B") used in Waste 1 in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C.

[0122] The granules were molded into 2 mm thick plates at 230°C using an injection molding machine. The haze of the plates was analyzed as described in Example 1a). The results are listed in Table 2.

[0123] Table 2: Haze of 2mm plate

[0124] Data from this model system used for recycled polyolefins showed that the clarified polyolefin waste model containing only sorbitol B (“Waste 2”) exhibited increased haze when attempts were made to clarify it by adding another sorbitol clarifying agent (“Recycled Comparison B”). However, the haze remained at a similar level to “Waste 2” in “Recycled 4”, or even decreased by adding triamide A (“Recycled 3”).

[0125] Example 2 a) Clarified polyolefin waste containing sorbitol clarifying agent The clarified polyolefin waste model system was prepared as follows: Polyolefin A powder was mixed with 1800 ppm sorbitol A (“Waste 3”) or 1800 ppm sorbitol B (“Waste 4”) in a high-speed mixer and then compounded into granules using a twin-screw extruder at 230°C. The granules were then injection molded into sheets with a thickness of 1 mm at 200°C and 230°C (see Table 3), respectively. The haze of the sheets was analyzed as described in Example 1a). The results are listed in Tables 3 or 4.

[0126] b) Regenerated polyolefins containing sorbitol A and triamide A A model system of recycled polyolefin waste containing 1800 ppm sorbitol A and added triamide A was prepared as follows: Powdered polyolefin A was mixed with 1800 ppm sorbitol A and an additional 100 or 150 ppm triamide A (samples "Recycled 5 or 6") used in Waste 3 in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C. For comparison, random copolymer polypropylene was mixed with 150 ppm triamide A (instead of 1800 ppm sorbitol A) (sample "Comparison C") in a high-speed mixer and compounded into pellets by a twin-screw extruder at 230°C.

[0127] The granules were molded into 1 mm thick plates at 200°C and 230°C (see Table 3) using an injection molding machine. The haze of the plates was analyzed as described in Example 1a). The results are listed in Table 3.

[0128] Table 3: Haze of 1mm plate

[0129] Data from this model system for recycled polyolefins indicate that the addition of triamide A (“Recycled 5” and “Recycled 6”) reduced the haze of the clarified polyolefin waste model (“Waste 3”) containing only sorbitol A. For comparison, the haze was even worse than that of Waste 3 when triamide A was used in the absence of any sorbitol clarifying agent (“Comparison C”).

[0130] c) Regenerated polyolefins containing sorbitol B and triamide A The following is a model system of recycled polyolefin waste containing 1800 ppm sorbitol B and added triamide A: the powdered form of polyolefin A is mixed with 1800 ppm sorbitol B and an additional 100 or 150 ppm triamide A (sample “Recycled 7 or 8”) used in waste 4 in a high-speed mixer and compounded into granules by a twin-screw extruder at 230°C.

[0131] The granules were molded into 1 mm thick plates at 230°C using an injection molding machine. The haze of the plates was analyzed as described in Example 1a). The results are listed in Table 4.

[0132] Table 4: Haze of 1mm plate

[0133] Data from this model system for recycled polyolefins indicate that the addition of triamide A (“Recycled 7” and “Recycled 8”) reduced the haze of the clarified polyolefin waste model (“Waste 4”) containing only sorbitol B. This was also observed when the clarified polyolefin waste model contained a higher concentration of sorbitol B.

[0134] Example 3 The following example illustrates a model of a recycled material stream where only 20% of the material was clarified during the first lifecycle. Therefore, this recycled material stream requires reclarification by replenishing the remaining conventional clarifying agent level (the original 20%) with at least 80% new clarifying agent. A suitable waste model is prepared as follows: a) Waste model containing 20% ​​polymer pre-clarified with sorbitol A ("Waste 6") 360 ppm sorbitol A (20% of the conventional 1800 ppm loading) was compounded with PP (Borealis RD204CF) in a twin-screw extruder at 230°C. To simulate the additional processing steps during recycling, a subsequent single-screw extrusion was performed at 230°C.

[0135] b) Waste model containing 20% ​​polymer pre-clarified with sorbitol A and then re-clarified with phosphate A ("recycled pair") (Compared to D) For comparison, the commercial clarifying agent ADK Stab® NA-71 (“Phosphate A”, containing lithium 2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate) from Adeka Co., Japan, was used. 360 ppm sorbitol A (20% of the conventional 1800 ppm load) and 1440 ppm phosphate A (80% of the conventional 1800 ppm load) were compounded with PP (Borealis RD204CF) in a twin-screw extruder at 230°C. To simulate the additional processing steps during recycling, a subsequent single-screw extrusion was performed at 230°C.

[0136] c) Waste model containing 20% ​​polymer pre-clarified with sorbitol A and re-clarified with triamide A ("recycled") 12”) 360 ppm sorbitol A (20% of the conventional 1800 ppm load) and 96 ppm triamide (80% of the 120 ppm load) were compounded with PP (Borealis RD204CF) in a twin-screw extruder at 230°C. To simulate the additional processing steps during recycling, a subsequent single-screw extrusion was performed at 230°C.

[0137] All granules were molded into 1 mm thick plates at 230°C using an injection molding machine. The haze of the plates was analyzed as described in Example 1a). The results are listed in Table 5.

[0138] Table 5: Haze of 1mm plate

[0139] This example demonstrates, using sorbitol A, sorbitol B, and triamide A, that the reclarification of recycled feed streams already containing a pre-clarified polymer fraction is excellent when using triamide A. Data from these model systems of recycled polyolefins indicate that, in the case of a mixed clarifying agent system resulting from the presence of conventional clarifying agents in the recycled feed stream, using triamide A as the reclarifier achieves better haze. This is also evident for recycled feed streams being reclared containing sorbitol A as a conventional stabilizer (triamide A is better than phosphate A).

Claims

1. A method for recycling clarified polyolefin waste, comprising the following steps: a) Collect clarified polyolefin waste containing sorbitol clarifying agent, and b) Add an amide clarifying agent to the clarified polyolefin waste to form recycled polyolefin.

2. The method according to claim 1, wherein 0.0001 to 0.1% by weight of the amide clarifying agent is added to the clarified polyolefin waste.

3. The method according to claim 1 or 2, wherein the amide clarifying agent is added to the clarified polyolefin waste at a weight ratio of 1:4 to 1:80 between the amide clarifying agent and the sorbitol clarifying agent.

4. The method according to any one of claims 1 to 3, wherein the amide clarifying agent is added to the clarified polyolefin waste by melting the clarified polyolefin waste and by mixing the clarified polyolefin waste with the amide clarifying agent.

5. The method according to any one of claims 1 to 4, wherein the amide clarifying agent is added to the clarified polyolefin waste in the following form -Pure form, - In masterbatch form, comprising the amide clarifying agent incorporated into the carrier polymer, or - A compounded polymer form comprising the amide clarifying agent incorporated into a polymer matrix.

6. The method according to any one of claims 1 to 5, wherein the clarified polyolefin waste contains 0.01 to 3% by weight of the sorbitol clarifying agent.

7. The method according to any one of claims 1 or 6, wherein in step a), the clarified polyolefin waste from different batches is mixed to adjust the concentration of the sorbitol clarifying agent in the clarified polyolefin waste.

8. The method according to any one of claims 1 to 7, wherein the clarified polyolefin waste is - Pre-consumer waste, such as production waste collected from manufacturers or processors; - Post-consumer waste, such as household packaging collected via curbside collection or designated recycling systems, or discarded products returned by consumers; or - Demolition waste, such as waste from the demolition of civil buildings.

9. The method according to any one of claims 1 to 8, wherein the amide clarifying agent is a bisamide, triamide, or tetraamide of any one of formulas (IA), (IB), and (IC): in x and y are 2, 3, or 4; z' and z" are independently 1, 2 or 3, provided that the sum of z' and z" is 2, 3 or 4; X0 is a residue formed by eliminating x carboxyl groups of a saturated or unsaturated aliphatic polycarboxylic acid having 3 to 25 carbon atoms, a residue formed by eliminating x carboxyl groups of a saturated or unsaturated alicyclic polycarboxylic acid having 7 to 25 carbon atoms, or a residue formed by eliminating x carboxyl groups of an aromatic polycarboxylic acid having 8 to 25 carbon atoms; any of the polycarboxylic acids optionally contains other heteroatoms in its skeleton. Group X1 is independent of each other as follows: C1-C 20 Alkyl groups, which are unsubstituted or substituted with one or more hydroxyl, amino, and / or nitro groups; C2-C 20 Alkenyl groups, which are unsubstituted or substituted with one or more hydroxyl, amino, and / or nitro groups; C2-C interrupted by oxygen or sulfur 20 alkyl; C3-C 12 Cycloalkyl groups, which are unsubstituted or substituted by one or more C1-C2 groups. 20 Alkyl-substituted; Double [C3-C] 12 [cycloalkyl]-C1-C 10 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; A bicyclic or tricyclic hydrocarbon group having 5-20 carbon atoms, which is unsubstituted or surrounded by one or more C1-C2 groups. 20 Alkyl-substituted; Phenyl, which is unsubstituted or substituted with one or more compounds selected from C1-C2. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylamino, di(C1-C) 20 Substituted with alkyl, amino, hydroxyl, and nitro groups; Phenyl-C1-C 20 Alkyl groups, which are unsubstituted or composed of one or more compounds selected from C1-C2. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylamino, di-(C1-C) 20 Substituted with alkyl, amino, hydroxyl, and nitro groups; Phenyl vinyl groups, which are unsubstituted or converted by one or more C1-C2 groups. 20 Alkyl-substituted; Biphenyl-(C1-C) 10 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthyl group, which is unsubstituted or surrounded by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthyl-C1-C 20 Alkyl groups, which are unsubstituted or formed by one or more C1-C2 groups. 20 Alkyl-substituted; Naphthoxymethyl, which is unsubstituted or converted by one or more C1-C2 groups. 20 Alkyl-substituted; Biphenylene, fluorenyl, anthracene; 5- to 6-membered heterocyclic groups, which are unsubstituted or surrounded by one or more C1-C1 groups. 20 Alkyl-substituted; C1-C containing one or more halogens or pseudohalogens 20 hydrocarbon group; Three (C1-C) 10 alkyl)silyl; or Three (C1-C) 10 Alkyl)silyl (C1-C) 10 alkyl), Y0 is formed by eliminating y amino groups of a saturated or unsaturated aliphatic polyamine having 3-25 carbon atoms, by eliminating y amino groups of a saturated or unsaturated alicyclic polyamine having 6-25 carbon atoms, or by eliminating y amino groups of an aromatic polyamine having 6-25 carbon atoms; any of the polyamines optionally contains other heteroatoms in its backbone. Y1 has the same definition as X1; Z0 is formed by eliminating z' amino groups and z” carboxyl groups of an unsaturated or saturated aliphatic aminocarboxylic acid having 2-25 carbon atoms, by eliminating z' amino groups and z” carboxyl groups of a saturated or unsaturated alicyclic aminocarboxylic acid having 7-25 carbon atoms, or by eliminating z' amino groups and z” carboxyl groups of an aromatic aminocarboxylic acid having 7-25 carbon atoms; any of the aminocarboxylic acids optionally contains other heteroatoms in its skeleton. Groups Z1 and Z2 independently have the same definition as X1.

10. The method according to any one of claims 1 to 9, wherein the amide clarifying agent is an aromatic triamide of formula (VII): (VII) R1, R2 and R3 are each independently selected from straight-chain or branched C1-C5 alkyl or substituted or unsubstituted C3-C6 cycloalkyl, preferably R1, R2 and R3 are all tert-butyl.

11. The method according to any one of claims 1 to 10, wherein the sorbitol clarifying agent is a sorbitol clarifying agent of formula (I): (I) Where R 1 R 2 and R 3 It is independently selected from H or C1-C6 alkyl groups.

12. The method according to any one of claims 1 to 11, wherein the sorbitol clarifying agent is a sorbitol clarifying agent of formula (I), wherein R 1 Independently selected from H, methyl, ethyl, or propyl, R 2 Independently selected from H or methyl, and R 3 It is H or propyl.

13. The method according to any one of claims 1 to 12, wherein no additional sorbitol clarifying agent is added in the recovery method.

14. The recycled polyolefin as defined in any of the preceding claims, comprising an amide clarifying agent and a clarified polyolefin waste containing a sorbitol clarifying agent.

15. The recycled polyolefin according to claim 14, which is obtained by the method according to any one of claims 1 to 13.

16. Use of amide clarifying agents, specifically for reducing the haze of clarified polyolefin waste after recycling sorbitol clarifying agents.

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