Recycled polymer composition

Abstract

To provide a recycled polymer composition, a method for preparing the same, and applications thereof.SOLUTION: Disclosed is a recycled polymer composition comprising (a) a recycled polymer blend consisting of: (a1) a recycled polyamide, and (a2) a recycled synthetic fibrous material, (b) a block copolymer selected from a functionalized HSBC and a non-functionalized HSBC, and (c) optional additives. The functionalized HSBC comprises functional groups selected from maleic anhydride, epoxy and silane. The recycled synthetic fiber material comprises one or more polymers selected from the group consisting of polyether-polyurea copolymers, polyether-polyester copolymers, polyester-polyurea copolymers, and polyureas derived from paraphenylene-diisocyanate and paraphenylenediamine. The recycled polymer blend has a weight ratio of the recycled polyamide to the recycled synthetic fiber material ranging from 1:10 to 10:1. The recycled polymer composition exhibits an improved melt flow rate and balance of mechanical properties compared to a corresponding composition without the block copolymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to recycled polymer compositions, methods for their preparation, and uses thereof. [Background technology]

[0002] The three "R" principles, collectively known as reduce, reuse, and recycle, have great potential for long-term resource conservation. Among these, plastic recycling has attracted global attention due to the widespread use of plastics in daily life. One of the main challenges in plastic recycling is the collection and sorting of plastics based on their type.

[0003] Fiber recycling, especially when recycling fibers from recycled materials, presents additional challenges. Most fibers are made from thermoplastics such as polyamide, polyester, polypropylene, and spandex. These materials have limited recyclability, and the unrecycled portion typically goes to energy recovery processes or landfills. Challenges to fiber recycling include mixed material composition, contamination, fiber degradation during use and handling, downcycling (i.e., recycling into lower-quality products), and inadequate recycling infrastructure. Spandex fiber possesses excellent stretch and elastic recovery due to its unique chemical structure. However, spandex is difficult to detect and separate from other fibers in textile recycling facilities. Its elasticity can clog shredding machines or result in small spandex fragments appearing in other recycled fabrics. Recycling spandex or blends of spandex with other materials, such as polyester or polyamide, can affect desirable properties such as processability, rheological properties (e.g., melt flow rate), and mechanical properties. Summary of the Invention [Problem to be solved by the invention]

[0004] There remains a need for recycled polymer compositions that include compatibilizers to improve melt flow rate, processability, and mechanical performance. [Means for solving the problem]

[0005] (Summary of the Invention) In one aspect, the present disclosure relates to a recycled polymer composition comprising, consisting essentially of, or consisting of: (a) 80-99 wt% recycled polymer blend consisting of: (a1) recycled polyamide, and (a2) recycled synthetic fiber material; (b) 1-20 wt% block copolymer; and (c) 0-10 wt% of at least one additive. The recycled synthetic fiber material comprises one or more polymers selected from the group consisting of polyether-polyurea copolymer, polyether-polyester copolymer, polyester-polyurea copolymer, and polyurea derived from paraphenylene diisocyanate and paraphenylenediamine. The weight ratio of (a1) to (a2) is 1:10 to 10:1. The block copolymer is selected from (i) functionalized hydrogenated styrenic block copolymer (functionalized HSBC) and (ii) unfunctionalized hydrogenated styrenic block copolymer (unfunctionalized HSBC). Each of the block copolymers (i) and (ii) is independently SRS, (SR) n X, (SRS) nThe block copolymer has a general structure selected from the group consisting of , ...

[0006] In a second embodiment, the block copolymer is a non-functionalized HSBC having the structure SRS.

[0007] In a third embodiment, the block copolymer is a functionalized HBSC comprising at least one functional group selected from the group consisting of maleic anhydride, epoxy, and silane.

[0008] In a fourth embodiment, the block copolymer comprises a blend of functionalized hydrogenated HSBC and non-functionalized HSBC in a weight ratio of 1:10 to 10:1.

[0009] Detailed Description of the Invention The following terms are used in this specification:

[0010] "Consisting essentially of" means that the composition comprises primarily the recited components, and may additionally contain one or more components that do not materially affect the novel properties or intended function of the invention. In embodiments, such additional components are present in an amount of <30 wt%, <20 wt%, or <10 wt%, based on the total weight of the composition.

[0011] "At least one of [a group such as A, B, and C]" or "any of [a group such as A, B, and C]" means a single member from the group, multiple members from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, or A, B and C; or all other combinations of A, B, and C.

[0012] A recitation of an embodiment presented as "A, B, or C" is to be interpreted as including the embodiments A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C."

[0013] "Either A, B or C" refers to one option from A, B or C.

[0014] "Any of A, B, and C" refers to one or more options from A, B, and C.

[0015] "Post-industrial recycling" or PIR refers to plastic scrap material generated from industrial processes. PIR is typically in an uncontaminated state, and the input resin type is known.

[0016] "Post-consumer recycled" or PCR, or PCR material, or PCR polymer, or PCR resin, can be used interchangeably with "recycled composition," "recycled polymer," "waste polymer," and "recycled resin," and includes PIR, different PIR, PIR from different sources, reground PCR, different PCR, PCR from different sources, recycled, and mixtures thereof. PCR does not include or exclude virgin polymer.

[0017] "Virgin polymer" refers to a polymer as produced that has not yet been processed and / or formed into an industrial or consumer end-use article. Virgin polymers may include additives commonly used in the preparation of virgin polymers.

[0018] The "vinyl aromatic unit content" or VAC of a block copolymer refers to the weight percentage of polymerized vinyl aromatic monomers, such as styrene, paramethylstyrene, etc., in the block copolymer. VAC is calculated by dividing the total molecular weight of all vinyl aromatic units by the total molecular weight of the block copolymer. 1 H NMR) and 13 It can be determined using C NMR. VAC is sometimes used interchangeably with PSC (polystyrene content).

[0019] "Butylene unit content" refers to the butylene unit ("B") content, expressed as a weight percentage, relative to all diene-based units in a given polymer (e.g., a hydrogenated block copolymer). Butylene units are formed by polymerizing 1,3-butadiene monomers via 1,2-addition followed by hydrogenation. 1,3-butadiene monomers can also be polymerized via 1,4-addition, which upon hydrogenation result in ethylene units ("E"). Both butylene and ethylene units can be present in the hydrogenated block copolymer, which can also contain vinyl aromatic units and / or other units derived from conjugated diene monomers, arranged in any order. Butylene unit content is 1 H NMR and 13 It can be measured by C NMR. The butylene unit ("B") content is sometimes used interchangeably with the "vinyl content" before hydrogenation.

[0020] "Molecular weight" or M W M refers to the styrene-equivalent molecular weight (kg / mol) of a polymer block or block copolymer. Wcan be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, such as performed in accordance with ASTM 5296-19. The GPC detector can be an ultraviolet detector, a refractive index detector, or a combination thereof. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M of a polymer measured using such a calibrated GPC is W is the styrene equivalent molecular weight or apparent molecular weight. W is measured at the peak of the GPC trace and is generally called the "peak molecular weight" in styrene equivalents, and M p It is shown as follows.

[0021] "Coupling efficiency" or CE refers to the weight percent of coupled polymer molecules relative to the total weight of both coupled and uncoupled polymer molecules. CE is expressed as a percentage (%) and can be used to estimate the diblock structure content, or more generally, the proportion of "uncoupled arms" in a block copolymer. For example, a CE of 80% indicates that the block polymer contains 20% by weight of diblock (uncoupled) species and 80% by weight of triblock and multiarm species.

[0022] "Spandex" may be used interchangeably with "Lycra," "elastane," or other synthetic fiber materials. It refers to yarns and / or fibers made from polymers such as polyurethane, polyether-polyurea copolymer, polyether-polyester copolymer, and similar materials known for their exceptional elasticity and stretchability.

[0023] "Non-hydrogenated SBC" or USBC refers to a styrenic block copolymer (SBC) containing non-hydrogenated diene units and vinyl aromatic units.

[0024] "Partially hydrogenated SBC" or pHSBC refers to an SBC in which the diene units have been hydrogenated to a level of 40-90 mol % and the vinyl aromatic units have been hydrogenated to <20 mol %, preferably <10 mol %, and more preferably <5 mol %.

[0025] "Hydrogenated SBC" or HSBC refers to a styrenic block copolymer (SBC) in which the diene units have been hydrogenated to a level of >90 mol%, preferably >95 mol%, more preferably >98 mol%, or <100 mol%, and the vinyl aromatic units have been hydrogenated to <20 mol%, preferably <10 mol%, more preferably <5 mol%.

[0026] "Maleated styrenic block copolymer" or SBC-g-MA or maleic anhydride grafted SBC or maleic anhydride functionalized SBC are used interchangeably. These refer to SBCs in which at least one maleic anhydride group is grafted onto the polymer backbone or attached to a vinyl group adjacent to the polymer backbone. The SBC may also be an HSBC.

[0027] "Epoxidized styrenic block copolymer" or e-SBC or epoxy-grafted SBC or epoxy-functionalized SBC are used interchangeably. These refer to SBCs in which at least one epoxy group is grafted onto the polymer backbone or attached to a vinyl group adjacent to the polymer backbone. The SBC may also be an HSBC.

[0028] "Silated styrenic block copolymer" or Si-SBC or silane-grafted SBC or silane-functionalized SBC are used interchangeably. These refer to SBCs in which at least one silane group is grafted onto the polymer backbone or attached to a vinyl group adjacent to the polymer backbone. The SBC may also be an HSBC. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present disclosure relates to a recycled polymer composition comprising: (a) a recycled polymer blend comprising recycled polyamide and recycled synthetic fiber material; (b) at least one block copolymer selected from functionalized HSBC and non-functionalized HSBC; and (c) optional additives. The recycled polymer composition exhibits a balanced combination of mechanical properties and improved melt flow rate compared to a similar composition without the added block copolymer.

[0030] (Recycled polymer blend): The recycled polymer blend contains recycled polyamide and recycled synthetic fiber material in a weight ratio of 1:10 to 10:1, or 1:8 to 8:1, or 1:5 to 5:1, or 1:3 to 3:1.

[0031] In embodiments, the recycled synthetic fiber material comprises one or more polymers selected from the group consisting of polyether-polyurea copolymers, polyether-polyester copolymers, polyester-polyurea copolymers, and polyureas of paraphenylene diisocyanate and paraphenylenediamine.

[0032] In embodiments, the recycled polymer composition comprises the recycled polymer blend in an amount of 80 to 99, or 85 to 99, or 88 to 99, or 90 to 99 weight percent, based on the total weight of the recycled polymer composition.

[0033] (Recycled Polyamide): The recycled polyamide is selected from the group consisting of aliphatic polyamides, aromatic polyamides, copolymers, and mixtures thereof.

[0034] Recycled polyamides are obtained by recycling polyamides or polyamide articles, such as fibers, films, sheets, and molded articles. Polyamides are generally obtained by polymerizing dicarboxylic acids and diamines using conventional methods. Common examples of dicarboxylic acids include adipic acid, sebacic acid, terephthalic acid, azelaic acid, and 1,12-dodecanedioic acid. Suitable diamines include hexamethylenediamine, octamethylenediamine, ethylenediamine, 1,6-diaminohexane, 1,4-diaminobutane, and 1,12-dodecanediamine. Alternatively, polyamides can be derived from suitable monomers such as caprolactam, 11-aminoundecanoic acid, laurolactam, or combinations thereof.

[0035] Examples of recycled polyamides include recycled polyphthalamide (PPA), polyarylamide (PAA), poly(metaxylylene adipamide), amorphous semi-aromatic polyamide, poly(paraphenylene terephthalamide), nylon 6, nylon 11, nylon 12, nylon 6-6, nylon 6-9, nylon 6-10, nylon 6-12, nylon 4-6, nylon 12-12, and mixtures thereof.

[0036] In an embodiment, the recycled polyamide is recycled polyamide 6 (nylon 6).

[0037] (Recycled Synthetic Fiber Material): Recycled synthetic fiber material comprises one or more polymers selected from the group consisting of polyether-polyurea copolymer, polyether-polyester copolymer, polyester-polyurea copolymer, polyurea derived from paraphenylene diisocyanate and paraphenylenediamine, and mixtures thereof, all of which are recycled. As used herein, the terms "fiber" and "fibrous material" are used interchangeably.

[0038] In embodiments, the recycled synthetic fiber material comprises a polyether-polyester copolymer containing both ether and ester units. The polyether-polyester copolymer may be either aliphatic or aromatic in nature. The ether units of the polyether-polyester copolymer are represented by the formula (I): -[CR 1 2] p -O- (wherein p is an integer of 2 to 4, and each R 1 can be represented by: (each independently represents an aliphatic / alicyclic group containing 1 to 30 carbon atoms or an aromatic group having 6 or more carbon atoms). Depending on the integer p (1, 2, or 3), the ether unit can be represented by 4, 6, or 8 R 1 groups, and each R 1 The groups independently represent an organic group having 1 to 20 carbon atoms or hydrogen.

[0039] The ester units of the polyether-polyester copolymer are represented by the formula (ii):-(D) q It can be represented by -C(=O)-O- (wherein q is an integer of 1 to 10, and D represents an aliphatic / alicyclic group containing 2 to 30 carbon atoms or an aromatic group containing 6 or more carbon atoms). In an embodiment, the polyether unit is composed of a polyoxyalkylene block, and the polyester unit includes a polyoxycaproyl block.

[0040] In embodiments, the ether and ester units in the polyether-polyester copolymer are arranged in random order along the polymer chain. As used herein, "random order" means that the ether and ester units are distributed irregularly throughout the copolymer backbone. Alternatively, the polyether-polyester copolymer may be a block copolymer, in which the polyether and polyester segments are arranged in distinct blocks. A representative example of such a block copolymer is polyethylene terephthalate-poly(tetramethylene oxide) glycol.

[0041] In an embodiment, the recycled synthetic fiber material comprises a polyether-polyurea copolymer.

[0042] In embodiments, the recycled synthetic fiber material comprises recycled spandex polymer. Examples of spandex-containing materials include commercially available products such as Acepora, Creora, Dorlastan, Elaspan, INVIYA, Linen, Lycra, ROICA, and Elastane. Spandex polymers are typically produced by reacting a prepolymer, such as one derived from ethylene glycol and a diisocyanate, with a diamine via a chain extension process. The recycled spandex may include polyester-based spandex, polyether-based spandex, or a combination thereof. In embodiments, the recycled spandex is subjected to a bleaching process using a suitable oxidizing agent, such as hydrogen peroxide, to remove dyes or colorants prior to reuse.

[0043] Recycled synthetic fiber materials can be of either industrial or post-consumer origin, including waste materials such as consumer packaging, films, fibers, fabrics, yarns, textiles, scraps, woven fabrics, nonwoven fabrics, and the like.

[0044] In an embodiment, in preparation for recycling, recycled polymers comprising polyamide and / or synthetic fibers are subjected to a mechanical pre-treatment, which serves to remove foreign objects (e.g., clips, fasteners, decorative elements, labels, etc.), dirt and other impurities.

[0045] (Block copolymer): The block copolymer can be selected from the group consisting of functionalized hydrogenated styrenic block copolymers (functionalized HSBC), unfunctionalized hydrogenated styrenic block copolymers (unfunctionalized HSBC), and mixtures thereof. Functionalized HSBC contains at least one functional group selected from the group consisting of maleic anhydride, epoxy, silane, and combinations thereof, while unfunctionalized HSBC does not contain any functional group. Unfunctionalized HSBC may contain coupling agent residues, but if a coupling agent is used, it is used to couple the polymer chains, not to introduce functional groups. Unless otherwise specified, the term "HSBC" refers collectively to both unfunctionalized HSBC and the base polymer used to prepare functionalized HSBC.

[0046] HSBCs can be linear, branched, or radial block copolymers comprising at least one block "S" composed of vinyl aromatic units and at least one rubbery block "R" (block "R") composed of hydrogenated diene units and optionally vinyl aromatic units. The vinyl aromatic units are derived from polymerized vinyl aromatic monomers, and the hydrogenated diene units are derived from polymerized conjugated diene monomers prior to hydrogenation.

[0047] In embodiments, the recycled polymer composition includes an optional styrenic block copolymer (SBC) instead of, or in addition to, the functionalized HSBC and / or the non-functionalized HSBC. The SBC may be selected from unhydrogenated SBC (USBC), partially hydrogenated SBC (pHSBC), and mixtures thereof. In embodiments, the USBC and / or pHSBC may be functionalized with suitable functional groups, such as maleic anhydride, epoxy, and silane.

[0048] In embodiments, HSBC provides SR, SRS, (SR) n X, (SRS) n X, and mixtures thereof, where n is an integer from 2 to 30, and X is the residue of a coupling agent.

[0049] In an embodiment, each block "R" is a block selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB and combinations thereof.

[0050] In embodiments, the block "R" is in the form E / B, composed of ethylene ("E") and butylene ("B") units, which are hydrogenated 1,4-butadiene and hydrogenated 1,2-butadiene units, respectively.

[0051] In embodiments, the block "R" is in the form E / B / S, consisting of ethylene ("E") units, butylene ("B") units, and vinyl aromatic units.

[0052] In an embodiment, the block "R" is in the form of ethylene-propylene (EP) and methylene-butylene (MB) units, each EP unit being a hydrogenated 1,4-isoprene unit and each MB unit being a hydrogenated 3,4-isoprene unit and a hydrogenated 1,2-isoprene unit.

[0053] In embodiments, the block "R" is in the form EP / MB / S, which is composed of EP units, MB units and vinyl aromatic units.

[0054] In embodiments, the block "R" is in the form E / B / EP / MB, which is composed of ethylene ("E"), butylene ("B"), EP and MB units.

[0055] In embodiments, coupling agent X includes a difunctional or polyfunctional compound, such as a halide of an aliphatic or araliphatic hydrocarbon, such as divinylbenzene, 1,2-dibromoethane, or bis(chloromethyl)benzene; a polyfunctional aldehyde, such as silicon tetrachloride, dialkyl- or diaryl silicon dichloride, alkyl- or aryl silicon trichloride, tin tetrachloride, alkyl silicon methoxide, alkyl silicon ethoxide, or terephthalic dialdehyde, a ketone, an ester, anhydride, or an epoxide. In embodiments, the coupling agent is selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, dimethyl adipate, γ-glycidoxypropyltrimethoxysilane, and mixtures thereof. In embodiments, the HSBC has a coupling efficiency (CE) of >60%, or >65%, or >70%, or >75%, or >80%, or <95%.

[0056] In embodiments, the vinyl aromatic monomer is selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrenes, meta-substituted styrenes, α-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0057] In embodiments, the conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, myrcene, farnesene, 1,3-cyclohexadiene, piperylene, and mixtures thereof.

[0058] In embodiments, each block "S" has a hydrogenation level of <30%, or <20%, or <10%, or <5%, based on the total double bonds present in block "S". In embodiments, the diene units in each block "R" have a hydrogenation level of >90%, or >95%, or >98%, or up to 100%, or 80-99%, or 90-98%.

[0059] In embodiments, the HSBC comprises a mixture of at least two block copolymers selected from (i) diblock copolymers, and (ii) multiblock copolymers having more than two blocks (e.g., triblock, tetrablock, pentablock, etc.). In embodiments, based on the total weight of the HSBC, the diblock copolymers comprise 10-50, or 12-40, or 10-35, or >5, or <40 wt. %; and the multiblock copolymers comprise 85-90, or 60-88, or 65-90, or >60, or <95 wt. %.

[0060] In embodiments, the HSBC has a butylene (“B”) unit content of 25-60, or 30-55, or 35-50, or 30-50, or 25-50, or >25, or <60 wt. %, based on the total hydrogenated diene units in the block “R.”

[0061] In embodiments, the HSBC has a vinyl aromatic unit content (VAC) of 8 to 35, or 10 to 35, or 10 to 25, or 5 to 20, or 12 to 45, or 15 to 30, or 5 to 32, or 25 to 35, or >7, or <40 wt. %, based on the total weight of the HSBC.

[0062] In embodiments, each block "S" has a molecular weight (M) of 2 to 25, or 3 to 20, or 4 to 15, or 3 to 10, or 2 to 12, or >2, or <25 kg / mol. p )

[0063] In embodiments, the HSBC has a molecular weight (M) of 40-300, or 50-250, or 60-220, or 40-180, or 65-160, or 80-140, or 100-180, or >50, or <200 kg / mol. p )

[0064] In embodiments, the HSBC has a melt flow rate (MFR) at 230°C under a 5 kg load of 2 to 40, or 3 to 35, or 5 to 30, or 4 to 28, or 10 to 28, or 7 to 20, or 2 to 25, or >4, or <30 g / 10 min, measured according to ASTM D1238.

[0065] In embodiments, the HSBC has the structure SE / BS, where each block "S" is made up of styrene units and the block E / B contains ethylene ("E") and butylene ("B") units.

[0066] Examples of SBC include styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-isoprene (SI), styrene-isoprene-styrene (SIS), styrene-isoprene / butadiene (SI / B), styrene-isoprene / butadiene-styrene (SI / BS), styrene-butadiene / styrene (SB / S), styrene-butadiene / styrene-styrene (SB / SS), styrene-isoprene / styrene (SI / S), styrene-isoprene / styrene-styrene (SI / SS), and combinations thereof. Examples of HSBC include styrene-ethylene / butylene-styrene (SE / BS), styrene-ethylene-propylene / methylene-butylene-styrene (S-EP / MB-S), styrene-ethylene / butylene / ethylene-propylene / methylene-butylene-styrene (SE / B / EP / MB-S), styrene-ethylene / butylene / styrene-styrene (SE / B / SS), styrene-ethylene-propylene / methylene-butylene / styrene-styrene (S-EP / MB / SS), and mixtures thereof.

[0067] In embodiments, the functionalized HSBC includes, instead of or in addition to maleic anhydride, epoxy, and silane, other functional groups selected from the group consisting of amino, phosphino, acrylate, hydroxy, carboxylic acid / salt, sulfonic acid, phosphate, phosphine oxide, phosphoric acid, alkoxide, nitrile, thioether, thiol, silicon or boron containing compounds, fumaric acid, itaconic acid, citraconic acid, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, and combinations thereof.

[0068] In embodiments, HSBC is functionalized with maleic anhydride functional groups to obtain maleated HSBC (HSBC-g-MA). Maleation of HSBC can be carried out in the melt, solution, or solid state, and the process can be carried out in either continuous or batch mode. Various free radical initiators, such as peroxides and azo compounds, can be employed to facilitate the grafting of maleic anhydride. In embodiments, HSBC-g-MA has a grafted maleic anhydride content of >0.5, or <10, or 0.5-10, or 0.5-5, or 0.5-2.5 wt. %, based on the total weight of the maleated HSBC.

[0069] The recycled polymer composition may contain other types of functionalized HSBC instead of or in addition to HSBC-g-MA. Examples include epoxy-functionalized HSBC (e-HSBC), epoxy-functionalized USBC (e-USBC), epoxy-functionalized pHSBC (e-pHSBC), etc. e-HSBC can be prepared by first hydrogenating SBC to a hydrogenation level of at least 97%, followed by epoxidation to introduce epoxy functionality. 1 H NMR can be used to confirm and characterize the structure of functionalized polymers (e-HSBC, e-USBC, e-pHSBC, etc.).

[0070] In embodiments, the e-HSBC has epoxy functionality in an amount of 1 to 40, or 2 to 35, or 3 to 30, or 5 to 25, or 4 to 20 wt %, based on the total weight of the R blocks.

[0071] In embodiments, the e-HSBC has a degree of epoxidation of up to 100%, or from 15 to 99%, or from 10 to 92%, or from 40 to 80%, or from 55 to 95%, or from 60 to 85%, relative to the polymer block susceptible to epoxidation.

[0072] In embodiments, HSBC is functionalized with a silane to obtain silane-functionalized HSBC (Si-HSBC). Examples of silanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, dimethoxymethylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and mixtures thereof.

[0073] In embodiments, the Si-HSBC comprises silane functional groups in an amount of 0.1 to 15, or 0.5 to 12, or 1 to 10, or 1.5 to 8, or 2 to 6 weight percent, based on the total weight of the Si-HSBC.

[0074] In embodiments, the Si-HSBC has a degree of silane functionalization of up to 100%, or from 5 to 95%, or from 10 to 90%, or from 20 to 80%, or from 30 to 75% relative to the polymer block susceptible to silanization.

[0075] In embodiments, the block copolymer comprises a blend of functionalized HSBC and non-functionalized HSBC in a weight ratio of 1:10 to 10:1, or 1:7 to 7:1, or 1:5 to 5:1, or 1:3 to 3:1. In embodiments, the functionalized HSBC is HSBC-g-MA.

[0076] In embodiments, the block copolymer is added in an amount of from 1 to 20, or from 1 to 15, or from 2 to 10, or from 3 to 7 weight percent based on the total weight of the recycled polymer composition, including functionalized HSBC, if present.

[0077] Optional Additives: In embodiments, the recycled polymer composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, UV stabilizers, plasticizers, processing aids, nucleating agents, flame retardants, antistatic agents, colorants, pigments, fillers, reinforcing agents, coupling agents, dispersing aids, and mixtures thereof.

[0078] In embodiments, additives, if used, are in an amount of up to 10 wt.%, or 0.1-10, or 0.5-5, or >0.1, or <10 wt.%, based on the total weight of the recycled polymer composition.

[0079] (Optional Virgin Polymer): In embodiments, the recycled polymer composition further comprises a virgin polymer that is fossil-fuel based, bio-based, or a mixture thereof in an amount of up to 75, or 1-50, or 5-40, or 10-60, or 5-50, or >10, or <70 wt%, based on the total weight of the recycled polymer composition. The virgin polymer can be selected from polyamide, polyether-polyurea copolymer, polyether-polyester copolymer, polyester-polyurea copolymer, polyurea of ​​paraphenylene diisocyanate and paraphenylenediamine, and mixtures thereof.

[0080] Other polymers commonly used in textile manufacturing may be used in place of or alongside polyamides, whether recycled or virgin, including polyester, acrylic (e.g., acrylic fibers), cellulosic fibers, polylactic acid, polyolefins, cotton, wool, and similar materials.

[0081] (Recycled Polymer Composition): The recycled polymer composition comprises, based on the total weight of the composition, (a) 80-99 wt. % of a recycled polymer blend; (b) 1-20 wt. % of a block copolymer; and (c) 0-10 wt. % of at least an additive. The amounts of (a)-(c) are independently selected within the specified ranges such that the sum of all components adds up to 100 wt. %.

[0082] In embodiments, recycled polyamide and recycled synthetic fiber materials are combined with the block copolymer, either as separate components or in a pre-blended form.

[0083] (Preparation of Recycled Polymer Composition): The recycled polymer composition can be prepared using known methods, such as compounding, dry blending, etc. In an embodiment, the composition is prepared by compounding, in which all components are mixed and extruded at an appropriate compounding temperature (e.g., 180-260°C). After extrusion, the material is cooled and pelletized for subsequent use. Compounding can be carried out using conventional equipment, such as single-screw and twin-screw extruders, mixers, etc.

[0084] In embodiments, the recycled polymer composition is compounded at a temperature ranging from 170 to 260°C, or from 180 to 255°C, or from 190 to 250°C, or from 205 to 245°C, or from 210 to 250°C, or from 205 to 245°C.

[0085] Properties of the recycled polymer composition: The recycled polymer composition exhibits improved mechanical properties, desirable rheological behavior, and enhanced processability compared to a corresponding composition that does not contain the block copolymer. The composition also exhibits excellent moldability, for example, in injection molding and extrusion processes, while maintaining excellent mechanical strength.

[0086] In embodiments, fibers obtained from recycled polymer compositions exhibit improved modulus, strength, toughness, and environmental resistance.

[0087] In embodiments, the recycled polymer composition has a melt flow rate (MFR) of >45, or >50, or <70, or 45-70, or 50-65, or 45-65, or 50-70 dg / min, measured according to ISO 1133 at 230°C under a 2.16 kg load.

[0088] In embodiments, the recycled polymer composition has a tensile strength at yield, measured according to ASTM D638, of >25, or <60, or from 25 to 60, or from 28 to 50, or from 25 to 40 MPa.

[0089] In embodiments, the recycled polymer composition has a tensile strength at break, measured according to ASTM D638, of >22, or <50, or from 22 to 50, or from 25 to 45, or from 28 to 40, or from 25 to 35 MPa.

[0090] In an embodiment, the recycled polymer composition has a densitometric value of >4, or <15, or 4 to 15, or 4.2 to 10, or 4.4 to 8, or 4 to 6.5 kJ / m, measured at 25°C according to ISO 180. 2 It has a notched Izod impact strength of

[0091] In embodiments, the recycled polymer composition has an elongation at yield, measured according to ASTM D638, of >3%, or <10%, or from 3 to 10%, or from 4 to 8%, or from 4.5 to 7.5%, or from 4 to 8%.

[0092] In embodiments, the recycled polymer composition has an ultimate elongation, measured according to ASTM D638, of >12%, or <60%, or from 12 to 60%, or from 15 to 55%, or from 17 to 50%, or from 15 to 45%.

[0093] In embodiments, the recycled polymer composition has a tear strength, measured according to ASTM D624C, of ​​>200, or >210, or <350, or 200-350, or 210-330, or 215-310 lb / in.

[0094] (End Uses): The recycled polymer composition can be used to produce molded articles, such as films, sheets, cables, etc., by employing any suitable molding technique, including, for example, extrusion, injection molding, compression molding, etc.

[0095] In embodiments, the recycled polymer composition is utilized to produce fibers, yarns, fabrics, textiles, garments, and related products. In embodiments, a synthetic fiber composition comprises the recycled polymer composition.

[0096] The recycled polymer compositions can also be employed to form fabricated articles such as beverage bottles and molded parts for household products, appliances, civil engineering applications, building materials, and the like.

[0097] Analytical Methods: The presence and amount of recycled polyamide and recycled synthetic fiber materials in recycled polymer compositions can be determined using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) in conjunction with elemental and structural characterization techniques such as NMR and pyrolysis-gas chromatography-mass spectrometry (Py-GC / MS). These methods can be used to confirm the identity of the polyamide structure and fiber-derived copolymers, and to estimate the weight ratio of recycled polyamide to recycled synthetic fiber materials.

[0098] To detect HSBC in a composition, gel permeation chromatography (GPC) coupled with multi-angle light scattering (MALS) can be employed to determine the block architecture. Additionally, FTIR and NMR can be used to determine SRS or (SR) nThe presence of vinyl aromatic units and hydrogenated diene units in HSBC, including structural features such as X configuration, can be confirmed, and the presence of functional groups (e.g., maleic anhydride, epoxy groups, silanes, etc.) can be assessed. The vinyl aromatic unit content (VAC), butylene unit content, and diblock content of HSBC can be further quantified using NMR and spectral deconvolution techniques, optionally supported by solvent extraction and fractionation methods.

[0099] To determine the presence of recycled synthetic fiber materials, samples can be subjected to morphological and thermal analysis to identify fiber-derived polymer components. TGA and DSC can be used to evaluate thermal decomposition profiles and melting transitions characteristic of fiber-forming polymers. The "recycled" nature of the components can be inferred from the absence of manufacturing additives present in virgin fiber grades and changes in molecular weight distribution as determined by GPC.

[0100] The presence of recycled polyamides can be confirmed by evaluating the PDI using GPC, which shows a broader distribution and a shift to lower Mw due to chain scission during prior melt processing. Furthermore, the thermal degradation behavior analyzed by TGA may differ from that of virgin polyamides due to the presence of oxidative degradation products and residual contaminants.

[0101] Mechanical testing of the samples can be performed to measure physical properties according to standard test methods, such as tensile strength at break according to ASTM D638. [Example]

[0102] The following examples are intended to be non-limiting.

[0103] Ingredients used in the examples include: Recycled Polymer Blend-1 is a PIR mixture containing 76 wt% recycled polyamide 6 and 24 wt% polyether-polyurea copolymer.

[0104] HSBC-1 contains 13.3% by weight of VAC, M p 5 block "S", 71% CE, 44% by weight butylene ("B") unit content, M p The block copolymer is an unfunctionalized linear hydrogenated triblock copolymer (SE / BS) with a .DELTA. of 145 kg / mol, a MFR at 230.degree. C. / 5 kg of 22 g / 10 min, and a diblock content of 29 wt.%.

[0105] HSBC-g-MA-1 contains 21.65 wt% VAC, M p The block copolymer has a CE of 6 kg / mol for block "S", a CE of 85%, a butylene ("B") unit content of 41 wt%, and an M of 111 kg / mol. p This is a maleated HSBC (functionalized HSBC) derived from a linear hydrogenated triblock copolymer (SE / BS) with a diblock content of 15 wt% and a MFR of 14 g / 10 min at 230 °C / 5 kg. HSBC-g-MA-1 has a grafted maleic anhydride content of 0.7-2 wt%.

[0106] AO-1 is an antioxidant, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

[0107] Example 1: Preparation of recycled polymer composition. The components of the recycled polymer composition were mixed at room temperature (25°C). The blended mixture was then fed into a feeder and compounded using a twin-screw extruder operating at a temperature range of 200-250°C, and then pelletized. Test specimens were then prepared by injection molding at a temperature range of 220-250°C and compression molding at a temperature of 240°C. C-Ex.1 represents a comparative example.

[0108] [Table 1]

Claims

1. (a) 80-99 wt. % recycled polymer blend consisting of: (a1) recycled polyamide, and (a2) A recycled synthetic fiber material comprising one or more polymers selected from the group consisting of polyether-polyurea copolymers, polyether-polyester copolymers, polyester-polyurea copolymers, and polyureas derived from paraphenylene diisocyanate and paraphenylenediamine; wherein the weight ratio of (a1) to (a2) is 1:10 to 10:1; (b) 1 to 20 wt. % of a block copolymer selected from: (i) a functionalized hydrogenated styrenic block copolymer, and (ii) non-functionalized hydrogenated styrenic block copolymers; wherein each of the block copolymers (i) and (ii) is independently S-R-S, (S-R) ｎ X, (S-R-S) ｎ X, and mixtures thereof; (In the formula, X is a residue of a coupling agent; n is an integer from 2 to 30, each block "S" is composed of vinyl aromatic units, and Each block "R" is composed of hydrogenated diene units, When the block copolymer is a functionalized hydrogenated styrenic block copolymer, the block "R" contains at least one functional group selected from maleic anhydride, epoxy, and silane; When the block copolymer is a non-functionalized hydrogenated styrenic block copolymer, the block copolymer is a vinyl aromatic unit content (VAC) of 8 to 35 wt. %; a butylene (“B”) unit content of 25 to 60% by weight; and Diblock content of 10 to 50% by weight and (C) 0 to 10 wt. % of at least one additive, based on the total weight of the recycled polymer composition; Where: The recycled polymer composition has a tensile strength at break of >22 MPa measured according to ASTM D638; 1. A recycled polymer composition comprising:

2. 10. The recycled polymer composition of claim 1, wherein the block copolymer is a non-functionalized hydrogenated styrenic block copolymer having an S-R-S structure.

3. 10. The recycled polymer composition of claim 1, wherein the block copolymer is a functionalized hydrogenated styrenic block copolymer comprising at least one functional group selected from the group consisting of maleic anhydride, epoxy, and silane.

4. 10. The recycled polymer composition of claim 1, wherein the block copolymer comprises a blend of a functionalized hydrogenated styrenic block copolymer and a non-functionalized hydrogenated styrenic block copolymer in a weight ratio of 1:10 to 10:

1.

5. 5. The recycled polymer composition of any of claims 1 to 4, having a melt flow rate (MFR) of >45 dg / min measured at 230°C under a load of 2.16 kg according to ISO 1133.

6. The recycled polymer composition according to any one of claims 1 to 4, wherein the recycled polyamide is nylon 6.

7. The recycled polymer composition of any one of claims 1 to 4, wherein the recycled synthetic fiber material is a polyether-polyurea copolymer.

8. The block "S" has a molecular weight (M ｐ 5. The recycled polymer composition according to claim 1, wherein the polymer is a hydroxyl group or a hydroxy group.

9. The block copolymer is a vinyl aromatic content (VAC) of 10 to 25 wt. %; and a butylene (“B”) unit content of 35 to 50 wt. % based on the total hydrogenated diene units in block “R”; 10. The recycled polymer composition of claim 1, wherein the polymer is a non-functionalized hydrogenated styrenic block copolymer having the formula:

10. The block copolymer is a butylene (“B”) unit content of 30 to 55% by weight; The molecular weight of the block "S" (M ｐ ); Molecular weight of block copolymer (M ｐ ); a vinyl aromatic unit content (VAC) of 5 to 20 wt. %; and a diblock content of 10 to 35 wt. %; 10. The recycled polymer composition of claim 1, wherein the polymer is a non-functionalized hydrogenated styrenic block copolymer having the formula:

11. 10. The recycled polymer composition of claim 1, wherein the block copolymer is a functionalized hydrogenated styrenic block copolymer, said functionalized hydrogenated styrenic block copolymer being a maleic anhydride grafted hydrogenated styrenic block copolymer.

12. The maleic anhydride-grafted hydrogenated styrenic block copolymer is a triblock copolymer having an SE / BS structure before grafting, wherein: each block S is composed of styrene units, and block E / B is composed of ethylene ("E") and butylene ("B") units; The recycled polymer composition of claim 11.

13. 13. The recycled polymer composition of claim 11 or 12, wherein the maleic anhydride grafted hydrogenated styrenic block copolymer has a grafted maleic anhydride content of >0.5 wt.%, based on the total weight of the maleic anhydride grafted hydrogenated styrenic block copolymer.

14. Both were measured according to ASTM D638. Tensile strength at yield >25 MPa; Tensile strength at break of 22 to 50 MPa; Elongation at yield >3%; and >12% ultimate elongation; The recycled polymer composition according to any one of claims 1 to 4, comprising at least one of the following:

15. A synthetic fiber composition comprising the recycled polymer composition of any one of claims 1 to 4.

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