High-performance TPEE composite monofilament as well as preparation method and application thereof

Abstract

The invention relates to the technical field of spinning raw materials, in particular to a high-performance TPEE composite monofilament and a preparation method and application thereof. The TPEE composite monofilament comprises a TPEE core layer and a polymer coating layer, the polymer coating layer contains a maleic anhydride terpolymer; and the mass ratio of the polymer coating layer to the TPEE core layer is selected from 1: (3-8). According to the invention, the TPEE composite monofilament with good stretch resistance and flame retardation capability is prepared.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of spinning raw materials, and particularly relates to a high-performance TPEE composite monofilament and a preparation method and application thereof. BACKGROUND

[0002] Thermoplastic polyester elastomer (TPEE) is also called polyester rubber, which is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment. TPEE has excellent elasticity of rubber and easy processability of thermoplastic plastic, and has adjustable softness and design freedom, and is a new variety of thermoplastic elastomer that attracts much attention.

[0003] Although the existing large-diameter TPEE monofilament has certain tensile resistance, it is still easy to be damaged once the stretching angle is too large. In addition, although the TPEE material has superior comprehensive performance, it is extremely easy to burn, and the limiting oxygen index (LOI) is only about 19%, and it will produce dripping when burning. When a fire occurs, dripping can cause flame spread or scalding hazards, so it is very important to improve the flame retardant effect of the TPEE material.

[0004] Therefore, a new TPEE composite monofilament with good tensile resistance and flame retardant capacity is continuously designed. SUMMARY

[0005] The present disclosure provides a high-performance TPEE composite monofilament and a preparation method and application thereof to solve the problems in the related art.

[0006] According to a first aspect of an embodiment of the present disclosure, a high-performance TPEE composite monofilament is provided, the TPEE composite monofilament comprising a TPEE core layer and a polymer cladding layer; the polymer cladding layer comprises a maleic anhydride terpolymer; and the mass ratio of the polymer cladding layer to the TPEE core layer is selected from 1:(3-8).

[0007] In one aspect of an embodiment of the present disclosure, the maleic anhydride terpolymer has a structural formula represented by the following formula I-A:

[0008]

[0009] wherein R1, R3, R4, R5 are each independently selected from H, amino, hydroxyl, carboxyl, nitro, cyano, halogen atom, C1-10 alkyl or C1-10 alkoxy;

[0010] T1, T2 are each independently selected from O, NH or CH2;

[0011] R2, R6 are each independently selected from a direct bond, C1-10 alkyl or C1-10 alkoxy;

[0012] R8is selected from C1-10alkyl, C1-10alkoxy, C6-C30aryl, or 5-30 membered heteroaryl;

[0013] R7is selected from amino, hydroxyl, carboxyl, nitro, cyano, sulfonic acid group, or phosphoric acid group.

[0014] In one aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer has a structural formula represented by the following Formula I-B:

[0015]

[0016] wherein R1, R3, R4, R5are each independently selected from H, C1-5alkyl, or C1-5alkoxy;

[0017] R2, R6are each independently selected from a direct bond, C1-10alkyl, or C1-10alkoxy;

[0018] R8is selected from C6-C12aryl, or 5-10 membered heteroaryl.

[0019] In one aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer has a structural formula represented by the following Formula I-C:

[0020]

[0021] wherein R3, R5are each independently selected from H or C1-5alkyl;

[0022] R2is selected from a direct bond or C1-5alkyl;

[0023] R6is selected from C1-5alkyl.

[0024] In one aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer has a structural formula represented by the following Formula D-1 to D-4:

[0025]

[0026]

[0027]

[0028]

[0029] In an aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer has a structural formula represented by Formula D-4 or Formula D-7:

[0030]

[0031] In an aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer is prepared by the following steps:

[0032] The maleic anhydride, the phenyl compound having the following II-1 structural formula, and the sulfonic acid group compound having the following III-1 structural formula are provided;

[0033]

[0034] The maleic anhydride, the phenyl compound having the following II-1 structural formula, and the sulfonic acid group compound having the following III-1 structural formula are provided;

[0035] In an aspect of the embodiments of the present disclosure, the maleic anhydride terpolymer is prepared by the following steps:

[0036] The maleic anhydride, the phenyl compound having the following II-1 structural formula, and the sulfonic acid group compound having the following III-1 structural formula are provided;

[0037] In an aspect of the embodiments of the present disclosure, the mass ratio of the maleic anhydride, the benzyl methacrylate or phenyl methacrylate, and the 2-acrylamido-2-methylpropanesulfonic acid is selected from 2:3:5.

[0038] In an aspect of the embodiments of the present disclosure, the polymer coating layer further comprises a plasticizing agent and / or a first inorganic filler.

[0039] In an aspect of the embodiments of the present disclosure, the TPEE core layer further comprises a compatibilizing agent and / or a second inorganic filler.

[0040] In an aspect of the embodiments of the present disclosure, the plasticizing agent is selected from at least one of butyl epoxy oleate, cresyl phosphate, cresyldiphenyl phosphate, dioctyl adipate, and dioctyl sebacate.

[0041] In an aspect of the embodiments of the present disclosure, the first inorganic filler is selected from silica nanoparticles, calcium sulfate whiskers, kaolin, zinc oxide nanoparticles, or potassium titanate whiskers.

[0042] In an aspect of the embodiments of the present disclosure, the compatibilizer is selected from glycidyl methacrylate grafted polyolefin elastomer or acrylic acid grafted polypropylene.

[0043] In an aspect of the embodiments of the present disclosure, the second inorganic filler is selected from silica nanoparticles, montmorillonite, chopped basalt fiber, or chopped glass fiber.

[0044] According to a second aspect of the embodiments of the present disclosure, there is provided a method for preparing the aforementioned high-performance TPEE composite monofilament, the method comprising:

[0045] Step 1: preparing a maleic anhydride terpolymer;

[0046] Step 2: mixing at least one of the compatibilizer and the second inorganic filler, and the TPEE, and then adding them into a pressurized screw extruder, proportionally metering the TPEE core layer raw material into the chamber of the composite spinning device through the melt shear feeding metering pump;

[0047] Step 3: mixing at least one of the plasticizer and the first inorganic filler, and the maleic anhydride terpolymer prepared in Step 1, and then adding them into a pressurized screw extruder, proportionally metering the polymer coating layer raw material into the chamber of the composite spinning device through the melt shear feeding metering pump;

[0048] Step 4: simultaneously spinning the TPEE core layer raw material and the polymer coating layer raw material, and forming a composite monofilament by coating the polymer coating layer on the TPEE core layer;

[0049] Step 5: the composite monofilament spun out by the spinneret plate enters a cooling water tank for cooling; and then the product is obtained by oiling, drawing, setting, and winding.

[0050] According to a third aspect of the embodiments of the present disclosure, there is provided an application of the aforementioned high-performance TPEE composite monofilament in textile materials.

[0051] The technical solutions provided by the embodiments of the present disclosure can have the following beneficial effects:

[0052] As can be seen from the above embodiments, the present disclosure prepares a TPEE composite monofilament which has enhanced tensile strength and also has flame retardant capability.

[0053] It should be understood that the foregoing general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. DETAILED DESCRIPTION

[0054] The implementations described in the following exemplary embodiments are not meant to be representative of all implementations consistent with the present disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of the present disclosure as detailed in the appended claims.

[0055] For the purpose of clarity, technical solutions in the present application will be clearly and completely described with embodiments combined below. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of the present application. The embodiments of the present application should not be interpreted as a limitation of the present application.

[0056] For the sake of brevity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with any other lower limit to form a range not explicitly recited, and likewise any upper limit can be combined with any other upper limit to form a range not explicitly recited. Further, each individual disclosed point or singular value can be combined with any other point or singular value to form a range not explicitly recited, either as a lower or upper limit, or in combination with other lower or upper limits.

[0057] In this document, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by "comprises... a" does not, without more constraints, exclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0058] In the description of the document, unless otherwise stated, "above", "below" include the number itself.

[0059] Unless otherwise defined, the terms used in the present disclosure have the meanings commonly understood by those skilled in the art. Unless otherwise stated, the values of each parameter mentioned in the present disclosure can be measured by various measurement methods commonly used in the art (for example, can be tested according to the method given in the embodiments of the present disclosure).

[0060] The term "about" is used to describe and account for small variations. When used in connection with a quantity, the term can refer to a range of variation less than or equal to ±10% of that quantity, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%, for example. Additionally, quantities, ratios and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be taken as a literal disclosure of all individual values and subranges falling within the range. Any numerical value, however, can inherently contain undesirable tolerances.

[0061] A list of items joined by "at least one of" or "one or more of" can mean any combination of the listed terms. For example, if a list of items includes A, B, and C, then "at least one of A, B, and C" or "one or more of A, B, and C" can mean A alone; B alone; C alone; A and B together; A and C together; B and C together; or A, B, and C together. An item can be included in a list of items even if the item is not specifically listed. A list of items can be limited to only those items specifically listed. A list of items can be limited to only those items specifically listed, even if other items are listed in association with the list. A list of items can be limited to only those items specifically listed, even if other items are listed in association with the list.

[0062] In the present disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group that can be straight-chain or branched. Branched is meant to indicate one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to the linear alkyl chain. "Lower alkyl" refers to a group having from about 1 to about 6 carbon atoms in the chain, which can be straight or branched.

[0063] In the present disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group that contains at least one carbon-carbon double bond, which can be straight-chain or branched. Branched is meant to indicate one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to the linear alkenyl chain. "Lower alkenyl" refers to a group having from about 2 to about 6 carbon atoms in the chain, which can be straight or branched.

[0064] In the present disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to the linear alkynyl chain. "Lower alkynyl" refers to an alkynyl group containing from about 2 to about 6 carbon atoms, which can be straight-chain or branched. Non-limiting examples of alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl.

[0065] In the present disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. The aryl group can be optionally substituted with one or more "ring system substituents," which can be the same or different, as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0066] In the present disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system in which one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen, or sulfur, alone or in combination. Preferred heteroaryls contain from about 5 to about 6 ring atoms. The "heteroaryl" group can be optionally substituted with one or more "ring system substituents," which can be the same or different, as defined herein. The prefix naphtho-, oxazepin-, thiazepin-, or oxazocin- before a heteroaryl group name indicates the presence of at least one nitrogen, oxygen, or sulfur atom, respectively, as a ring atom. The nitrogen atom of a heteroaryl group can optionally be oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl groups include pyridyl, pyrazinyl, furanyl, thiophenyl, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[l,2-a]pyridyl, imidazo[2,l-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothiophenyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindolyl, 1,2,4-triazinyl, benzothiazolyl, and the like.

[0067] In the present disclosure, the term "amino" refers to a -NR'R" group. The amino group can optionally be substituted. In an unsubstituted amino group, R' and R" are hydrogen. In a substituted amino group, R' and R" can each independently be, but are not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkylcarbonyl, aryl, arylalkyl, or heteroaryl, provided that R' and R" are not both hydrogen. In a substituted amino group, R' and R" can cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups can incorporate additional heteroatoms, such as to form a piperazinyl or morpholinyl group. Such cyclic amino groups can optionally be substituted, such as with amino, hydroxy, or oxo.

[0068] In the present disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to linear, branched, or cyclic, saturated or unsaturated oxy-hydrocarbon chains, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, and pentoxy. Alkoxy can be optionally substituted with one or more alkoxy substituents ("substituted alkoxy").

[0069] In the present disclosure, the term "cycloalkyl" refers to non-aromatic mono- or polycyclic ring systems, with preferred cycloalkyl rings containing from about 5 to about 7 ring atoms. Cycloalkyl can be optionally substituted with one or more "ring system substituents," which can be the same or different, as defined above. Non-limiting examples of suitable monocyclic cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Non-limiting examples of suitable polycyclic cycloalkyl groups include 1-decalinyl, norbornyl, adamantyl, and the like. In the present disclosure, the term "cycloalkoxy" refers to a group in which one or more of the carbon atoms of a mono- or polycyclic ring system of "cycloalkyl" is replaced with an oxygen atom.

[0070] In the present disclosure, the term "heterocyclyl" refers to a non-aromatic saturated monocyclic or polycyclic ring system in which one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen, or sulfur, alone or in combination. There are no adjacent oxygen and / or sulfur atoms in the ring system, with preferred heterocycles containing from about 5 to about 6 ring atoms. The prefix n-, o-, or s- before a heterocyclyl group name indicates the presence of at least one nitrogen, oxygen, or sulfur atom, respectively, as a ring atom. Heterocyclyl can be optionally substituted with one or more "ring system substituents," which can be the same or different, as defined herein. The nitrogen or sulfur atom of a heterocyclyl group can be optionally oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, and the like.

[0071] The present disclosure is further illustrated in the following non-limiting examples. The various chemical reagents used in the examples of the present disclosure are obtained from common commercial sources unless otherwise specified. The amounts described below are mass amounts unless otherwise specified. Room temperature is understood to mean, unless otherwise specified, room temperature.

[0072] Examples and Comparative Examples:

[0073] Example 1:

[0074] Example 1 includes the following steps:

[0075] 1. Preparation of the maleic anhydride terpolymer of Example 1:

[0076] Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and phenyl methacrylate are provided; the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and phenyl methacrylate is 2:3:5; the raw materials are put into a three-necked flask, then an initiator V50 (the mass of the initiator is 1 / 15 of the mass of maleic anhydride, the initiator is dissolved in phenyl methacrylate and added) is added; nitrogen is introduced for protection, and polymerization is carried out at 70℃ for 4h; the reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60℃, then washed with acetone, washed with water, and dried at 60℃ again, to obtain the maleic anhydride terpolymer of example 1, and the reaction process is as follows:

[0077]

[0078] 2. Preparation of the TPEE composite monofilament of example 1:

[0079] The compatible agent glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed according to a mass ratio of 7:93, then added into a pressurized screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing of the pressurized screw extruder; the plasticizer and the prepared maleic anhydride terpolymer are mixed according to a mass ratio of 5:95, then added into a pressurized screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing of the pressurized screw extruder, wherein the amount of the polymer coating layer raw material sent is 1 / 5 of the amount of the TPEE core layer raw material sent. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite monofilament; wherein the screw extruder temperature for processing the polymer coating layer is 175℃; the screw extruder temperature for processing the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0080] The composite monofilament sprayed by the spinneret enters a cooling water tank for cooling; then is oiled, drawn and set (the draw ratio is respectively 4 times in zone 1, 2 times in zone 2, and 1.5 times in zone 3; the draw setting temperature is 140℃), and wound into a product, to obtain the TPEE composite monofilament of example 1.

[0081] Example 2:

[0082] The steps of example 2 are the same as those of example 1, except that in example 2, the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and phenyl methacrylate is 3:5:5.

[0083] Example 3:

[0084] The procedure of Example 3 is the same as that of Example 1, except that in Example 3, the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and phenyl methacrylate is 1:2:5.

[0085] Example 4:

[0086] Example 4 includes the following steps:

[0087] 1. Preparation of maleic anhydride terpolymer of Example 4:

[0088] Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and benzyl methacrylate are provided; wherein the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and benzyl methacrylate is 2:3:5; the raw materials are put into a three-necked flask, then an initiator V50 (the mass of the initiator is 1 / 15 of the mass of maleic anhydride, the initiator is dissolved in benzyl methacrylate and added) is added; nitrogen is introduced for protection, and polymerization is carried out at 70°C for 4h; the reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60°C, then washed with acetone and water, and dried again at 60°C to obtain the maleic anhydride terpolymer of Example 4, and the reaction process is as shown below:

[0089]

[0090] 2. Preparation of TPEE composite monofilament of Example 4:

[0091] The compatible agent glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed according to a mass ratio of 7:93, then added into a pressurized screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box according to the proportioning of the melt shearing feeding metering pump; the plasticizer and the prepared maleic anhydride terpolymer are mixed according to a mass ratio of 5:95, then added into a pressurized screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box according to the proportioning of the melt shearing feeding metering pump, wherein the amount of the polymer coating layer raw material sent is 1 / 5 of the amount of the TPEE core layer raw material sent. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite monofilament; wherein the screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0092] The composite filaments sprayed from the spinneret enter a cooling water tank for cooling; then, after oiling, drawing and setting (the drawing ratio is 4 times in Zone 1, 2 times in Zone 2, and 1.5 times in Zone 3; the drawing and setting temperature is 140°C), the product is wound to obtain the TPEE composite filaments of Example 4.

[0093] Example 5:

[0094] The steps of Example 5 are the same as those of Example 4, except that in Example 5, the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and benzyl methacrylate is 3:5:5.

[0095] Example 6:

[0096] The steps of Example 6 are the same as those of Example 1, except that in Example 6, the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and benzyl methacrylate is 1:2:5.

[0097] Comparative Example 1:

[0098] Comparative Example 1 includes the following steps:

[0099] 1. Preparation of the maleic anhydride terpolymer of Comparative Example 1:

[0100] Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and styrene are provided; the feeding ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and styrene is 2:3:5; the raw materials are put into a three-necked flask, then an initiator V50 (the mass of the initiator is 1 / 15 of the mass of maleic anhydride, and the initiator is dissolved in styrene and added) is added; nitrogen is introduced for protection, and polymerization is carried out at 70°C for 4h; the reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride terpolymer of Comparative Example 1, and the reaction process is as shown below:

[0101]

[0102] 2. Preparation of the TPEE composite filaments of Comparative Example 1:

[0103] The compatible agent glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed in a mass ratio of 7:93, and then added to a pressure screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The plasticizer and the prepared maleic anhydride terpolymer are mixed in a mass ratio of 5:95, and then added to a pressure screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The feeding amount of the polymer coating layer raw material is 1 / 5 of the feeding amount of the TPEE core layer raw material. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite filament. The screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0104] The composite filament sprayed from the spinneret enters a cooling water tank for cooling; then is oiled, drawn and set (the draw ratio is 4 times in zone 1, 2 times in zone 2, and 1.5 times in zone 3; the draw setting temperature is 140°C), and wound into a finished product to obtain the TPEE composite filament of Comparative Example 1.

[0105] Comparative Example 2:

[0106] Comparative Example 2 includes the following steps:

[0107] 1. Preparation of the maleic anhydride binary copolymer of Comparative Example 2:

[0108] Maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid are provided; the feeding ratio of maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid is 1:4; the raw materials are put into a three-necked flask, dissolved in anhydrous ethanol, and then an initiator V50 (the mass of the initiator is 1 / 15 of the mass of maleic anhydride, and the initiator is dissolved in anhydrous ethanol and added) is added; nitrogen is introduced for protection, and the polymerization reaction is carried out at 70°C for 4h; the reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride binary copolymer of Comparative Example 2.

[0109] 2. Preparation of the TPEE composite filament of Comparative Example 2:

[0110] The compatible agent glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed in a mass ratio of 7:93, and then added to a pressure screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The plasticizer and the prepared maleic anhydride copolymer are mixed in a mass ratio of 5:95, and then added to a pressure screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The amount of the polymer coating layer raw material is 1 / 5 of the amount of the TPEE core layer raw material. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0111] The composite monofilament discharged from the spinneret enters a cooling water tank for cooling; then is oiled, drawn and set (the draw ratio is 4 times in zone 1, 2 times in zone 2, and 1.5 times in zone 3; the draw setting temperature is 140°C), and wound into a finished product to obtain the TPEE composite monofilament of Comparative Example 2.

[0112] Comparative Example 3:

[0113] Comparative Example 3 includes the following steps:

[0114] 1. Preparation of the acrylic terpolymer of Comparative Example 3:

[0115] Methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, and phenyl methacrylate are provided; the feeding ratio of the methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, and phenyl methacrylate is 2:3:5; the raw materials are put into a three-necked flask, and then an initiator V50 (the mass of the initiator is 1 / 15 of the maleic anhydride, and the initiator is dissolved in phenyl methacrylate and added) is added; nitrogen is introduced for protection, and the polymerization reaction is carried out at 70°C for 4h; the reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the acrylic terpolymer of Comparative Example 3. The reaction process is as follows:

[0116]

[0117] 2. Preparation of the TPEE composite monofilament of Comparative Example 3:

[0118] The compatible agent glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed in a mass ratio of 7:93, and then added to a pressure screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The plasticizer and the prepared acrylic acid terpolymer are mixed in a mass ratio of 5:95, and then added to a pressure screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The feeding amount of the polymer coating layer raw material is 1 / 5 of the feeding amount of the TPEE core layer raw material. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite filament. The screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0119] The composite filament sprayed from the spinneret enters a cooling water tank for cooling, and then is oiled, drawn and set (the draw ratio is 4:2:1.5 in the first, second and third zones, respectively), and the drawn and set product is wound to obtain the TPEE composite filament of Comparative Example 3.

[0120] Comparative Example 4:

[0121] Comparative Example 4 includes the following steps:

[0122] 1. Preparation of the maleic anhydride terpolymer of Comparative Example 4:

[0123] Maleic anhydride, N-(2-aminoethyl) acrylamide and phenyl methacrylate are provided, and the feeding ratio of maleic anhydride, N-(2-aminoethyl) acrylamide and phenyl methacrylate is 2:3:5. The raw materials are put into a three-necked flask, and then an initiator V50 (the mass of the initiator is 1 / 15 of the mass of maleic anhydride, and the initiator is dissolved in phenyl methacrylate and added) is added. Nitrogen is introduced for protection, and the polymerization reaction is carried out at 70°C for 4h. The reaction product is taken out, washed with ethanol, washed with water, washed with ethanol, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride terpolymer of Comparative Example 4. The reaction process is as follows:

[0124]

[0125] 2. Preparation of the TPEE composite filament of Comparative Example 4:

[0126] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed in a mass ratio of 7:93, and then added to a pressure screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The plasticizer and the prepared maleic anhydride terpolymer are mixed in a mass ratio of 5:95, and then added to a pressure screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The feeding amount of the polymer coating layer raw material is 1 / 5 of the feeding amount of the TPEE core layer raw material. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0127] The composite monofilament sprayed from the spinneret enters a cooling water tank for cooling, and then is oiled, drawn and set (the draw ratio is 4 times in zone 1, 2 times in zone 2, and 1.5 times in zone 3, and the draw setting temperature is 140°C), and wound into a finished product to obtain the TPEE composite monofilament of Comparative Example 4.

[0128] Comparative Example 5 includes the following steps:

[0129] Comparative Example 5 includes the following steps:

[0130] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and the TPEE masterbatch (Hytrel TPEE 40CB) are mixed in a mass ratio of 7:93, and then added to a pressure screw extruder, and the TPEE core layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The plasticizer and the prepared maleic anhydride terpolymer are mixed in a mass ratio of 5:95, and then added to a pressure screw extruder, and the polymer coating layer raw material is sent into the core layer cavity of the composite assembly in the composite spinning box through the proportioning of the melt shearing feeding pump. The feeding amount of the polymer coating layer raw material is 1 / 5 of the feeding amount of the TPEE core layer raw material. The TPEE core layer raw material and the polymer coating layer raw material are spun at the same time, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for processing the polymer coating layer is 175°C; the screw extruder temperature for processing the TPEE core layer is 250°C; and the composite spinning box temperature is 210°C.

[0131] The composite monofilament sprayed from the spinneret enters a cooling water tank for cooling, and then is oiled, drawn and set (the draw ratio is 4 times in zone 1, 2 times in zone 2, and 1.5 times in zone 3, and the draw setting temperature is 140°C), and wound into a finished product to obtain the TPEE composite monofilament of Comparative Example 4.

[0132] Performance test:

[0133] 1. Flame retardant performance test: American UL94 test standard is adopted;

[0134] 2. Mechanical property test: ASTM D638-89 standard is adopted, and the drawing speed is selected as 500nn / min;

[0135] The above test results are shown in Table 1 below:

[0136] Table 1

[0137] Example Elongation at break (%) Tensile strength (MPa) Flame retardant rating UL94 Example 1 634 29.8 V-1 Example 2 615 29.0 V-1 Example 3 587 27.6 V-1 Example 4 647 30.5 V-1 Example 5 627 29.7 V-1 Example 6 590 27.3 V-1 Comparative Example 1 581 27.2 V-1 Comparative Example 2 554 25.3 V-1 Comparative Example 3 567 25.7 V-1 Comparative Example 4 620 29.5 V-2 Comparative Example 5 502 18.1 HB

[0138] It can be seen that, compared with Comparative Examples 1-5, all of the Examples 1-6 have better mechanical properties; this is because the MAH groups in the polymer coating layer can esterify / amidate with the ester groups, carboxyl groups or hydroxyl groups in the TPEE, forming a covalently bonded interface, significantly enhancing the adhesion of the coating layer to the TPEE core layer; in addition, MAH can also form hydrogen bonds or dipole-dipole interactions with the TPEE segments, further improving the interface stability (therefore, the mechanical properties of the Examples are significantly better than those of Comparative Example 3 which uses acrylic acid instead of maleic anhydride); in addition, the sulfonic acid groups in the polymer structure have strong polarity and ionicity, and can form ionic-dipole or hydrogen bond interactions with the polar segments in the TPEE; further enhancing the mechanical properties. And it can be seen that, compared with Comparative Example 1 which uses styrene instead of benzyl methacrylate / phenyl methacrylate, the mechanical properties of the Examples are still better; this is because (1) the benzyl methacrylate / phenyl methacrylate group contains an ester group, which can form a hydrogen bond with the TPEE segment; and, although the benzyl methacrylate / phenyl methacrylate segment has a rigid aromatic ring, it also has flexibility, which can further crosslink with the TPEE segment. In addition, the sulfonic acid groups in the polymer coating layer have flame retardancy, and their flame retardant effect is better than that of Comparative Example 4 (Comparative Example 4 uses N-(2-aminoethyl) acrylamide instead of 2-acrylamido-2-methylpropanesulfonic acid).

[0139] Other embodiments of the present disclosure will be apparent to those skilled in the art with the consideration of the specification and practice of the disclosure disclosed herein. The present disclosure is intended to cover any and all variations of the present disclosure which follow, in general, the principles of the present disclosure and include typical errors inherent to the art or experimental results which are apparent to those skilled in the art.

Claims

1. A high-performance TPEE composite monofilament, characterized in that, The TPEE composite monofilament comprises a TPEE core layer and a polymer coating layer; the polymer coating layer contains a maleic anhydride terpolymer; and... The mass ratio of the polymer coating layer to the TPEE core layer is selected from 1:(3-8).

2. The high-performance TPEE composite monofilament according to claim 1, characterized in that, The maleic anhydride terpolymer has the following structural formula represented by formula IA: Among them, R1, R3, R4, and R5 are each independently selected from H, amino, hydroxyl, carboxyl, nitro, cyano, halogen atom, C1-10 alkyl or C1-10 alkoxy. T1 and T2 are each independently selected from O, NH or CH2; R2 and R6 are each independently selected from direct bonds, C1-10 alkyl groups, or C1-10 alkoxy groups; R8 is selected from C1-10 alkyl, C1-10 alkoxy, C6-C30 aryl, or 5-30 heteroaryl; R7 is selected from amino, hydroxy, carboxyl, nitro, cyano, sulfonic acid, or phosphate groups.

3. The high-performance TPEE composite monofilament according to claim 2, characterized in that, The maleic anhydride terpolymer has the following structural formula represented by formula IB: Among them, R1, R3, R4, and R5 are each independently selected from H, C1-5 alkyl, or C1-5 alkoxy. R2 and R6 are each independently selected from direct bonds, C1-10 alkyl groups, or C1-10 alkoxy groups; R8 is selected from C6-C12 aryl or 5-10 heteroaryl.

4. The high-performance TPEE composite monofilament according to claim 3, characterized in that, The maleic anhydride terpolymer has the following structural formula represented by IC: R3 and R5 are each independently selected from H or C1-5 alkyl groups; R2 is selected from a direct bond or a C1-5 alkyl group; R6 is selected from C1-5 alkyl groups.

5. The high-performance TPEE composite monofilament according to claim 4, characterized in that, The maleic anhydride terpolymer has the following structural formulas represented by formulas D-1 to D-8: 。 6. The high-performance TPEE composite monofilament according to claim 4 or 5, characterized in that, The maleic anhydride terpolymer was prepared by the following steps: Provides maleic anhydride, phenyl compounds having the following II-1 structural formula, and sulfonic acid compounds having the following III-1 structural formula; The maleic anhydride, a phenyl compound having the following II-1 structural formula, and a sulfonic acid compound having the following III-1 structural formula are added to a reaction vessel, and then an initiator is added. Under nitrogen protection, a polymerization reaction is carried out at 60°C-75°C to obtain the maleic anhydride terpolymer.

7. The high-performance TPEE composite monofilament according to any one of claims 1-5, characterized in that, The polymer coating layer also includes a plasticizer and / or a first inorganic filler; The TPEE core layer also includes a compatibilizer and / or a second inorganic filler.

8. The high-performance TPEE composite monofilament according to claim 7, characterized in that, At least one of the following conditions must be met: (1) The plasticizer is selected from at least one of epoxy oleate butyl ester, tricresyl phosphate, diphenyl phosphate, dioctyl adipate and dioctyl sebacate; (2) The first inorganic filler is selected from silica nanoparticles, calcium sulfate whiskers, kaolin, zinc oxide nanoparticles or potassium titanate whiskers; (3) The compatibilizer is selected from glycidyl methacrylate-grafted polyolefin elastomer or acrylic acid-grafted polypropylene; (4) The second inorganic filler is selected from silica nanoparticles, montmorillonite, chopped basalt fibers or chopped glass fibers.

9. A method for preparing the high-performance TPEE composite monofilament according to any one of claims 1-8, characterized in that, The method includes: Step 1: Preparation of maleic anhydride terpolymer; Step 2: Mix at least one of the compatibilizer and the second inorganic filler, and TPEE, and then add it to the pressurized screw extruder. The TPEE core material is fed into the chamber of the composite spinning device by the melt shear of the extruder and metered proportionally by the metering pump. Step 3: Mix at least one of the plasticizer and the first inorganic filler, and the maleic anhydride terpolymer prepared in Step 1, and then add it to the pressurized screw extruder. The extruder melts and shears the mixture into the metering pump to meter it in proportion, and then feeds the polymer coating material into the chamber of the composite spinning device. Step 4: Simultaneously spin the TPEE core layer material and the polymer coating layer material, and the polymer coating layer coats the TPEE core layer to form a composite monofilament; Step 5: The composite monofilaments ejected from the spinneret enter the cooling water tank for cooling; then, after oiling, stretching and shaping, and winding into finished products, the high-performance TPEE composite monofilaments are obtained.

10. The application of the high-performance TPEE composite monofilament according to any one of claims 1-8 in textile materials.

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