High-performance tpee composite monofilament, preparation method and application thereof

Abstract

The present disclosure relates to the technical field of spinning raw materials, and particularly relates to a high-performance TPEE composite monofilament, a preparation method and application thereof; the TPEE composite monofilament comprises a TPEE core layer and a polymer coating layer; the polymer coating layer comprises a maleic anhydride terpolymer; and the mass ratio of the polymer coating layer and the TPEE core layer is selected from 1:(3-8). The present disclosure prepares a TPEE composite monofilament which has good tensile resistance and flame resistance.

Description

Technical Field

[0001] This disclosure relates to the field of spinning raw material technology, and in particular to a high-performance TPEE composite monofilament, its preparation method, and its application. Background Technology

[0002] Thermoplastic polyester elastomer (TPEE), also known as polyester rubber, is a type of linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segments and aliphatic polyester or polyether soft segments. TPEE combines the excellent elasticity of rubber with the easy processing of thermoplastic plastics. Its hardness can be adjusted, allowing for free design, making it a new and highly anticipated variety of thermoplastic elastomer.

[0003] While existing large-diameter TPEE monofilaments possess a certain tensile strength, they are still easily damaged when stretched at excessive angles. Furthermore, although TPEE material exhibits superior overall performance, it is extremely flammable, with a limiting oxygen index (LOI) of only around 19%, and it drips during combustion. In the event of a fire, these drips can cause flame spread or burns, posing a significant risk. Therefore, improving the flame-retardant properties of TPEE materials is of paramount importance.

[0004] Therefore, we continue to design a new type of TPEE composite monofilament that combines good tensile strength and flame retardancy. Summary of the Invention

[0005] This disclosure provides a high-performance TPEE composite monofilament, its preparation method, and its application, in order to address the shortcomings of related technologies.

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

[0007] In one aspect of this disclosure, the maleic anhydride terpolymer has the structural formula represented by formula IA:

[0008]

[0009] 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.

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

[0011] R2 and R6 are each independently selected from direct bonds, C1-10 alkyl groups, or C1-10 alkoxy groups;

[0012] R8 is selected from C1-10 alkyl, C1-10 alkoxy, C6-C30 aryl, or 5-30 heteroaryl;

[0013] R7 is selected from amino, hydroxy, carboxyl, nitro, cyano, sulfonic acid, or phosphate groups.

[0014] In one aspect of this disclosure, the maleic anhydride terpolymer has the structural formula represented by formula IB:

[0015]

[0016] R1, R3, R4, and R5 are each independently selected from H, C1-5 alkyl, or C1-5 alkoxy.

[0017] R2 and R6 are each independently selected from direct bonds, C1-10 alkyl groups, or C1-10 alkoxy groups;

[0018] R8 is selected from C6-C12 aryl or 5-10 heteroaryl.

[0019] In one aspect of this disclosure, the maleic anhydride terpolymer has the structural formula represented by the following formula IC:

[0020]

[0021] R3 and R5 are each independently selected from H or C1-5 alkyl groups;

[0022] R2 is selected from a direct bond or a C1-5 alkyl group;

[0023] R6 is selected from C1-5 alkyl groups.

[0024] In one aspect of the embodiments of this disclosure, the maleic anhydride terpolymer has the structural formulas represented by formulas D-1 to D-4:

[0025]

[0026]

[0027]

[0028]

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

[0030]

[0031] In one aspect of this disclosure, the maleic anhydride terpolymer is prepared by the following steps:

[0032] Provides maleic anhydride, phenyl compounds having the following II-1 structural formula, and sulfonic acid compounds having the following III-1 structural formula;

[0033]

[0034] 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.

[0035] In one aspect of this disclosure, the maleic anhydride terpolymer is prepared by the following steps:

[0036] Maleic anhydride, benzyl methacrylate or phenyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid are provided; maleic anhydride, benzyl methacrylate or phenyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid 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.

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

[0038] In one aspect of this disclosure, the polymer coating layer further includes a plasticizer and / or a first inorganic filler.

[0039] In one aspect of this disclosure, the TPEE core layer further includes a compatibilizer and / or a second inorganic filler.

[0040] In one aspect of this disclosure, the plasticizer is selected from at least one of epoxy oleate butyl ester, tricresyl phosphate, diphenyl phosphate, dioctyl adipate, and dioctyl sebacate.

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

[0042] In one aspect of this disclosure, the compatibilizer is selected from glycidyl methacrylate-grafted polyolefin elastomer or acrylic acid-grafted polypropylene.

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

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

[0045] Step 1: Preparation of maleic anhydride terpolymer;

[0046] 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.

[0047] 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.

[0048] 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;

[0049] 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.

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

[0051] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects:

[0052] As can be seen from the above embodiments, this disclosure prepares a TPEE composite monofilament that enhances tensile strength and also possesses flame retardant properties.

[0053] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Detailed Implementation

[0054] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0055] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0056] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0057] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0058] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0059] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0060] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, 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%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0061] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

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

[0063] In this disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double 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 a linear alkenyl chain. "Lower alkenyl" refers to a group containing about 2 to about 6 carbon atoms in the chain, which can be straight-chain or branched.

[0064] In this 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. Branching refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkynyl chain. "Lower alkynyl" refers to a chain containing 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 this disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. An aryl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0066] In this disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system, wherein one or more ring atoms are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination, and preferably a heteroaryl contains about 5 to about 6 ring atoms. A "heteroaryl" may optionally be substituted by one or more "cyclic substituents," which may be the same or different, as defined herein. The prefixes azido, oxa, or thiado preceding the name of a heteroaryl root indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The nitrogen atom of a heteroaryl may optionally be oxidized to the corresponding N-oxide. Suitable, non-limiting examples of heteroaryl groups include pyridyl, pyrazinyl, furanyl, phenylthio, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrroleyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-diazanaphthyl, imidazo[1,2-a]pyridyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indoleyl, azaindoleyl, benzimidazolyl, benzothiopheneyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindoleyl, 1,2,4-triazinyl, benzothiazolyl, etc.

[0067] In this disclosure, the term "amino" refers to the -NR′R′′ group. The amino group may optionally be substituted. In an unsubstituted amino group, R′ and R′′ are hydrogen. In a substituted amino group, R′ and R′′ may each independently be, but not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl, or heteroaryl, provided that R′ and R′′ are not both hydrogen. In a substituted amino group, R′ and R′′ may cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups may incorporate other heteroatoms, for example, to form piperazine or morpholine groups. Such cyclic amino groups may optionally be substituted, for example, by an amino, hydroxyl, or oxo group.

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

[0069] In this disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably containing about 5 to about 7 ring atoms. The cycloalkyl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined above. Suitable monocyclic cycloalkyl groups, without limitation, include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Suitable polycyclic cycloalkyl groups, without limitation, include 1-decahydronaphthyl, norcamphenyl, adamantyl, etc. In this disclosure, the term "cycloalkoxy" refers to a group in which one or more carbon atoms in the mono- or polycyclic ring system of the "cycloalkyl" group are substituted with oxygen atoms.

[0070] In this disclosure, the term "heterocyclic group" refers to a non-aromatic saturated monocyclic or polycyclic ring system, wherein one or more ring atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination. Adjacent oxygen and / or sulfur atoms are absent in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefixes aza, oxa, or thioa preceding the name of the heterocyclic group indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The heterocyclic group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclic group may optionally be oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclic rings include piperidinyl, pyrrolyl, piperazine, morpholinyl, thiomorpholinyl, thiazolyl, 1,3-dioxolanecycloyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, etc.

[0071] The present disclosure will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present disclosure are obtained through conventional commercial means. Unless otherwise specified, all contents mentioned below are mass contents. Unless otherwise specified, it is understood that the process was carried out at 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 were provided; wherein the feed ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and phenyl methacrylate was 2:3:5; the raw materials were added to a three-necked flask, and then initiator V50 (the mass of the initiator was 1 / 15 of that of maleic anhydride, and the initiator was dissolved in phenyl methacrylate before being added); nitrogen gas was introduced for protection, and the polymerization reaction was carried out at 70°C for 4 hours; the reactants were removed, washed with ethanol, washed with water, washed with ethanol again, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride terpolymer of Example 1, the reaction process of which is shown below:

[0077]

[0078] 2. Preparation of TPEE composite monofilaments from Example 1:

[0079] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared maleic anhydride terpolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0080] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then, after oiling, stretching and setting (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and setting temperature is 140℃), and winding, the TPEE composite monofilaments of Example 1 are obtained.

[0081] Example 2:

[0082] The steps in Example 2 are the same as those in 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 steps in Example 3 are the same as those in 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 the maleic anhydride terpolymer of Example 4:

[0088] Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and benzyl methacrylate were provided; wherein the feed ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and benzyl methacrylate was 2:3:5; the raw materials were added to a three-necked flask, and then initiator V50 (the mass of the initiator was 1 / 15 of that of maleic anhydride, and the initiator was dissolved in benzyl methacrylate before being added); nitrogen gas was introduced for protection, and the polymerization reaction was carried out at 70°C for 4 hours; the reactants were removed, washed with ethanol, washed with water, washed with ethanol again, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride terpolymer of Example 4, the reaction process of which is shown below:

[0089]

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

[0091] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared maleic anhydride terpolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0092] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then, after oiling, stretching and setting (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and setting temperature is 140℃), and winding, the TPEE composite monofilaments of Example 4 are obtained.

[0093] Example 5:

[0094] The steps in Example 5 are the same as those in 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 in Example 6 are the same as those in 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 maleic anhydride terpolymer of Comparative Example 1:

[0100] Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and styrene are provided; wherein the feed ratio of maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and styrene is 2:3:5; the raw materials are added to a three-necked flask, and then initiator V50 (the mass of the initiator is 1 / 15 of that of maleic anhydride, and the initiator is dissolved in styrene before addition); nitrogen gas is introduced for protection, and the polymerization reaction is carried out at 70°C for 4 hours; the reactants are removed, washed with ethanol, washed with water, washed with ethanol again, 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, the reaction process of which is shown below:

[0101]

[0102] 2. Preparation of TPEE composite monofilaments in Comparative Example 1:

[0103] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared maleic anhydride terpolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0104] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then they are oiled, stretched and shaped (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and shaped temperature is 140℃), and wound into finished products to obtain the TPEE composite monofilaments of Comparative Example 1.

[0105] Comparative Example 2:

[0106] Comparative Example 2 includes the following steps:

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

[0108] Maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid are provided; wherein the feed ratio of maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid is 1:4; the raw materials are added to a three-necked flask, dissolved in anhydrous ethanol, and then initiator V50 (the mass of the initiator is 1 / 15 of that of maleic anhydride, dissolved in anhydrous ethanol and added); nitrogen gas is introduced for protection, and polymerization is carried out at 70°C for 4 hours; the reactants are taken out, washed with ethanol, washed with water, washed with ethanol again, 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 TPEE composite monofilaments in Comparative Example 2:

[0110] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared maleic anhydride binary copolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0111] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then they are oiled, stretched and shaped (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and shaped temperature is 140℃), and wound into finished products to obtain the TPEE composite monofilaments 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-methylpropanesulfonic acid, and phenyl methacrylate are provided; wherein the feed ratio of methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and phenyl methacrylate is 2:3:5; the raw materials are added to a three-necked flask, and then initiator V50 (the mass of the initiator is 1 / 15 of maleic anhydride, and the initiator is dissolved in phenyl methacrylate before addition); nitrogen gas is introduced for protection, and the polymerization reaction is carried out at 70°C for 4 hours; the reactants are removed, washed with ethanol, washed with water, washed with ethanol again, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the acrylic acid terpolymer of Comparative Example 3, the reaction process of which is shown below:

[0116]

[0117] 2. Preparation of TPEE composite monofilaments in Comparative Example 3:

[0118] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared acrylic terpolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0119] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then they are oiled, stretched and shaped (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and shaped temperature is 140℃), and wound into finished products to obtain the TPEE composite monofilaments of Comparative Example 3.

[0120] Comparative Example 4:

[0121] Comparative Example 4 includes the following steps:

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

[0123] Maleic anhydride, N-(2-aminoethyl)acrylamide, and phenyl methacrylate were provided; wherein the feed ratio of maleic anhydride, N-(2-aminoethyl)acrylamide, and phenyl methacrylate was 2:3:5; the raw materials were added to a three-necked flask, and then initiator V50 (the mass of the initiator was 1 / 15 of that of maleic anhydride, and the initiator was dissolved in phenyl methacrylate before being added); nitrogen gas was introduced for protection, and the polymerization reaction was carried out at 70°C for 4 hours; the reactants were removed, washed with ethanol, washed with water, washed with ethanol again, 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 of which is shown below:

[0124]

[0125] 2. Preparation of TPEE composite monofilaments in Comparative Example 4:

[0126] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) are mixed at a mass ratio of 7:93, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the TPEE core layer material into the core cavity of the composite component in the composite spinning box. The plasticizer and the prepared maleic anhydride terpolymer are mixed at a mass ratio of 5:95, and then added to a booster screw extruder. The mixture is fed into a metering pump through melt shearing to meter the polymer coating material into the core cavity of the composite component in the composite spinning box. The amount of polymer coating material fed into the extruder is 1 / 5 of the amount of TPEE core layer material fed into the extruder. The TPEE core material and the polymer coating material are spun simultaneously, and the polymer coating layer coats the TPEE core layer to form a composite monofilament. The screw extruder temperature for treating the polymer coating layer is 175℃; the screw extruder temperature for treating the TPEE core layer is 250℃; and the composite spinning box temperature is 210℃.

[0127] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then they are oiled, stretched and shaped (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3; stretching and shaped temperature is 140℃), and wound into finished products to obtain the TPEE composite monofilaments of Comparative Example 4.

[0128] Comparative Example 5:

[0129] Comparative Example 5 includes the following steps:

[0130] The compatibilizer glycidyl methacrylate grafted polyolefin elastomer (SOG02 POE-g-GMA) and TPEE masterbatch (Hytrel TPEE 40CB) were mixed at a mass ratio of 7:93, and then added to a pressurized screw extruder. The TPEE core layer material was then fed into the core layer cavity of the composite component in the composite spinning box for spinning. Spinning was carried out, with the screw extruder temperature at 250℃ and the composite spinning box temperature at 210℃.

[0131] The composite monofilaments ejected from the spinneret enter a cooling water tank for cooling; then they are oiled, stretched and shaped (stretch ratios are: 4 times for zone 1; 2 times for zone 2; 1.5 times for zone 3, stretching and shaped at a temperature of 140℃), and wound into finished products to obtain the TPEE composite monofilaments of Comparative Example 5.

[0132] Performance testing:

[0133] 1. Flame retardant performance test: Adopted according to the US UL94 test standard;

[0134] 2. Mechanical property testing: ASTM D638-89 standard was adopted, and the tensile speed was selected as 500 mm / min;

[0135] The 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] As can be seen, Examples 1-6 exhibit better mechanical properties compared to Comparative Examples 1-5. This is because the MAH groups in the polymer coating can undergo esterification / amidation reactions with the ester, carboxyl, or hydroxyl groups in the TPEE, forming a covalent bond interface and significantly enhancing the adhesion between the coating and the TPEE core. Furthermore, MAH can also form hydrogen bonds or dipole-dipole interactions with TPEE segments, further improving interface stability (therefore, the mechanical properties of these 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 bonds with the polar segments in the TPEE, further enhancing the mechanical properties. Furthermore, it can be seen that the mechanical properties of Comparative Example 1, which uses styrene instead of benzyl methacrylate / phenyl methacrylate, are still inferior to those of the Examples. This is because (1) the groups of benzyl methacrylate / phenyl methacrylate contain ester groups, which can form hydrogen bonds with TPEE segments; and although the segments of benzyl methacrylate / phenyl methacrylate have rigid aromatic rings, they also have flexibility, which can further crosslink with TPEE segments. 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 this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

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); The maleic anhydride terpolymer was prepared by the following steps: The apparatus provides one of phenyl methacrylate or benzyl methacrylate, maleic anhydride, and 2-acrylamido-2-methylpropanesulfonic acid; wherein the feed ratio of one of phenyl methacrylate or benzyl methacrylate to maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid is 5:2:3; the raw materials are added to a three-necked flask, and then initiator V50 is added; nitrogen gas is introduced for protection, and the polymerization reaction is carried out at 70°C for 4 hours; the reactants are removed, washed with ethanol, washed with water, washed with ethanol again, dried at 60°C, washed with acetone, washed with water, and then dried again at 60°C to obtain the maleic anhydride terpolymer.

2. The high-performance TPEE composite monofilament according to claim 1, 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.

3. The high-performance TPEE composite monofilament according to claim 2, 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.

4. A method for preparing the high-performance TPEE composite monofilament as described in claim 3, 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.

5. The application of the high-performance TPEE composite monofilament according to any one of claims 1-3 in textile materials.

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