High-weldability, high-rebound, anti-static thermoplastic polyether ester elastomer material and its preparation method, low-pressure deformation, excellent fatigue resistance and durability, and high-permeability 3D hollow fiber structure

Abstract

The present invention discloses a high-welding, high-rebound, anti-static thermoplastic polyether ester elastomer material and a preparation method thereof, as well as a 3D hollow fiber structure with low pressure deformation, excellent fatigue resistance, durability, and high permeability. The thermoplastic polyether ester elastomer material is prepared from the following components in parts by weight: 100 parts of a thermoplastic polyether ester elastomer, 10 to 30 parts of a polyether alcohol, 0.1 to 0.5 parts of a glycidyl ether curing agent, 0.5 to 1 parts of a two-dimensional carbon / nitrogen / carbonitride material, 0.5 to 1.5 parts of a high-temperature foaming agent, 5 to 15 parts of an elastomer-grafted maleic anhydride, and 1 to 5 parts of a plasticizer; wherein the two-dimensional carbon / nitrogen / carbonitride materials are all modified with polypeptides or dopamine. The present invention first adds a curing agent and a dispersed foaming agent at a relatively low temperature and then performs high-temperature spinning and spraying to micro-foam the material. The obtained thermoplastic polyether ester elastomer and its 3D hollow fiber structure have low compression permanent deformation, bending permanent deformation and dynamic compression fatigue durability, can significantly enhance the rapid rebound response performance, and can completely replace foam sponge, latex, spring beds / cushions and other materials.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer modification, and specifically to a high-welding, high-rebound, anti-static thermoplastic polyether ester elastomer material and a preparation method thereof, and a high-permeability 3D hollow fiber structure with low pressure deformation, excellent fatigue resistance and durability. Background Art

[0002] Thermoplastic polyetherester elastomer (TPEE), also known as polyetherester synthetic rubber, is a copolymeric polymer with physical properties intermediate between those of thermosetting rubber and thermoplastics. It combines the elasticity of rubber with the processability of plastics, and can be recycled and reprocessed without significant loss of performance. Due to its excellent resistance to high and low temperatures, weathering, and chemicals, as well as its thermoplastic-like molding and reusability, polyetherester elastomers are gradually replacing thermosetting rubber materials and are widely used in the automotive industry, rail transportation, household goods, and other fields.

[0003] Everyday seats, backrests, beds, sofas, and other items come into direct contact with the user's body. Safe and comfortable cushioning for seats, backrests, mattresses, and other materials can help reduce physical and mental fatigue and enhance enjoyment. For example, a good seat / backrest can cushion and absorb energy during vehicle deceleration and acceleration, ensuring safety and comfort while driving, which is becoming increasingly important for travelers. Currently, most car seats / backrests use polyurethane foam as a cushioning layer. However, polyurethane foam products experience a stiffness during initial compression, and also suffer from drawbacks such as a lack of breathability, poor resilience after long-term compression, and yellowing with prolonged use. Thermoplastic polyetherester elastomers, due to their excellent physical support, chemical resistance, and anti-yellowing properties, can also be spun into fibers like polyester resins. These materials can be used in various seat cushion cores, mattress cores, and backrests. Compared to polyurethane foam, latex products, and spring / sponge composites, they offer superior support, breathability, and user comfort, effectively overcoming the shortcomings of polyurethane foam and other products. The patent with publication number CN105683434A discloses three non-antistatic network structures: polyester thermoplastic elastomer, ethylene-ethyl acetate copolymer, and polyolefin thermoplastic elastomer. Among them, polyester thermoplastic elastomer is polymerized by DMT and has a relatively high hardness. Although it has good support, its elasticity, ride comfort and touch are deviated, and its long-term durability will inevitably deteriorate. Ethylene-ethyl acetate copolymer and polyolefin thermoplastic elastomer are relatively soft and do not have the gravity support of polyester thermoplastic elastomer, which limits their application range. Summary of the Invention

[0004] In view of this, the present invention provides a high-welding, high-rebound, anti-static thermoplastic polyether ester elastomer material and its preparation method, and a high-permeability 3D hollow fiber structure with low pressure deformation, excellent fatigue resistance and durability, to solve the chronic problems of low adhesion (poor bonding) of the polyether ester thermoplastic elastomer structure fiber body in the above-mentioned background technology, easy generation of static electricity due to fiber friction, and poor durability under high hardness dynamic repeated compression.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] The first aspect of the present invention discloses a high-weldability, high-rebound, antistatic thermoplastic polyetherester elastomer material, which is prepared from the following components in parts by weight:

[0007]

[0008] Among them, the two-dimensional carbon / nitrogen / carbon nitride materials are all surface-modified with one of the peptides and dopamine.

[0009] Further solution: The melting point of the thermoplastic polyether ester elastomer is 140-170° C., and the thermoplastic polyether ester elastomer is a linear or branched thermoplastic polyether ester elastomer.

[0010] Further solution: the polyether alcohol is at least one of polyoxypropylene polyol, diethylene glycol diethyl ether, polyoxytetramethylene polyol, tetrahydrofuran-propylene oxide copolymer glycol, and fatty alcohol polyoxyethylene ether.

[0011] Further solution: the glycidyl ether curing agent is at least one of tetraphenol ethane tetraglycidyl ether, 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether, resorcinol formaldehyde tetraglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, triphenol methane triglycidyl ether, and 1,4-butanediol diglycidyl ether; and / or,

[0012] The two-dimensional carbon / nitrogen / carbon nitride material is at least one of graphene, nitrogen-doped graphyne, nitrogen-sulfur co-doped graphyne oxide and their derivatives; and / or,

[0013] The high-temperature foaming agent is one of an azo compound, a sulfonylhydrazide compound, and a nitroso compound, preferably one of barium azodicarboxylate, p-toluenesulfonylsemicarbazide, 4,4'-oxybis(benzenesulfonylsemicarbazide), trihydrazinotriazine, and 5-phenyltetrazole; and / or has a decomposition temperature of 220-260° C. and a foaming volume of 100-150 ml / g.

[0014] A further solution: the elastomer in the elastomer grafted with maleic anhydride is at least one of ethylene propylene diene monomer rubber, polyolefin elastomer, hydrogenated product of styrene-butadiene-styrene block copolymer, hydrogenated product of styrene-isoprene-styrene block copolymer, and hydrogenated product of styrene-butadiene-isoprene-styrene block copolymer; the grafting rate of the elastomer grafted with maleic anhydride is greater than 0.8%.

[0015] A further solution: the plasticizer is trioctyl trimellitate, tricresyl phosphate, trioctyl phosphate, tetraoctyl pyromellitate, sebacic acid series, adipic acid series polyester, dimethyl cyclohexyl phthalate, polypropylene glycol alkyl phenyl ether, epoxy plasticizers including epoxy soybean oil, epoxidized linseed oil, epoxidized fatty acid monoester, epoxidized tetrahydrophthalate and 4,5-epoxytetrahydrophthalic acid di(2-ethylhexyl) ester, pentaerythritol tetrabenzoate, diethylene glycol dibenzoate alum, resin plasticizer diethylene glycol dibenzoate, triethylene glycol dibenzoate and dipropylene glycol dibenzoate, 1,2-cyclohexanedicarboxylic acid diisononyl ester, sodium lauryl sulfate, sodium allyl sulfonate, potassium alkyl sulfonate, glycerol monostearyl ester, stearyl citrate, and at least one of quaternary ammonium salts;

[0016] And / or, the quaternary ammonium salt is at least one of a diquaternary ammonium salt, a polyquaternary ammonium salt, and a superquaternary ammonium salt.

[0017] The second aspect of the present invention discloses a method for preparing the above-mentioned high-weldability, high-resilience, antistatic thermoplastic polyether ester elastomer material, comprising the following steps:

[0018] S1. Under a constant temperature of 60-100° C. and stirring conditions, a two-dimensional carbon / nitrogen / carbonitride material and a high-temperature foaming agent are successively added to the polyether alcohol to fully react, the temperature is lowered to 5-10° C., and a glycidyl ether curing agent is added to obtain a uniform polyether alcohol mixture;

[0019] S2. Under a nitrogen atmosphere, the dried thermoplastic polyether ester elastomer and the polyether alcohol mixture are added to a reaction kettle and mixed evenly. The temperature is raised to 170-180° C. and vacuumed. The copolymerization reaction is carried out with continuous stirring for 40-120 min. The stirring is stopped and the reaction is continued for 0.5-2 h. Finally, the copolymer is pressurized and extruded into granules in a molten state to obtain a copolymerized thermoplastic polyether ester elastomer.

[0020] S3. Mixing the copolymerized thermoplastic polyether ester elastomer obtained in S2 with the elastomer-grafted maleic anhydride and a plasticizer, discharging the material and granulating the mixture to obtain a high-melting, high-resilience, antistatic thermoplastic polyether ester elastomer material.

[0021] The third aspect of the present invention discloses a method for preparing a 3D hollow fiber structure with low pressure change, excellent fatigue resistance, durability and high permeability, comprising the following steps:

[0022] Under constant temperature, the highly weldable, highly resilient, and antistatic thermoplastic polyetherester elastomer material is extruded through a melt spinning plate into continuous strands. The strands are then directly dropped into cooling water for cooling, causing them to bend and curl. The contacting portions are then welded together to form a 3D hollow fiber structure. The melt spinning temperature is 220-250°C. The nozzles in the melt spinning plate are hollow, with an outer diameter of 0.2-2 mm.

[0023] The fourth aspect of the present invention discloses a high-permeability 3D hollow fiber structure with low pressure change, excellent fatigue resistance and durability, which is obtained by the above-mentioned preparation method.

[0024] The fifth aspect of the present invention discloses the application of the above-mentioned 3D hollow fiber structure, which is used as a cushioning material for seats, cushions, baby carriages, and large children's toys, as well as an impact-absorbing pad for floors and clamping components.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The present invention adopts a micro-crosslinking combined with micro-foaming preparation process, that is, the material is first micro-foamed by cross-linking and dispersing the foaming agent at a relatively low temperature and then spinning at a high temperature. The obtained thermoplastic polyether ester elastomer and its 3D hollow fiber structure have low compression permanent deformation, bending permanent deformation and dynamic compression fatigue durability, which can significantly enhance the rapid rebound response performance and can completely replace foam sponge, latex, spring bed / cushion and other materials;

[0027] (2) The present invention introduces two-dimensional carbon materials into the main chain or side chain through functionalized grafting, which greatly improves the intrinsic conductivity of the thermoplastic polyether ester elastomer and the antistatic properties of the finished product, avoiding the disadvantage of adding a large amount of metal antistatic agents with certain toxicity during traditional melt blending;

[0028] (3) The 3D hollow fiber structure of the hollow monofilament prepared by the present invention has better compression rebound performance than the solid monofilament, has very low compression deformation and good bending deformation rapid recovery, and can be designed according to the human body shape curve and the natural spinal shape curve of the human body. It has high air permeability, fast heat dissipation, anti-mite, dust-proof and antibacterial properties, is durable, easy to clean, non-toxic and harmless, and is healthy and environmentally friendly. DETAILED DESCRIPTION

[0029] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0031] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0032] Polyether alcohol:

[0033] The CAS number of diethylene glycol diethyl ether is 112-36-7, and the manufacturer is Shanghai Chuangsai Technology Co., Ltd.

[0034] The CAS number of polytetramethylene ether glycol is 25190-06-1, and the manufacturer is Shanghai Aladdin Biochemical Technology Co., Ltd.

[0035] The CAS number of fatty alcohol polyoxyethylene ether is 68213-23-0, and it was purchased from Shandong Sanju Chemical Technology Co., Ltd.

[0036] Glycidyl ether curing agent:

[0037] The brand of tetraphenol ethane tetraglycidyl ether is EPON 1031-A-70, which was purchased from Hanson Chemical Company in the United States;

[0038] Pentaerythritol tetraglycidyl ether CAS number is 3126-63-4, purchased from Hubei Xingyan New Material Technology Co., Ltd.

[0039] Glycerol triglycidyl ether (CAS number: 27043-36-3) was purchased from Merck.

[0040] Two-dimensional carbon materials:

[0041] The graphene ethanol slurry is branded as TNAPRGO and manufactured by Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences;

[0042] The brand of nitrogen-sulfur co-doped graphene oxide is Bk20211130001, which has been modified with peptide or dopamine. The manufacturer is Beijing Beike Nano New Materials Technology Co., Ltd.

[0043] High temperature foaming agent:

[0044] The CAS number of p-toluenesulfonyl semicarbazide is 10396-10-8, which was purchased from Beijing Bailingwei Technology Co., Ltd.

[0045] 4,4'-Oxybis(phenylsulfonylamino urea) CAS number is 10195-67-2, purchased from Shanghai Hehuan Chemical Co., Ltd.

[0046] Trihydrazinotriazine CAS number is 10105-42-7, purchased from Hangzhou Hairui Chemical Co., Ltd.

[0047] Elastomer grafted with maleic anhydride:

[0048] The brand of EPDM rubber grafted with maleic anhydride is W1P-2, and the manufacturer is Coase Chemical Co., Ltd.

[0049] The polyolefin elastomer grafted with maleic anhydride is VA1801, and the manufacturer is ExxonMobil Corporation of the United States;

[0050] The brand of SEBS grafted maleic anhydride is FG1901, and the manufacturer is Kraton Corporation of the United States.

[0051] High temperature resistant plasticizer:

[0052] The CAS numbers of trioctyl trimellitate and dioctyl sebacate are 3319-31-1 and 122-62-3 respectively, and the manufacturer is Shandong Shengfan Chemical Co., Ltd.

[0053] The CAS number of diethylene glycol dibenzoate is 120-55-8, and the manufacturer is Shanghai MacLean Biochemical Technology Co., Ltd.

[0054] The CAS number of bis(2-ethylhexyl) 4,5-epoxytetrahydrophthalate is 10138-36-0, and the manufacturer is Shaanxi Xihua Chemical Industry Co., Ltd.

[0055] Low melting point thermoplastic polyether ester elastomer (TPEE) is a homemade material with hardness of 45D and 50D respectively, and is prepared according to the preparation method of Chinese patent CN 113429551 B.

[0056] The preparation steps of low melting point TPEE with a hardness of 50D are as follows (by weight):

[0057] S1. Add 35.6 parts of dimethyl terephthalate, 1.9 parts of dimethyl isophthalate, 29.2 parts of 1,4-butanediol, 0.5 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.2 parts of tetrabutyl titanate, 0.4 parts of alkyl sulfate, and 0.6 parts of trimethylolpropane into a polymerization reactor filled with inert gas, mix well, and perform the first transesterification reaction at a reaction temperature of 200° C. for 60 minutes.

[0058] S2. When the amount of methanol in the polymerization kettle reaches 160% of the total amount of dimethyl terephthalate and dimethyl isophthalate, 16.7 parts of polytetrahydrofuran ether and 16.7 parts of a polymer of a dicarboxylic acid and a diol are added to the polymerization kettle to carry out a second transesterification reaction for 30 minutes;

[0059] S3. The polymerization kettle temperature was raised to 250° C. and vacuumed to conduct a polycondensation reaction for 60 min to obtain a low-melting-point TPEE with a hardness of 50D and a melt mass flow rate of 60.8 g / 10 min at 230° C. and a 2.16 kg weight load (see below for measurement standards).

[0060] The preparation steps of low melting point TPEE with a hardness of 45D are as follows (by weight):

[0061] S1. 33.75 parts of dimethyl terephthalate, 3.75 parts of dimethyl isophthalate, 29.2 parts of 1,4-butanediol, 0.5 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.2 parts of tetrabutyl titanate, 0.4 parts of alkyl sulfate, and 0.6 parts of trimethylolpropane were added to a polymerization kettle filled with inert gas and mixed uniformly to carry out the first transesterification reaction at a reaction temperature of 200° C. for 60 minutes.

[0062] S2. When the amount of methanol in the polymerization kettle reaches 160% of the total amount of dimethyl terephthalate and dimethyl isophthalate, 25 parts of polytetrahydrofuran ether and 8.3 parts of a polymer of a dicarboxylic acid and a diol are added to the polymerization kettle, and a second transesterification reaction is carried out under inert gas protection for 30 minutes;

[0063] S3. The polymerization kettle temperature was raised to 250° C. and vacuumed to conduct a polycondensation reaction for 120 min to obtain a low-melting-point TPEE with a hardness of 45D and a melt mass flow rate of 43.2 g / 10 min measured at 230° C. and a 2.16 kg weight load (see below for measurement standards).

[0064] All materials are commercially available common products.

[0065] It is understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, which make the technical solution of the present invention clearer, and do not mean that the present invention can only adopt the above reagents. The specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0066] Any range described in the present invention includes the end value and any numerical value between the end values and any sub-range formed by the end value or any numerical value between the end values.

[0067] Example 1

[0068] S1. Add 0.5 parts of nitrogen-sulfur co-doped graphene oxide to 10 parts of diethylene glycol diethyl ether at a constant temperature of 80° C., then add 1.5 parts of p-toluenesulfonyl semicarbazide and continue ultrasonic stirring. Then, cool to 5° C., add 0.1 parts of tetraphenol ethane tetraglycidyl ether and stir thoroughly to obtain a uniform diethylene glycol diethyl ether mixture.

[0069] S2. At room temperature, 100 parts of dried low-melting-point TPEE (hardness 50D) and the mixture of diethylene glycol diethyl ether obtained in S1 were added to a polymerization kettle filled with protective gas and mixed evenly. The temperature in the kettle was then raised to 180° C. and vacuumed. The copolymerization reaction was carried out with continuous stirring for 40 minutes (for a duration of 0.5 hours). Finally, the copolymerized TPEE was extruded and granulated under increased pressure in the molten state to obtain copolymerized TPEE.

[0070] S3. The copolymerized TPEE obtained in S2 is mixed with 15 parts of EPDM rubber grafted maleic anhydride and 5 parts of trioctyl trimellitate, and the material is discharged and granulated to obtain a high-melting, high-rebound and antistatic thermoplastic polyether ester elastomer material.

[0071] S4. The thermoplastic polyetherester elastomer prepared in S3 is extruded into continuous strands through a hollow circular fiber hole melt spinning nozzle (10,000 holes) at a temperature of 240°C. The strands are then directly dropped into cooling water for cooling, bending them into rings. The contacting portions are fused together to obtain a 3D hollow fiber structure with hollow circular fiber filaments. The outer diameter of the nozzle holes in the melt spinning nozzle is 0.5 mm.

[0072] Comparative Example 1-1

[0073] The preparation method is different from that in Example 1 except that nitrogen-sulfur co-doped graphene oxide, p-toluenesulfonyl semicarbazide, diethylene glycol diethyl ether, tetraphenolethane tetraglycidyl ether and EPDM rubber grafted maleic anhydride are not introduced.

[0074] Comparative Example 1-2

[0075] The preparation method is different from that of Example 1 in that nitrogen and sulfur co-doped GO and p-toluenesulfonylamino urea are not introduced.

[0076] Comparative Examples 1-3

[0077] The preparation method is different from that of Example 1 in that nitrogen and sulfur co-doped GO and tetraphenolethane tetraglycidyl ether are not introduced.

[0078] Comparative Examples 1-4

[0079] The preparation method is different from that of Example 1 in that nitrogen and sulfur co-doped GO is not introduced.

[0080] Comparative Examples 1-5

[0081] The preparation method is different from that of Example 1 in that p-toluenesulfonyl semicarbazide and tetraphenolethane tetraglycidyl ether are not introduced.

[0082] Example 2

[0083] S1. Add 1 part of nitrogen-sulfur co-doped graphene oxide to 30 parts of polytetramethylene oxide at a constant temperature of 100° C., and ultrasonically stir. Then, add 1 part of 4,4'-oxybis(phenylsulfonylamino urea) and continue ultrasonically stirring. Then, cool to 10° C., add 0.5 part of pentaerythritol tetraglycidyl ether, and stir thoroughly to obtain a uniform polytetramethylene oxide mixture.

[0084] S2, at room temperature, add 100 parts of low melting point TPEE (hardness 45D, homemade) and the polytetrahydrofuran ether glycol mixture obtained in S1 into a polymerization kettle filled with protective gas and mix them evenly, then raise the temperature in the kettle to 170

[0085] C and evacuate, continue to stir and carry out copolymerization reaction for 80min, the time lasts for 1h, and finally pressurize and granulate in the molten state to obtain copolymerized TPEE;

[0086] S3. Mix the copolymerized TPEE obtained in S2 with 5 parts of polyolefin elastomer grafted maleic anhydride and 1 part of dioctyl sebacate, and granulate the mixture to obtain a high-melting, high-resilience, antistatic thermoplastic polyether ester elastomer material.

[0087] S4. The thermoplastic polyetherester elastomer prepared in S3 was extruded into continuous strands through a hollow circular fiber hole melt spinning nozzle (10,000 holes) at a temperature of 240°C. The strands were then directly dropped into cooling water for cooling, bending them into rings. The contacting portions were fused together to obtain a 3D hollow fiber structure with hollow circular fiber filaments. The outer diameter of the nozzle holes in the melt spinning nozzle was 1 mm.

[0088] Comparative Example 2

[0089] The preparation method is different from that of Example 2 in that the thermoplastic polyether ester elastomer material prepared in S3 is prepared using a solid circular fiber hole melt spinning nozzle to prepare a 3D hollow fiber structure.

[0090] Example 3

[0091] S1. Add 0.8 parts of graphene ethanol slurry to 20 parts of fatty alcohol polyoxyethylene ether at a constant temperature of 60°C, and then add 0.5 parts of trihydrazinotriazine and continue ultrasonic stirring. Then, cool to 5°C and add 0.25 parts of glycerol triglycidyl ether at a constant temperature and stir thoroughly to obtain a uniform fatty alcohol polyoxyethylene ether mixture;

[0092] S2. At room temperature, 100 parts of dried low-melting-point TPEE (hardness 50D, homemade) and the fatty alcohol polyoxyethylene ether mixture obtained in S1 were added to a polymerization kettle filled with protective gas and mixed evenly. The temperature in the kettle was then raised to 180° C. and vacuumed. The copolymerization reaction was carried out with continuous stirring for 120 minutes, the reaction time lasting for 2 hours, and finally, pressurized extrusion and granulation were performed in the molten state to obtain copolymerized TPEE.

[0093] S3. The copolymerized TPEE obtained in S2 is mixed with 10 parts of SEBS grafted maleic anhydride and 2.5 parts of 4,5-epoxytetrahydrophthalic acid di(2-ethylhexyl) ester, and the material is discharged and granulated to obtain a high-melting, high-rebound and antistatic thermoplastic polyether ester elastomer material.

[0094] S4. The thermoplastic polyetherester elastomer prepared in S3 is extruded into continuous strands through a hollow circular fiber hole melt spinning nozzle (10,000 holes) at a temperature of 240°C. The strands are then directly dropped into cooling water for cooling, bending them into rings. The contacting portions are fused together to obtain a 3D hollow fiber structure with hollow circular fiber filaments. The outer diameter of the nozzle holes in the melt spinning nozzle is 0.5 mm.

[0095] Comparative Example 3

[0096] The preparation method is different from that of Example 3, except that the thermoplastic polyether ester elastomer material prepared in S3 is prepared by using a hollow circular fiber hole melt spinning nozzle plate with a nozzle outer diameter of 1.5 mm to prepare a 3D hollow fiber structure.

[0097] The performance test standards of the materials obtained in the following examples and comparative examples are as follows:

[0098] Crystallinity (%): GB / T 19466.3-2004.

[0099] β-crystal content (%): DB35 / T 1914-2020.

[0100] Melt flow rate (MFR) (g / 10min): GB / T 3682.1-2018.

[0101] Surface resistivity (Ohm): GB / T 1410.

[0102] Spline bending permanent deformation (%): The prepared thermoplastic polyetherester elastomer material was first injection molded into a 80mm×10mm×1mm standard rectangular spline at the respective spinning temperatures. After being placed at a constant temperature of 70°C for 6 hours, it was immediately bent and clamped on a guide rail clamp (the clamp can be moved on the guide rail to change the bending deformation or length of the spline) and a slot on the base range. The bending deformation was set to 50%. The spline was then placed at a constant temperature of 70°C for 24 hours. The spline was immediately taken out and allowed to stand at room temperature for 30 minutes. The length of the bent spline was measured and calculated based on the length of the spline before and after the test.

[0103] Porosity of 3D hollow fiber structure (cm): The pores in the cross section of the sample are regarded as equilateral circles, and the diameters of as many pores as possible are roughly measured and the average value is taken.

[0104] 70°C Compression Set (%), also known as Compressive Residual Strain: Refer to the method for measuring the 70°C compressive residual strain of 3D hollow fiber structures disclosed in Patent Publication No. CN 105683434 A. This involves repeatedly compressing a cut fiber block (30 cm × 30 cm × 10 cm) at 50% constant displacement at 70°C for 24 hours. The thickness is then measured and the residual strain is calculated based on the change in thickness before and after the test. Residual strain is used here to characterize the rapid rebound performance and compression set of the 3D hollow fiber structure. A smaller residual strain indicates a faster material rebound response.

[0105] Permanent deformation after 50% constant displacement repeated compression (%): Refer to the method for measuring the residual strain of 3D hollow fiber structures under 50% constant displacement repeated compression disclosed in the patent publication number CN 105026632 A, that is, the 3D hollow fiber structure sample with measured thickness is placed in a constant temperature environment of 20±2°C and repeatedly compressed and recovered at a cycle of 1 Hz until it becomes 50% thick. The number of times is set to 80,000 times. After that, the thickness is measured after standing for 24 hours, and the thickness is calculated based on the change in sample thickness before and after the test.

[0106] 750N Constant Stress Repeated Compression Set (%): The residual strain measurement method for 3D hollow fiber structures subjected to 750N constant stress repeated compression was used, as described in Patent Publication No. CN 105683434 A. The thickness of the 3D hollow fiber structure was measured before the experiment. During the experiment, the stress load was set to 750±20N, the compression frequency was set to 70±5 cycles / min, the number of compressions was set to 80,000, and the time the stress reached a maximum value of 750±20N was set to 25% of the time required for repeated compression. After repeated compression, the 3D hollow fiber structure was allowed to rest for 10±0.5 minutes without being stressed, and the thickness was measured. The thickness was calculated based on the change in specimen thickness before and after the test.

[0107] 40% compression hardness (N / φ200mm): The hardness measurement method disclosed in CN 105683434 A is performed by placing a compression plate with a diameter of 200 mm at the center of the sample and compressing the sample to 40% of its thickness.

[0108] Rebound height of falling ball impact (cm): Place a standard 1 kg solid ball 100 cm above the center of the sample block (40 cm × 40 cm × 10 cm) in the air and let it fall freely vertically. Measure the height to which the ball rebounds after hitting the sample block.

[0109] Hysteresis loss (%): The method for measuring the dynamic compression hysteresis loss of a 3D hollow fiber structure sample disclosed in Patent Publication No. CN 105026632 A was used for reference.

[0110] Compression deflection coefficient: The compression deflection coefficient of a 3D hollow fiber structure sample block disclosed in the patent publication number CN 15683434 A was measured.

[0111] Air permeability [cm 3 / (cm 2 s)]:GB / T 24218.15-2018.

[0112] Water absorption (%): Determined according to the standard measurement method of GB / T 18944.1-2003, that is, at room temperature, the 3D hollow fiber structure sample is completely immersed in water for 30 minutes, and the change in its mass after immersion is measured, the sample is removed from the water, and the surface moisture is dried.

[0113] Difficulty of rinsing: The reference foam sponge and the example and comparative example samples (all with dimensions of 40 cm × 40 cm × 10 cm) were completely immersed in an immersion solution prepared by mixing sludge, waste cooking oil, and tap water in a weight ratio of 1:0.8:5 for 30 minutes. After taking them out, they were rinsed with 10 L of tap water and the cleaning status of the samples was observed.

[0114] The products prepared in each embodiment and comparative example were subjected to sample testing. The test samples were prepared and tested according to the standard. The performance parameters are shown in Table 1.

[0115] Table 1

[0116]

[0117]

[0118]

[0119] Note: * The hardness of the same size foam sponge is almost zero when it is compressed by 40% of its thickness; **The same size of foam sponge is hit by a falling ball and the rebound height is almost 0cm; ** The water absorption rate of foam sponges of the same size is generally 80-99%, and the weight increases significantly after absorbing water; the air permeability of foam sponges of the same size under the same conditions is only 8cm 3 / (cm 2 s); **** The foam sponge of the same size is difficult to rinse clean and still retains a lot of mud and oil stains.

[0120] As can be seen from the data in Table 1, by comparing Example 1 with Comparative Examples 1-1, 1-2, 1-3, 1-4 and 1-5, it can be seen that the use of micro-curing of the chemical structure of the curing agent or micro-foaming of the high-temperature foaming agent process can reduce the compression permanent deformation and compression deflection coefficient of the 3D hollow fiber structure prepared by TPEE spinneret molding, improve its dynamic compression durability, and significantly improve the compression rebound performance of the 3D hollow fiber structure, thereby improving the comfort and touch of the seat cushion / backrest and mattress; moreover, the 3D hollow fiber structures prepared in Example 1 and Comparative Examples 1-1, 1-2, 1-3, 1-4 and 1-5 are superior to the foam sponge in 40% compression hardness, ball rebound, air permeability, water absorption and ease of washing, which also shows that the 3D hollow fiber structure has better gravity support, permeability and easy cleaning than the foam sponge; it can also be seen that the micro-curing of the chemical structure of the curing agent and the micro-foaming of the high-temperature foaming agent have a synergistic effect on improving the compression rebound performance of the 3D hollow fiber structure. The curing agent not only chemically solidifies the TPEE structure but also participates in the same process with the elastomer-grafted maleic anhydride. Together, these two components form a thermosetting elastomer microparticle phase through melt shearing, which toughens the TPEE elastomer. Furthermore, the two-dimensional carbon / nitrogen / carbon-nitrogen compound induces the formation of more β crystals within the TPEE crystalline phase, improving the compression rebound and fatigue durability of the TPEE and its 3D hollow fiber structure. Furthermore, the two-dimensional carbon / nitrogen / carbon-nitrogen compound is grafted onto the TPEE molecular chain through surface treatment, where it, together with the polyether alcohol, reduces the surface resistivity and improves the antistatic properties of the TPEE and its 3D hollow fiber structure.

[0121] A comparison of Example 2 and Comparative Example 2 shows that the 3D hollow fiber structure, formed by spinning and spraying the same material, exhibits superior resilience and low-compression set durability compared to solid fibers. This is primarily due to the greater plastic deformation of solid fibers under compression, resulting in greater compression set under the same conditions. Similarly, a comparison of Example 3 and Comparative Example 3 shows that a larger fiber diameter leads to greater compression set, decreased elasticity, and poorer compression fatigue durability for the TPEE and its 3D hollow fiber structure.

[0122] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0123] For the sake of convenience, the melt spinning blower plate described in Examples 1 to 3 only uses circular fiber holes and the melt spinning temperature is only set to 240°C. In fact, the same effect can be achieved by using a melt spinning blower plate with special-shaped fiber holes and other melt spinning temperatures.

[0124] The high-weldability, high-rebound, anti-static thermoplastic polyether ester elastomer material involved in the present invention is used for spinning to prepare 3D hollow fiber structures. It has the characteristics of low pressure deformation, excellent fatigue resistance, durability and high transparency. It can replace foam sponge mattresses, spring mattresses, latex pads, memory foam pads and other materials. It is suitable for use in high-speed rail seat cushion cores, backrest / pillow cores, car interior seats and backrest cushion cores, home mattresses, sofa cushions / backrests, pillows, beach chairs and other fields.

[0125] Although this specification is described according to implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0126] Therefore, the above description is only a preferred embodiment of the present application and is not intended to limit the scope of implementation of the present application; that is, all equivalent modifications made according to the scope of the claims of the present application are within the scope of protection of the claims of the present application.

Claims

1. A high-weldability, high-rebound, antistatic thermoplastic polyetherester elastomer material, characterized in that: It is prepared from the following components in parts by weight: Among them, the two-dimensional carbon / nitrogen / carbon nitride material is graphene, nitrogen-doped graphyne or nitrogen-sulfur co-doped graphyne oxide and its derivatives modified with polypeptide or dopamine surface.

2. The high-weldability, high-resilience, antistatic thermoplastic polyetherester elastomer material according to claim 1, characterized in that: The melting point of the thermoplastic polyether ester elastomer is 140-170°C, and it is a linear or branched thermoplastic polyether ester elastomer.

3. The high-weldability, high-resilience, antistatic thermoplastic polyetherester elastomer material according to claim 1, characterized in that: The polyether alcohol is at least one of polyoxypropylene polyol, diethylene glycol diethyl ether, polyoxytetramethylene polyol, tetrahydrofuran-propylene oxide copolymer glycol, and fatty alcohol polyoxyethylene ether.

4. The high-weldability, high-resilience, antistatic thermoplastic polyetherester elastomer material according to claim 1, characterized in that: The glycidyl ether curing agent is at least one of tetraphenol ethane tetraglycidyl ether, 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether, resorcinol formaldehyde tetraglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, triphenol methane triglycidyl ether, and 1,4-butanediol diglycidyl ether; and / or, The high-temperature foaming agent is one of an azo compound, a sulfonylhydrazine compound, and a nitroso compound; and / or the high-temperature foaming agent is one of barium azodicarboxylate, p-toluenesulfonyl semicarbazide, 4,4'-oxybis(benzenesulfonyl semicarbazide), trihydrazinotriazine, and 5-phenyltetrazole; And / or, the decomposition temperature is 220-260° C., and the foaming amount is 100-150 ml / g.

5. The high-weldability, high-resilience, antistatic thermoplastic polyetherester elastomer material according to claim 1, characterized in that: The elastomer in the elastomer grafted with maleic anhydride is at least one of ethylene propylene diene monomer rubber, polyolefin elastomer, hydrogenated product of styrene-butadiene-styrene block copolymer, hydrogenated product of styrene-isoprene-styrene block copolymer, and hydrogenated product of styrene-butadiene-isoprene-styrene block copolymer; the grafting rate of the elastomer grafted with maleic anhydride is greater than 0.8%.

6. The high-weldability, high-resilience, antistatic thermoplastic polyetherester elastomer material according to claim 1, characterized in that: The plasticizer is trioctyl trimellitate, tricresyl phosphate, trioctyl phosphate, tetraoctyl pyromellitate, sebacic acid series, adipic acid series polyester, dimethyl cyclohexyl phthalate, polypropylene glycol alkyl phenyl ether, epoxy plasticizers including epoxy soybean oil, epoxidized linseed oil, epoxidized fatty acid monoester, epoxidized tetrahydrophthalate and 4,5-epoxytetrahydrophthalic acid di(2-ethylhexyl) ester, pentaerythritol tetrabenzoate, diethylene glycol dibenzoate alum, resin plasticizer diethylene glycol dibenzoate, triethylene glycol dibenzoate and dipropylene glycol dibenzoate, 1,2-cyclohexanedicarboxylic acid diisononyl ester, sodium lauryl sulfate, sodium allyl sulfonate, potassium alkyl sulfonate, glycerol monostearyl ester, citrate stearyl ester, and quaternary ammonium salt; And / or, the quaternary ammonium salt is at least one of a diquaternary ammonium salt, a polyquaternary ammonium salt, and a superquaternary ammonium salt.

7. The method for preparing a high-welding, high-resilience, antistatic thermoplastic polyetherester elastomer material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. Under a constant temperature of 60-100° C. and stirring conditions, a two-dimensional carbon / nitrogen / carbonitride material and a high-temperature foaming agent are successively added to the polyether alcohol to fully react, the temperature is lowered to 5-10° C., and a glycidyl ether curing agent is added to obtain a uniform polyether alcohol mixture; S2. Under a nitrogen atmosphere, the dried thermoplastic polyether ester elastomer and the polyether alcohol mixture are added to a reaction kettle and mixed evenly. The temperature is raised to 170-180° C. and vacuumed. The copolymerization reaction is carried out with continuous stirring for 40-120 min. The stirring is stopped and the reaction is continued for 0.5-2 h. Finally, the copolymer is pressurized and extruded into granules in a molten state to obtain a copolymerized thermoplastic polyether ester elastomer. S3. Mixing the copolymerized thermoplastic polyether ester elastomer obtained in S2 with the elastomer-grafted maleic anhydride and a plasticizer, discharging the material and granulating the mixture to obtain a high-melting, high-resilience, antistatic thermoplastic polyether ester elastomer material.

8. A method for preparing a 3D hollow fiber structure with low pressure change, excellent fatigue resistance and high permeability, characterized in that: The following steps are involved: Under a molten constant temperature state, the high-melting, high-rebound, antistatic thermoplastic polyetherester elastomer material as described in any one of claims 1 to 6 is extruded into continuous lines through a melt spinning nozzle, directly dropped into cooling water for cooling so as to bend and curl, and the contact parts are welded to each other to obtain a 3D hollow fiber structure; wherein, the melt spinning temperature is 220-250°C; the nozzle of the melt spinning nozzle is hollow, and the outer diameter of the hole is 0.2-2 mm.

9. A high-permeability 3D hollow fiber structure with low pressure deformation, excellent fatigue resistance and durability obtained by the preparation method according to claim 8.

10. Use of the 3D hollow fiber structure according to claim 9, characterized in that: Used as cushioning materials for seats, cushions, strollers, large children's toys, as well as impact-absorbing pads for floors and clamping components.

Images