Air fiber mat not prone to deformation and preparation method thereof

Abstract

The invention relates to the field of air fiber materials, in particular to a non-deformable air fiber mat and a preparation method thereof.The non-deformable air fiber mat is prepared from, by weight, 60-80 parts of high-melting-point and high-strength TPEE, 5-10 parts of micro-crosslinking agent, 10-20 parts of filler, 0.05-0.2 part of initiator and 0.05-0.2 part of metal catalyst. The air fiber mat not easy to deform prepared by the invention has excellent mechanical properties and transparency and is not easy to deform.

Description

Technical Field

[0001] The invention relates to the field of air fiber materials, and in particular to an air fiber mat that is not easily deformed and a preparation method thereof. Background Art

[0002] Common mattress or seat cushion materials mainly include sponge, spring and latex. Sponge pads have poor rebound performance and are prone to dents; although spring pads have strong support, they are not soft enough and are easily damaged after long-term use, and the surface becomes uneven; latex pads are more expensive and may cause allergic reactions. Polymer fiber pads have strong support and good air permeability. They are not easy to breed bacteria and are easy to clean. They combine the elasticity of spring pads and the comfort of latex pads. However, polymer fiber pads often collapse over a large area during use, and the support hardness and rebound performance are significantly reduced, thereby shortening their service life. Studies have found that the connection points between fiber filaments are the main stress points. Therefore, increasing the number and strength of the connection points is the key to manufacturing polymer fiber pads that are not easily deformed.

[0003] Patent CN116219641A discloses a high fatigue resistance air fiber mat and its preparation method, the high fatigue resistance air fiber mat comprises thermoplastic elastomer resin, polyolefin resin, crosslinking agent, initiator, catalyst, antioxidant, and processing aid; the thermoplastic elastomer resin, polyolefin resin, crosslinking agent, initiator, catalyst, antioxidant, and processing aid are added to an extruder, melted to form a fluid, extruded through a die head to form fiber filaments, when the fiber filaments fall to the water surface, they are entangled and bonded to each other due to the buoyancy, and are water-cooled and shaped to obtain a high fatigue resistance air fiber mat. The high fatigue resistance air fiber mat prepared by the invention has better advantages of high elasticity, high permeability, high support, and high fatigue resistance than conventional air fiber mats, but the poor compatibility between polyolefin resin and thermoplastic polyester elastomer resin may affect the mechanical properties of the air fiber mat.

[0004] Patent CN115895207A discloses a 3D air fiber material for low-pressure variable seats and a preparation method thereof. The 3D air fiber material for low-pressure variable seats is prepared from the following components in parts by weight: TPEE resin, composite cross-linking agent, composite antioxidant, composite lubricant, and foaming agent masterbatch. The air fiber material prepared by this invention can reduce the compression deformation rate of the seat during use, improve air permeability, and increase the comfort of the seat. However, the composite cross-linking agent used is a trifunctional or higher epoxy compound or a trifunctional or higher isocyanate compound. On the one hand, the strong activity makes the reaction difficult to control, which may increase the difficulty of processing. On the other hand, there are fewer active hydroxyl groups in the system, and the isocyanate groups remaining in the system may cause the fiber to yellow easily.

[0005] Therefore, there is an urgent need for an air fiber pad with good mechanical properties and good transparency in the market. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to obtain an air fiber mat which has excellent mechanical properties, good transparency and is not easy to deform.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On one hand, the present invention provides an air fiber mat that is not easily deformed. The preparation of the air fiber mat that is not easily deformed includes the following raw materials, measured by weight: 60-80 parts of high melting point and high strength TPEE, 5-10 parts of micro-crosslinking agent, 10-20 parts of filler, 0.05-0.2 parts of initiator, and 0.05-0.2 parts of metal catalyst.

[0009] The present application obtains an air fiber mat having excellent mechanical properties, transparency and not easy to deform by blending high-melting-point and high-strength TPEE with a micro-crosslinking agent, a filler, an initiator and a metal catalyst and then melt-spinning the mixture.

[0010] In some embodiments, the method for preparing the high melting point and high strength TPEE comprises the following steps:

[0011] S1. Mixing: Add antioxidant, catalyst and BDO into a mixing kettle, stir at 160-200°C for 20-30 minutes, and obtain a mixing kettle product;

[0012] S2, pre-condensation: the mixed kettle product obtained in step S1 is put into the pre-condensation kettle, and then the molten polyester, polyether and modifier are pumped through the pipeline into the pre-condensation kettle and stirred for 20-30 minutes, and the temperature is raised to 230-250°C, and the pressure is -0.4 to -0.7 kg / cm 2 The reaction was continued for 1-3 hours to obtain a prepolymer;

[0013] S3, polycondensation: pump the prepolymer obtained in step S2 into a polycondensation reactor, react at 240-260°C for 1-3h, with a vacuum degree of 20-50Pa, cool and pelletize to obtain high melting point and high strength TPEE.

[0014] Preferably, the mass ratio of the polyester to BDO is 1:(1-3).

[0015] In some embodiments, the method of adding in step S2 is to alternately add materials into two mixing kettles.

[0016] In some embodiments, the temperature of the pipe is 220-240°C.

[0017] In some embodiments, the polyester is PBT or PET.

[0018] Preferably, the polyester is recycled PET.

[0019] In some embodiments, the mass ratio of the polyester, polyether and modifier is 1:(0.4-0.7):(0.1-0.4).

[0020] In some embodiments, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, and triphenyl phosphite.

[0021] Preferably, the antioxidant is antioxidant 1010.

[0022] In some embodiments, the catalyst is a composition of tetrabutyl titanate and magnesium acetate, and the mass ratio of the two is 1:(0.3-0.6).

[0023] In some embodiments, the method for preparing the modifier comprises the following steps:

[0024] A1. Add IPDI trimer, PTMG and dibutyltin dilaurate into a reaction vessel and react at 25-35° C. for 2-4 hours to obtain a compound;

[0025] A2. Add PCDL to the compound obtained in step A1, and react at 70-80°C for 1-2h to obtain a modifier.

[0026] In some embodiments, the mass ratio of the IPDI trimer to PTMG in step A1 is 1:(2.5-3.5).

[0027] In some embodiments, the mass ratio of the compound to PCDL in step A2 is 1:(1.5-2.5).

[0028] In some embodiments, the preparation method of the micro-crosslinking agent comprises the following steps: adding styrene maleic anhydride resin, triethylamine, polyethylene glycol monomethyl ether, and an inhibitor to a solvent, reacting at 75-85°C for 2-3 hours, cooling to 45-55°C, adding hydroxyethyl methacrylate, heating to 75-85°C, reacting for 2-3 hours, and drying to obtain a micro-crosslinking agent.

[0029] Styrene maleic anhydride resin can react with TPEE to form a micro-crosslinked structure, but the high rigid group content of styrene maleic anhydride resin may make the toughness of the air fiber worse. In view of the above problems, the present application introduces the polyether segment by reacting styrene maleic anhydride resin with polyethylene glycol monomethyl ether, which can not only improve the toughness of the air fiber but also reduce the content of the anhydride group on the styrene maleic anhydride resin, which is conducive to reducing the processing difficulty of TPEE. And the present application further reacts styrene maleic anhydride resin with hydroxyethyl methacrylate to prepare a micro-crosslinking agent containing both anhydride groups and double bond groups, which can not only improve the crosslinking degree between TPEE but also form a crosslinked structure with the filler, promote the dispersibility between the substances, further improve the mechanical properties of the air fiber mat and improve its fatigue resistance.

[0030] In some embodiments, the mass ratio of the styrene maleic anhydride resin to polyethylene glycol monomethyl ether is 1:(0.2-0.5).

[0031] In some embodiments, the mass ratio of the styrene maleic anhydride resin to hydroxyethyl methacrylate is 1:(0.1-0.4).

[0032] The present application can make the air fiber mat have better mechanical properties and fatigue resistance by limiting the ratio of styrene maleic anhydride resin and polyethylene glycol monomethyl ether and styrene maleic anhydride resin and hydroxyethyl methacrylate. This may be because a suitable amount of anhydride groups can be retained on the micro-crosslinker segment in the process of introducing polyether segments and double bond groups, so that the air fiber can have better mechanical properties while having better fatigue resistance.

[0033] In some embodiments, the method for preparing the filler comprises the following steps: adding hollow glass microspheres and KH570 silane coupling agent to 90-95wt% ethanol, ultrasonicating at room temperature for 1-2h, heating to 70-80°C for reaction for 4-6h, and drying to obtain the filler.

[0034] In some embodiments, the mass ratio of the hollow glass microspheres to the KH570 silane coupling agent is 1:(0.15-0.35).

[0035] The present application can introduce double bond groups on hollow glass microspheres by using KH-570 silane coupling agent, and then undergo cross-linking reaction with double bonds on micro cross-linking agent during the processing of air fiber, thereby increasing the cross-linking point content on air fiber mat. And the hollow glass microspheres distributed in air fiber can further improve the mechanical strength of air fiber mat.

[0036] In some embodiments, the hollow glass microspheres have a particle size of 3-20 μm.

[0037] The present application limits the particle size of the hollow glass microspheres to ensure that the air fiber mat has good toughness while having good mechanical strength. On the one hand, this may be because the hollow glass microspheres with this particle size have more active groups, which can increase the loading amount of the silane coupling agent on the hollow glass microspheres and thus increase the double bond polymerization cross-linking points on the air fiber. On the other hand, the use of air glass microspheres with this particle size may make TPEE easier to process and spin.

[0038] In some embodiments, the initiator is one or more of dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, and dibenzoyl peroxide.

[0039] In some embodiments, the metal catalyst is dibutyltin maleate or dibutyltin dimaleate.

[0040] Another aspect of the present invention provides a method for preparing an air fiber mat that is not easily deformed, comprising the following steps:

[0041] B1. Mix high melting point and high strength TPEE and filler for 10-30 minutes to obtain a premix;

[0042] B2. Put the premix obtained in step B1 into a screw injection molding machine, add a micro-crosslinking agent, an initiator, and a metal catalyst, heat to 220-230° C., melt spin, stretch and pull, and collect on a roller to obtain an air fiber mat that is not easily deformed.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] (1) The present invention obtains an air fiber mat having excellent mechanical properties, transparency and not easy to deform by blending high-melting-point and high-strength TPEE with a micro-crosslinking agent, a filler, an initiator and a catalyst and then melt-spinning the mixture.

[0045] (2) The present invention improves the fatigue resistance of the air fiber by forming a micro-crosslinked structure by reacting styrene maleic anhydride resin with TPEE, and introduces a polyether segment by reacting styrene maleic anhydride resin with polyethylene glycol monomethyl ether, which can not only improve the toughness of the air fiber but also reduce the content of anhydride groups on the styrene maleic anhydride resin, which is beneficial to reduce the processing difficulty of TPEE.

[0046] (3) In the present invention, styrene maleic anhydride resin and hydroxyethyl methacrylate are reacted to prepare a micro-crosslinking agent containing both anhydride groups and double bond groups, which can not only improve the crosslinking degree between TPEE but also form a crosslinking structure with the filler, thereby promoting the dispersibility between the various substances, further improving the mechanical properties of the air fiber mat and improving its fatigue resistance. DETAILED DESCRIPTION

[0047] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0048] In the following embodiments and comparative examples, except for high melting point and high strength TPEE, micro cross-linking agent, filler and modifier, the other compounds and related reagents used can be purchased from the market, among which the particle size of hollow glass microsphere-1 is 5-6.5 μm, purchased from Guangdong Fantian Technology Co., Ltd.; the average particle size of hollow glass microsphere-2 is 100 mesh, purchased from Lingshou County Chenyang Mineral Products Co., Ltd.; the number average molecular weight of PTMG is 2000; the number average molecular weight of PCDL is 1000; recycled PET is purchased from Chen Yi (Shanghai) Renewable Resources Recycling Co., Ltd.; the model of polyethylene glycol monomethyl ether is MPEG-400, purchased from Hai'an Petrochemical Plant in Jiangsu Province.

[0049] Preparation Example 1

[0050] The preparation method of the modifier comprises the following steps:

[0051] A1, add 10g IPDI trimer, 30g PTMG, and 0.1g dibutyltin dilaurate into a reaction container, react at 30°C for 3h to obtain a compound;

[0052] A2. Add 20 g of PCDL to 10 g of the compound obtained in step A1, and react at 75° C. for 1.5 h to obtain a modifier.

[0053] Preparation Example 2

[0054] The preparation method of micro-crosslinking agent-1 comprises the following steps: adding 10g styrene maleic anhydride resin, 0.2g triethylamine, 3.5g polyethylene glycol monomethyl ether, and 0.02g p-hydroxyanisole to 20g butanone, reacting at 80°C for 2.5h, cooling to 50°C, adding 2.5g hydroxyethyl methacrylate, heating to 80°C for 2.5h, and drying to obtain micro-crosslinking agent-1.

[0055] Preparation Example 3

[0056] The preparation method of micro-crosslinking agent-2 is the same as that of Preparation Example 2, except that the added amount of polyethylene glycol monomethyl ether is 6 g.

[0057] Preparation Example 4

[0058] The preparation method of micro-crosslinking agent-3 is the same as that of Preparation Example 2, except that the added amount of hydroxyethyl methacrylate is 5 g.

[0059] Preparation Example 5

[0060] The preparation method of filler-1 comprises the following steps: adding 10g hollow glass microsphere-1 and 2.5g KH570 silane coupling agent into 50g 93wt% ethanol, ultrasonicating at room temperature for 1.5h, heating to 75°C for reaction for 5h, and drying to obtain filler-1.

[0061] Preparation Example 6

[0062] The preparation method of filler-2 is the same as that of Preparation Example 5, except that an equal amount of hollow glass microspheres-1 is replaced by hollow glass microspheres-2.

[0063] Preparation Example 7

[0064] The preparation method of high melting point and high strength TPEE comprises the following steps:

[0065] S1, mixing: add 3g antioxidant 1010, 1g tetrabutyl titanate, 0.45g magnesium acetate, and 200g BDO into a mixing kettle, stir at 180°C for 25min, and obtain a mixing kettle product;

[0066] S2, pre-condensation: the mixing kettle product obtained in step S1 is put into the pre-condensation kettle, the two mixing kettles are fed alternately, and then 100g of molten recycled PET, 55g of PTMG and 25g of modifier-1 are pumped through a pipeline at 230°C and then pumped into the pre-condensation kettle, stirred for 25min, heated to 240°C, and heated at a pressure of -0.5kg / cm 2 The reaction was continued for 2 h to obtain a prepolymer;

[0067] S3, polycondensation: pump the prepolymer obtained in step S2 into a polycondensation reactor, react at 250°C for 2h, with a vacuum degree of 35Pa, cool and pelletize to obtain high-melting-point and high-strength TPEE.

[0068] Example 1

[0069] An air fiber mat that is not easily deformed comprises the following raw materials, measured by weight: 70 parts of high-melting-point and high-strength TPEE, 7.5 parts of micro-crosslinking agent-1, 15 parts of filler-1, 0.1 parts of dibenzoyl peroxide, and 0.1 parts of dibutyltin maleate.

[0070] The method for preparing the air fiber mat that is not easily deformed in this embodiment comprises the following steps:

[0071] B1, mix high melting point and high strength TPEE and filler-1 for 20 minutes to obtain a premix;

[0072] B2. Put the premix obtained in step B1 into a screw injection molding machine, add micro-crosslinking agent-1, dibenzoyl peroxide, and dibutyltin maleate, heat to 225° C., melt spin, stretch and pull, and collect on a roller to obtain an air fiber mat that is not easily deformed.

[0073] Example 2

[0074] An air fiber mat that is not easily deformed comprises the following raw materials, measured by weight: 60 parts of high-melting-point and high-strength TPEE, 5 parts of micro-crosslinking agent-1, 10 parts of filler-1, 0.05 parts of dibenzoyl peroxide, and 0.05 parts of dibutyltin maleate.

[0075] The method for preparing the air fiber mat that is not easily deformed in this embodiment comprises the following steps:

[0076] B1, mix high melting point and high strength TPEE and filler-1 for 10 minutes to obtain a premix;

[0077] B2. Put the premix obtained in step B1 into a screw injection molding machine, add micro-crosslinking agent-1, dibenzoyl peroxide, and dibutyltin maleate, heat to 220° C., melt spin, stretch and pull, and collect on a roller to obtain an air fiber mat that is not easily deformed.

[0078] Example 3

[0079] An air fiber mat that is not easily deformed comprises the following raw materials, measured by weight: 80 parts of high-melting-point and high-strength TPEE, 10 parts of micro-crosslinking agent-1, 20 parts of filler-1, 0.2 parts of dibenzoyl peroxide, and 0.2 parts of dibutyltin maleate.

[0080] The method for preparing the air fiber mat that is not easily deformed in this embodiment comprises the following steps:

[0081] B1, mix high melting point and high strength TPEE and filler-1 for 30 minutes to obtain a premix;

[0082] B2. Put the premix obtained in step B1 into a screw injection molding machine, add micro-crosslinking agent-1, dibenzoyl peroxide, and dibutyltin maleate, heat to 230° C., melt spin, stretch and pull, and collect on a roller to obtain an air fiber mat that is not easily deformed.

[0083] Example 4

[0084] An air fiber mat that is not easily deformed and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of micro-crosslinking agent-1 is replaced by micro-crosslinking agent-2.

[0085] Example 5

[0086] An air fiber mat that is not easily deformed and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of micro-crosslinking agent-1 is replaced by micro-crosslinking agent-3.

[0087] Example 6

[0088] An air fiber mat that is not easily deformed and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of micro-crosslinking agent-1 is replaced by styrene maleic anhydride resin.

[0089] Example 7

[0090] An air fiber mat that is not easily deformed and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of filler-1 is replaced by filler-2.

[0091] Example 8

[0092] An air fiber mat that is not easily deformed and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of filler-1 is replaced by hollow glass microsphere-1.

[0093] Performance Testing

[0094] The air fiber mats that are not easily deformed obtained in the above embodiments are tested:

[0095] (1) Mechanical properties: The test method used for tensile strength and elongation at break is ASTM D638.

[0096] (2) Fatigue resistance: The fatigue resistance of the air fiber mat is determined by the indentation fatigue hardness loss rate. The thickness of the air fiber mat is 10 cm. The fiber mat is repeatedly compressed 100,000 times. The difference in indentation hardness corresponding to 40% of the thickness before and after the air fiber mat is compressed 100,000 times is calculated, and the indentation fatigue hardness loss rate is calculated. The compression frequency is (70±5) times / min. The test method for indentation hardness refers to GB / T 10807-2006. The calculation formula for indentation fatigue hardness loss rate is as follows:

[0097] Indentation fatigue hardness loss rate = (difference in indentation hardness of the air fiber pad before and after compression 100,000 times when the thickness is 40% / indentation hardness of the air fiber pad before compression 100,000 times when the thickness is 40%) × 100%

[0098] The test results are shown in Table 1:

[0099] Table 1

[0100]

[0101]

[0102] It can be seen from the data in Table 1 that the air fiber mats in Examples 1-3 of the present invention have good mechanical properties and fatigue resistance. From the comparison between Examples 4 and 5 and Example 1, it can be seen that changing the ratio of styrene maleic anhydride resin and polyethylene glycol monomethyl ether or styrene maleic anhydride resin and hydroxyethyl methacrylate will make it difficult for the anhydride group to react with TPEE, thereby reducing the cross-linking points in the air fiber and thus reducing the mechanical properties and fatigue resistance of the air fiber mat; from the comparison between Example 6 and Example 1, it can be seen that directly adding styrene maleic anhydride resin will deteriorate the mechanical properties and fatigue resistance of the air fiber mat; from the comparison between Example 7 and Example 1, it can be seen that changing the particle size of the hollow glass microspheres will reduce the loading amount of the silane coupling agent on the hollow glass microspheres and affect the processing performance of TPEE, thereby reducing the mechanical properties and fatigue resistance of the air fiber mat; from the comparison between Example 8 and Example 1, it can be seen that directly adding hollow glass microspheres will result in poor mechanical properties and fatigue resistance of the air fiber mat.

[0103] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. An air fiber mat that is not easily deformed, characterized in that: The air fiber mat that is not easily deformed is prepared, and includes the following raw materials, by weight: 60-80 parts of high-melting-point and high-strength TPEE, 5-10 parts of micro-crosslinking agent, 10-20 parts of filler, 0.05-0.2 parts of initiator, and 0.05-0.2 parts of metal catalyst.

2. The non-deformable air fiber mat according to claim 1, characterized in that: The method for preparing the high melting point and high strength TPEE comprises the following steps: S1. Mixing: Add antioxidant, catalyst and BDO into a mixing kettle, stir at 160-200°C for 20-30 minutes, and obtain a mixing kettle product; S2, pre-condensation: put the mixed kettle product obtained in step S1 into the pre-condensation kettle, then add the polyester, polyether and modifier into the pre-condensation kettle and stir for 20-30 minutes, raise the temperature to 230-250°C, and heat at a pressure of -0.4 to -0.7 kg / cm 2 The reaction was continued for 1-3 hours to obtain a prepolymer; S3, polycondensation: pump the prepolymer obtained in step S2 into a polycondensation reactor, react at 240-260°C for 1-3h, with a vacuum degree of 20-50Pa, cool and pelletize to obtain high melting point and high strength TPEE.

3. The non-deformable air fiber mat according to claim 1, characterized in that: The preparation method of the micro-crosslinking agent comprises the following steps: adding styrene maleic anhydride resin, triethylamine, polyethylene glycol monomethyl ether and a polymerization inhibitor into a solvent, reacting at 75-85° C. for 2-3 hours, cooling to 45-55° C., adding hydroxyethyl methacrylate, heating to 75-85° C. for 2-3 hours, and drying to obtain the micro-crosslinking agent.

4. The non-deformable air fiber mat according to claim 3, characterized in that: The mass ratio of the styrene maleic anhydride resin to polyethylene glycol monomethyl ether is 1:(0.2-0.5).

5. The non-deformable air fiber mat according to claim 3, characterized in that: The mass ratio of the styrene maleic anhydride resin to hydroxyethyl methacrylate is 1:(0.1-0.4).

6. The non-deformable air fiber mat according to claim 1, characterized in that: The preparation method of the filler comprises the following steps: adding hollow glass microspheres and KH570 silane coupling agent into 90-95wt% ethanol, ultrasonicating at room temperature for 1-2h, heating to 70-80°C for reaction for 4-6h, and drying to obtain the filler.

7. The non-deformable air fiber mat according to claim 6, characterized in that: The mass ratio of the hollow glass microspheres to the KH570 silane coupling agent is 1:(0.15-0.35).

8. The non-deformable air fiber mat according to claim 6, characterized in that: The particle size of the hollow glass microspheres is 3-20 μm.

9. The non-deformable air fiber mat according to claim 1, characterized in that: The metal catalyst is dibutyltin maleate or dibutyltin dimaleate.

10. A method for preparing the non-deformable air fiber mat according to any one of claims 1 to 9, characterized in that: The following steps are involved: B1. Mix high melting point and high strength TPEE and filler for 10-30 minutes to obtain a premix; B2. Put the premix obtained in step B1 into a screw injection molding machine, add a micro-crosslinking agent, an initiator, and a catalyst, heat to 220-230° C., melt spin, stretch and pull, and collect on a roller to obtain an air fiber mat that is not easily deformed.

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