Polyester triple-effect functional modification auxiliary agent, preparation method and application of polyester triple-effect functional modification auxiliary agent

Abstract

The invention relates to a polyester triple-effect functional modification auxiliary agent as well as a preparation method and application thereof. The scheme comprises the following steps: synthesizing a single-layer MoS2 nanosheet by virtue of a space confinement method, then mixing the single-layer MoS2 nanosheet with an ethylene glycol solution, adding bis (hydroxydiethyl)-5-sodium sulfonate phthalate, carrying out a grafting reaction, and carrying out post-treatment, so as to obtain the auxiliary agent. In the preparation method of the additive, parameters of each step are clear, and synthesis, effective grafting and the like of the high-monolayer-rate nanosheet can be ensured. The auxiliary agent can be dispersed in a plurality of polymer liquid monomer media, and the functionalized polymer nano composite material is synthesized through in-situ polymerization. The problems of single function, poor dispersibility and the like of the existing polyester functional modification aid are solved, the polyester material is endowed with photo-thermal, antibacterial and stock solution coloring three-effect functions, the polyester functional modification aid is suitable for modification of various polyesters and related polymer materials, product upgrading is realized on the basis of not changing the existing process, the application market is widened, the added value of the product is improved, and the application prospect is wide. The method has important industrial application value and market prospect.

Description

Technical Field

[0001] The present invention relates to a polyester functional modification auxiliary agent, in particular to a polyester triple-effect functional modification auxiliary agent, a preparation method and application thereof, which can realize functional modification of polyester materials such as antibacterial, photothermal, and stock solution coloring. Background Art

[0002] Polyester products are diverse, including polyethylene terephthalate, polybutylene adipate / terephthalate, polyurethane, polyamide, etc. They have significant advantages such as excellent mechanical properties, good chemical stability, easy processing and low price. Because of this, they are widely used in many fields, such as in the textile field, they can be used to make clothing fabrics, etc.; in the packaging industry, they can be used to make various packaging materials to ensure the storage and transportation of products; in terms of coating, they can provide protection and special properties for the surface of objects; in the field of engineering plastics, they play an important role and are used to manufacture various engineering parts.

[0003] With the development of society and the improvement of quality of life, the disadvantage of traditional polyester materials with a single function has gradually emerged, and it can no longer meet people's demand for continuously upgraded products. This has led to a series of problems with polyester materials, with large production volume but serious homogeneity, and few varieties of high-function products with a small proportion. Its quality is difficult to meet the high-end requirements of the market, resulting in low industry profit margins and excess capacity structure. For example, in the current market, a large number of polyester products have similar functions and lack differentiated competitive advantages, which cannot meet consumers' demand for polyester products with special functions such as antibacterial and warmth retention, resulting in fierce market competition and compressed corporate profit margins.

[0004] During the synthesis or processing of polyester, by adding appropriate functional additives, many special functionalities such as antibacterial, photothermal, etc. can be given to the polymer, so that the product has more excellent performance and advanced functions, and high value-added precision manufacturing of polymer products can be achieved to meet the application of polyester materials in more abundant fields such as thermal insulation equipment, medical appliances, and agricultural production. For example, in thermal insulation equipment, polyester materials with photothermal functions can absorb solar energy and convert it into heat energy to provide warmth for users; in medical appliances, polyester materials with antibacterial functions can effectively prevent bacterial growth and ensure the safety of the medical environment.

[0005] Currently, there are existing polyester functional modification additives such as ZnO, TiO2, Ag2O nanoparticles, etc., but there are many defects. These additives often have a single material function and cannot meet multiple functional requirements at the same time. For example, the nano ZnO antibacterial functional modification additive only has antibacterial function, but cannot provide other functions such as light and heat. At the same time, they also have the problem of large addition amount, which not only increases the production cost, but may also have an adverse effect on the original performance of the material. Moreover, the dispersibility is poor, and it is difficult to disperse evenly in the polymer matrix, which will lead to uneven material performance. In addition, the high-temperature stability is insufficient. In some high-temperature processing processes, the performance of the additive may change, which seriously affects the subsequent processing, production and promotion and application of the material.

[0006] For example, the cesium tungsten bronze nanoparticle photothermal modification additive disclosed in patent CN202410342107.8 has problems such as large addition amount, high cost, and difficulty in scaling up production and application, which limits its application in large-scale industrial production. The nano ZnO antibacterial functional modification additive reported in patent CN116262989A has problems such as single product function, difficulty in dyeing, and poor dispersion of nanoparticles, which makes it subject to many restrictions in practical applications and cannot meet the market demand for multifunctional and high-performance polyester materials.

[0007] Among them, single-layer MoS2 is a unique two-dimensional layered material with extremely high specific surface area and many unique physical and chemical properties. When it is introduced into the polymer matrix as a functional additive, it can form a molecular composite material, and its reinforcement effect far exceeds that of traditional nanomaterials. At the same time, the addition of single-layer MoS2 can provide polymers with unique functions such as toughening, photothermal, and antibacterial, making it an ideal material as a special additive for functional modification of polyester materials. For example, its photothermal function can make polyester materials heat up under light, which has potential value in solar energy utilization; the antibacterial function can improve the hygienic properties of polyester materials.

[0008] However, there are some problems when single-layer MoS2 is used to modify polyester materials. Since single-layer MoS2 has a darker color and it is difficult for the dye material to form a tight chemical bond with the molecular chain, there is a weak interaction between the dye molecules and the polymer molecular chains, which can easily lead to the product being difficult to dye, easy to change color, and unstable color. This poses a great challenge to some application scenarios that have color requirements, such as textile dyeing, and limits its application and promotion in related fields.

[0009] In summary, there is an urgent need to develop a special polyester modification additive that can not only solve the problems of existing polyester functional modification additives, but also give full play to the multi-effect functional modification capabilities of single-layer MoS2, so as to realize the multifunctionality and high performance of polyester materials and meet the market's growing demand for polyester materials. Summary of the invention

[0010] The purpose of the present invention is to provide a polyester triple-effect functional modified auxiliary agent, a preparation method and application thereof in view of the above problems existing in the prior art.

[0011] In order to achieve the above application purpose, the present invention adopts the following technical scheme: A method for preparing a polyester triple-effect functional modified additive comprises the following steps:

[0012] S00, synthesis of single-layer MoS2 nanosheets by spatial confinement method;

[0013] S10, uniformly mixing the single-layer MoS2 nanosheets with the ethylene glycol solution by ultrasound and / or stirring to obtain a dispersion;

[0014] Wherein, the mass fraction of the dispersion is between 0.0001-20%;

[0015] S20, adding sodium 5-sulfonate of bis(hydroxyethyl)phthalate to the dispersion, wherein the mass ratio of sodium 5-sulfonate of bis(hydroxyethyl)phthalate to the monolayer MoS2 nanosheet is 3 to 5:1, so that the sodium 5-sulfonate undergoes a grafting reaction with the monolayer MoS2 nanosheet, and a polyester triple-effect functional modified auxiliary agent is obtained by post-treatment;

[0016] Among them, the grafting reaction is that the π bond of sodium bis(hydroxyethyl)phthalate-5-sulfonate is tightly combined with the surface site of the monolayer MoS2 nanosheet through the chemical coupling effect produced by the highly delocalized π electrons of the benzene ring and the external electrons of the sulfur atom, forming a tight grafting site.

[0017] Furthermore, in step S00, the spatial confinement method uses layered bimetallic oxides as micro-nano reactors, and uses the interlayer gaps as confined spaces to limit the MoS4 2- The longitudinal growth space of the single-layer MoS2 nanosheets is decomposed to ensure that the synthesized nanosheets have a high monolayer rate greater than 99%.

[0018] Furthermore, in step S00, the spatial confinement method is used to 2- After being intercalated between the layers of the layered bimetallic oxide, the mixture is calcined under the protection of an inert gas and then washed with acid to remove the mixed metal oxides, thereby obtaining a single-layer MoS2 nanosheet.

[0019] Furthermore, in step S20, the calcination temperature is 350-600° C., and the calcination time is 2-5 h.

[0020] Furthermore, in step S20, after sodium dihydroxyethyl phthalate-5-sulfonate is added, stirring or ultrasonic treatment is performed throughout the process to allow it to react with the single-layer MoS2 nanosheets. After the reaction is completed or the set time is reached, it is allowed to stand and then post-processed.

[0021] Furthermore, in step S20, the standing time is 12-20 hours.

[0022] Furthermore, in step S20, post-treatment includes: performing solid-liquid separation by suction filtration or centrifugation to retain solids; and washing the solids obtained by the reaction with ethylene glycol for multiple times and then drying them.

[0023] A polyester triple-effect functional modified auxiliary agent is prepared by the preparation method of the polyester triple-effect functional modified auxiliary agent.

[0024] The application of the above-mentioned polyester triple-effect functional modified auxiliary agent comprises the following steps:

[0025] Dispersing the polyester triple-effect functional modified additive in the polymer liquid monomer medium by ultrasonic or stirring to obtain a monomer dispersion with a mass fraction of 0.0001-20%;

[0026] The monomer dispersion is polycondensed into a functionalized polymer nanocomposite material by an in-situ polymerization method;

[0027] The polymer liquid monomer medium includes one or more of ethylene glycol, 1,4-butanediol, diphenylmethane diisocyanate, toluene diisocyanate, caprolactam, methyl methacrylate, lactide, and glycolide.

[0028] Further, the polymer nanocomposite material includes one or more of polyethylene terephthalate, polybutylene adipate / terephthalate, polyurethane, polyamide, polymethyl methacrylate, polylactic acid, polyglycolide, polybutylene succinate / terephthalate.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. Advantages of functional integration and added volume

[0031] The present invention overcomes the single function defect of existing additives. By grafting SIPE (sodium bis(hydroxyethyl)phthalate-5-sulfonate) with the surface of a single-layer MoS2 nanosheet, a photothermal / antibacterial / solution coloring triple-effect functional modification special additive is prepared. By adding only a single additive, the polyester material can have multiple excellent functions such as photothermal performance, antibacterial performance, liquid coloring performance and dyeability, which expands the application range of the material and meets the diverse market needs.

[0032] The amount of additives added is significantly reduced. Compared with existing additives, the amount of additives added in the present invention is extremely low, which effectively reduces the production cost, provides a cost advantage for the product to compete in the market, has broad application prospects, and can promote the development of related industries.

[0033] 2. High temperature stability and process simplification

[0034] It has good high temperature stability and can be directly added to the polymer monomer raw material liquid to directly carry out high temperature esterification, polycondensation and other process. Polyester products with excellent antibacterial properties, photothermal properties and dyeability can be obtained without post-processing, which simplifies the traditional production process, reduces production links and costs, and improves production efficiency.

[0035] This direct addition method effectively increases the added value of the product, giving the product more unique properties and meeting the needs of the high-end market. At the same time, it expands the application market and creates conditions for the application of polyester products in more fields.

[0036] 3. Solve the agglomeration problem and improve compatibility

[0037] The problem of functionalized additives being easily agglomerated in the polyester matrix is ​​effectively solved. In the additive prepared by the present invention, the ester bond end of SIPE can interact with the polar polymer matrix and be covalently grafted on the polymer chain segment through polymerization reaction, which greatly improves the compatibility of MoS2 nanosheets with the polyester matrix.

[0038] This high compatibility ensures that the MoS2 nanosheets are evenly dispersed in the polyester matrix, maximizing their functionality, improving the overall performance and stability of the material, and extending the service life of the material.

[0039] 4. Raw materials and dyeing advantages

[0040] The raw materials used in the present invention are all common raw materials in conventional polymer synthesis processes, which are low in price and reduce production costs. At the same time, the process is simple, easy to operate and control, and is conducive to large-scale production.

[0041] Sodium dihydroxydiethyl isophthalate-5-sulfonate is a common polymer dyeability modifier. Its sulfonate group easily interacts with cationic dyes, making the dye more closely bonded to the polymer molecular chain, improving dyeing efficiency and ensuring uniform dyeing. It successfully solves the problem of dark color and poor dyeability of MoS2 nanosheet modified materials, enriching the color selection and dyeing quality of the product.

[0042] 5. Synthesis conditions and industrial applicability

[0043] The preparation method of the additive has mild synthesis conditions, avoids the high requirements of harsh reaction conditions on equipment and energy, reduces production risks and costs, and has high synthesis quality, which can ensure the stable and reliable performance of the additive.

[0044] It is easy to produce on an industrial scale and can meet large-scale market demand. In addition, the present invention has no impact on conventional polymer synthesis processes. The modified additive can be directly added to the original synthesis process to synthesize functional polyester materials without large-scale transformation of existing production lines. It is suitable for industrial preparation at the current stage, reduces the cost and difficulty of industrial upgrading, and is conducive to rapid promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The infrared spectrum of the special auxiliary agent for photothermal / antibacterial / solution coloring triple-effect functional modification prepared by grafting sodium bis(hydroxyethyl)isophthalate-5-sulfonate (SIPE) with the surface of a single-layer MoS2 nanosheet of the present invention.

[0046] Figure 2 This is a fluorescence confocal image of the triple-effect functional modified polyethylene terephthalate material in Example 1 of the present invention.

[0047] Figure 3 This is a TEM image of the internal nanosheet dispersion of the triple-effect functional modified polyethylene terephthalate material in Example 1 of the present invention. DETAILED DESCRIPTION

[0048] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0049] Those skilled in the art should understand that, in the disclosure of the present invention, the orientation or position relationship indicated by terms such as "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inside" and "outside" are based on the orientation or position relationship shown in the accompanying drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the above terms should not be understood as limiting the present invention.

[0050] Example 1

[0051] In Example 1, the present invention selects ethylene glycol as a dispersion medium, adds 1% by mass of MoS2 nanosheets into the ethylene glycol, and disperses them uniformly through ultrasonic treatment.

[0052] In Example 1, the present invention adds sodium bis(hydroxyethyl isophthalate)-5-sulfonate in a mass ratio of 3:1 to MoS2 to the dispersion, ultrasonically treats the dispersion at room temperature for 16 hours, and then allows the dispersion to stand for 16 hours.

[0053] In Example 1, the present invention performs solid-liquid separation on the treated dispersion by suction filtration or centrifugation to retain the solid; the solid is washed multiple times with ethylene glycol and then dried to obtain a SIPE grafted single-layer MoS2 functionalized modification additive.

[0054] In Example 1, the present invention selects ethylene glycol and terephthalic acid as comonomers. Specifically, 0.680 g of SIPE grafted monolayer MoS2 functionalized modification agent is added to 40.3 g of ethylene glycol, and uniformly dispersed by ultrasound to obtain a SIPE-MoS2-ethylene glycol dispersion.

[0055] In Example 1, the present invention places the above-mentioned SIPE-MoS2-ethylene glycol dispersion and 83g terephthalic acid into a reactor (alcohol-acid ratio is 1.3:1). After being fully mixed and uniformly, mechanical stirring is continued. When the reaction system reaches 240°C, TBT is added as a catalyst in an amount of 0.15% of the acid molar content. The esterification reaction is stirred for 8h under the protection of a nitrogen atmosphere at 240°C. The reactant turns dark brown, the esterification rate exceeds 90%, and the esterification reaction is stopped after there is no distillate within half an hour. Subsequently, the vacuum degree of the reaction system is evacuated to 100pa by a vacuum pump, the temperature is raised to 280°C, and the reaction is stirred for 3h until the climbing phenomenon occurs, the viscosity of the reaction system no longer rises, and the reaction is stopped to obtain a functionalized modified polyethylene terephthalate product, wherein the content of the functionalized modified additive of SIPE grafted monolayer MoS2 is 0.5wt%.

[0056] In Example 1, the present invention cuts and granulates the obtained product material, and processes it by melt spinning to obtain a functionalized modified polyethylene terephthalate fiber material. The tensile strength is 100Mpa, the Young's modulus is 4.8Gpa, and the elongation at break is 450% as tested by a universal material testing machine.

[0057] In Example 1, the present invention performs an antibacterial property test on the obtained product material.

[0058] In Example 1, the present invention uses 1 standard sunlight to test the photothermal performance of the product at an ambient temperature of 23° C., and records the temperature change of the product with an infrared camera.

[0059] In Example 1, the fiber material obtained by the present invention is characterized by fluorescence confocal microscopy (eg Figure 2 As shown in the figure, it can be observed that the SIPE grafted monolayer MoS2 functionalized modified additive is well dispersed in the fiber without agglomeration. However, the comparative example 1 and comparative agent 2 mentioned later have some agglomeration.

[0060] Example 2

[0061] In Example 2, the present invention selects ethylene glycol as the dispersion medium, adds 1% by mass of MoS2 nanosheets into the ethylene glycol, and disperses them uniformly through ultrasonic treatment.

[0062] In Example 2, the present invention adds sodium bis(hydroxyethyl isophthalate)-5-sulfonate in a mass ratio of 3:1 to MoS2 to the dispersion, ultrasonically treats the dispersion for 16 hours at room temperature, and then leaves the dispersion to stand for 16 hours.

[0063] In Example 2, the present invention performs solid-liquid separation on the treated dispersion by suction filtration or centrifugation to retain the solid; the solid is washed multiple times with ethylene glycol and then dried to obtain a SIPE grafted single-layer MoS2 functionalized modification additive.

[0064] In Example 2, the present invention selects 1,4-butanediol, terephthalic acid and oxalic acid as comonomers. Specifically, 0.680 g of SIPE grafted monolayer MoS2 functionalized modification agent is added to 58.58 g of 1,4-butanediol, and uniformly dispersed by ultrasound to obtain a SIPE-MoS2-1,4-butanediol dispersion.

[0065] In Example 2, the present invention places the above-mentioned SIPE-MoS2-1,4-butanediol dispersion, 36.55g terephthalic acid and 40.92g adipic acid into a reactor (alcohol-acid ratio is 1.3:1). After being fully mixed, mechanical stirring is continued, and a nitrogen atmosphere is added for protection. When the reaction system reaches 180°C, TBT is added as a catalyst in an amount of 0.15% of the molar content of the acid, and the reaction is carried out at 180°C for 2h, and the temperature is raised to 200°C. After reacting for 2h, the temperature is raised to 220°C again, and the esterification reaction is stirred for 10h. The reactant turns dark brown, the esterification rate exceeds 90%, and the esterification reaction is stopped after there is no distillate within half an hour. Subsequently, the vacuum degree of the reaction system was evacuated to 100 Pa by a vacuum pump, the temperature was raised to 240°C, and the reaction was stirred for 4 hours until the pole climbing phenomenon occurred and the viscosity of the reaction system no longer increased. The reaction was stopped to obtain a functionalized modified poly(butylene adipate) / terephthalate product, in which the content of the functionalized modified additive of SIPE grafted monolayer MoS2 was 0.5wt%.

[0066] In Example 2, the present invention cuts and granulates the obtained product material, processes it by hot pressing to obtain a functionalized modified poly (butylene adipate / terephthalate) product film material, and cuts it to obtain a dumbbell-shaped strip. The tensile strength is 60 MPa, the Young's modulus is 100 MPa, and the elongation at break is 900% as measured by a universal material testing machine.

[0067] In Example 2, the present invention performs an antibacterial property test on the obtained product material.

[0068] Example 3

[0069] In Example 3, the present invention selects ethylene glycol as the dispersion medium, adds 1% by mass of MoS2 nanosheets into the ethylene glycol, and disperses them uniformly through ultrasonic treatment.

[0070] In Example 3, the present invention adds sodium bis(hydroxyethyl isophthalate)-5-sulfonate in a mass ratio of 3:1 to MoS2 to the dispersion, ultrasonically treats the dispersion at room temperature for 16 hours, and then leaves the dispersion to stand for 16 hours.

[0071] In Example 3, the present invention performs solid-liquid separation on the treated dispersion by suction filtration or centrifugation to retain the solid; the solid is washed multiple times with ethylene glycol and then dried to obtain a SIPE grafted single-layer MoS2 functionalized modification additive.

[0072] In Example 3, the present invention selects ethylene glycol and terephthalic acid as comonomers. Specifically, 0.136 g of SIPE grafted monolayer MoS2 functionalized modification agent is added to 40.3 g of ethylene glycol, and uniformly dispersed by ultrasound to obtain a SIPE-MoS2-ethylene glycol dispersion.

[0073] In Example 3, the present invention places the above-mentioned SIPE-MoS2-ethylene glycol dispersion and 83g terephthalic acid into a reactor (alcohol-acid ratio is 1.3: 1). After being fully mixed and uniformly, mechanical stirring is continued. When the reaction system reaches 240°C, TBT is added as a catalyst in an amount of 0.15% of the molar content of the acid. The esterification reaction is stirred for 8h under the protection of a nitrogen atmosphere at 240°C. The reactant turns dark brown, the esterification rate exceeds 90%, and the esterification reaction is stopped after there is no distillate within half an hour. Subsequently, the vacuum degree of the reaction system is evacuated to 100pa by a vacuum pump, the temperature is raised to 280°C, and the reaction is stirred for 3h until the climbing phenomenon occurs, the viscosity of the reaction system no longer rises, and the reaction is stopped to obtain a functionalized modified polyethylene terephthalate product, wherein the content of the functionalized modified additive of SIPE grafted monolayer MoS2 is 0.1wt%.

[0074] In Example 3, the present invention cuts and granulates the obtained product material, and processes it by melt spinning to obtain a functionalized modified polyethylene terephthalate fiber material. The tensile strength is 90Mpa, the Young's modulus is 3.5Gpa, and the elongation at break is 750% as measured by a universal material testing machine.

[0075] In Example 3, the present invention conducts an antibacterial property test on the obtained product material.

[0076] In Example 3, the present invention uses 1 standard sunlight to test the photothermal performance of the product at an ambient temperature of 23° C., and records the temperature change of the product with an infrared camera.

[0077] Example 4

[0078] Polyethylene terephthalate was prepared according to the method of Example 1, except that the mass ratio of MoS2 to sodium bis(hydroxyethyl)isophthalate-5-sulfonate was 5:1 in the dispersion.

[0079] Example 5

[0080] Polyethylene terephthalate was prepared according to the method of Example 1, except that the esterification temperature was 230°C and the polycondensation temperature was 300°C.

[0081] Comparative Example 1

[0082] Polyethylene terephthalate was prepared according to the method of Example 1, except that no SIPE grafted monolayer MoS2 functional modification agent was added, and other parameters were the same as those in Example 1.

[0083] Comparative Example 2

[0084] Polyethylene terephthalate was prepared according to the method of Example 1, except that only MoS2 was added as a modification aid, and SIPE was not added. Other parameters were the same as those of Example 1.

[0085] Comparative Example 3

[0086] Polyethylene terephthalate was prepared according to the method of Example 1, except that only SIPE was added as a modification aid, and MoS2 was not added. Other parameters were the same as those in Example 1.

[0087] Based on the above embodiments and comparative examples, Figure 1 As shown, Fourier infrared spectroscopy proved that the auxiliary material sodium bis(hydroxyethyl)-5-sulfonate (SIPE) was successfully grafted on the MoS2 surface.

[0088] The performance was compared by fluorescence confocal microscopy and transmission electron microscopy ( Figure 2 ) It can be found that in Example 1 with the addition of SIPE grafted MoS2 additive, the dispersibility of the single-layer MoS2 in the polymer matrix is ​​significantly improved compared with Comparative Example 2, and through the mechanical data (Table 1), it is found that the elongation at break of Example 1 with the addition of SIPE grafted MoS2 additive is significantly improved compared with Comparative Examples 1 and 2. This is also because the compatibility of the single-layer MoS2 with the polymer matrix is ​​improved after SIPE grafting, thereby reducing the occurrence of agglomeration.

[0089] Table 1 Mechanical properties of triple-effect functional modified polyethylene terephthalate materials

[0090]

[0091] The photothermal performance was compared by recording the temperature changes ( Figure 3 ) It can be seen that by comparing Example 1 with Comparative Example 1, the polyester material after adding the SIPE grafted monolayer MoS2 triple-effect functional modification agent obtains extremely excellent light and thermal performance. Under the irradiation of 1 standard sunlight, the material is heated to 70°C within 2 minutes. By comparing Example 1 with Comparative Example 2, it can be seen that after SIPE grafting, the monolayer MoS2 is well dispersed in the polyester matrix, and the functionality of the material is further improved. It can also be seen from the data of Example 4 and Example 5 that they are better than Comparative Examples 1 and 2.

[0092] It can be seen from Table 2 that the functional polyester materials obtained by adding the SIPE grafted monolayer MoS2 triple-effect functional modification agent in Examples 1-5 have excellent antibacterial properties, and the antibacterial rate reaches more than 96%, which meets the market demand.

[0093] Table 2 Antibacterial properties of triple-effect functional modified polyester materials

[0094]

[0095]

[0096] The fiber stock solution coloring of the materials of Example 1 and Comparative Example 3 found that the dyeing efficiency, dyeing uniformity, and color aging resistance of Example 1 after adding SIPE grafting were significantly improved, and after multiple washings, the color of Example 1 did not fall off, while the color of Comparative Example 3 fell off. Therefore, it can be seen that the triple-effect functional modification auxiliary provided by the present invention can effectively improve the dyeability of the product and meet the subsequent processing requirements.

[0097] By comparing the mechanical properties, photothermal properties and antibacterial properties of Example 1, Example 4 and Example 5, it was found that the present invention has excellent stability and versatility under different ratios of SIPE to single-layer MoS2 nanosheets and different reaction conditions.

[0098] The parts not described in detail in the present invention are prior art, so the present invention does not describe them in detail.

[0099] It is to be understood that the term "one" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple, and the term "one" should not be understood as a limitation on the quantity.

[0100] Although more professional terms are used in this article, the possibility of using other terms is not excluded. These terms are used only to more conveniently describe and explain the essence of the present invention; interpreting them as any additional restrictions is contrary to the spirit of the present invention.

[0101] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that are the same or similar to the present invention fall within the protection scope of the present invention.

Claims

1. A method for preparing a polyester triple-effect functional modified additive, characterized in that: The following steps are involved: S00, synthesis of single-layer MoS2 nanosheets by spatial confinement method; S10, uniformly mixing the single-layer MoS2 nanosheet with the ethylene glycol solution by ultrasound and / or stirring to obtain a dispersion; Wherein, the mass fraction of the dispersion is between 0.0001-20%; S20, adding sodium 5-sulfonate of dihydroxyethyl phthalate to the dispersion, wherein the mass ratio of sodium 5-sulfonate of dihydroxyethyl phthalate to the monolayer MoS2 nanosheet is 3 to 5:1, so that the sodium 5-sulfonate of dihydroxyethyl phthalate and the monolayer MoS2 nanosheet undergo a grafting reaction, and obtaining a polyester triple-effect functional modified auxiliary agent through post-treatment; Among them, the grafting reaction is that the π bond of the sodium bis(hydroxydiethyl phthalate-5-sulfonate) is tightly combined with the surface site of the monolayer MoS2 nanosheet through the chemical coupling effect produced by the highly delocalized π electrons of the benzene ring and the external electrons of the sulfur atom, forming a tight grafting site.

2. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 1, characterized in that: In step S00, the spatial confinement method uses a layered bimetallic oxide as a micro-nano reactor and uses the interlayer gap as a confined space to limit the MoS4 in the calcination process. 2- The longitudinal growth space of the single-layer MoS2 nanosheets is decomposed to ensure that the synthesized nanosheets have a high monolayer rate greater than 99%.

3. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 2, characterized in that: In step S00, the spatial confinement method is carried out by 2- After being intercalated between the layers of the layered bimetallic oxide, the mixture is calcined under the protection of an inert gas and then washed with acid to remove the mixed metal oxides, thereby obtaining a single-layer MoS2 nanosheet.

4. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 3, characterized in that: In step S20, the calcination temperature is 350-600° C., and the calcination time is 2-5 hours.

5. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 1, characterized in that: In step S20, after sodium bis(hydroxydiethyl phthalate-5-sulfonate) is added, stirring or ultrasonic treatment is performed throughout the process to allow it to react with the single-layer MoS2 nanosheet. After the reaction is completed or the set time is reached, it is allowed to stand and then post-processed.

6. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 5, characterized in that: In step S20, the standing time is 12-20 hours.

7. The method for preparing the polyester triple-effect functional modification auxiliary agent according to claim 5, characterized in that: In step S20, the post-treatment includes: performing solid-liquid separation by suction filtration or centrifugation to retain the solid; and washing the solid obtained by the reaction with ethylene glycol for multiple times and then drying it.

8. A polyester triple-effect functional modification auxiliary agent, characterized in that: The polyester triple-effect functional modified auxiliary agent is prepared by the preparation method of any one of claims 1 to 7.

9. The use of a polyester triple-effect functional modification auxiliary agent as claimed in claim 8, characterized in that: The following steps are involved: Dispersing the polyester triple-effect functional modified additive in the polymer liquid monomer medium by ultrasonic or stirring to obtain a monomer dispersion with a mass fraction of 0.0001-20%; Polycondensing the monomer dispersion into a functionalized polymer nanocomposite material by an in-situ polymerization method; The polymer liquid monomer medium includes one or more of ethylene glycol, 1,4-butanediol, diphenylmethane diisocyanate, toluene diisocyanate, caprolactam, methyl methacrylate, lactide, and glycolide.

10. The use of a polyester triple-effect functional modification auxiliary agent according to claim 9, characterized in that: The polymer nanocomposite material comprises one or more of polyethylene terephthalate, polybutylene adipate / terephthalate, polyurethane, polyamide, polymethyl methacrylate, polylactic acid, polyglycolide, and polybutylene succinate / terephthalate.

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