Long-acting antibacterial TPU (thermoplastic polyurethane) material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of TPU materials, and particularly relates to a long-acting antibacterial TPU material as well as a preparation method and application thereof. The long-acting antibacterial TPU material comprises a carboxyl silicone oil modified inorganic antibacterial agent and quaternary ammonium salt modified polyurethane in a mass ratio of (3-8): 100, the quaternary ammonium salt modified polyurethane is prepared from the following raw materials in parts by mass: 45 to 90 parts of polyester polyol, 10 to 20 parts of diisocyanate and 3 to 8 parts of hydroxyl-containing quaternary ammonium salt modified organic silicon. The TPU material prepared from the carboxyl silicone oil modified inorganic antibacterial agent and the quaternary ammonium salt modified polyurethane has the antibacterial rate of more than 99% on staphylococcus aureus and escherichia coli, and has lasting antibacterial property.

Description

Technical Field

[0001] The present invention belongs to the technical field of TPU materials, and particularly relates to a long-acting antibacterial TPU material, a preparation method thereof, and an application thereof. Background Art

[0002] TPU (thermoplastic polyurethane elastomer) materials are widely used in the fields of food, medical, automotive, electronics, footwear, etc. due to their advantages such as high strength, high toughness, wear resistance, and oil resistance. However, due to the hydrophobicity of conventional TPU itself, bacteria are prone to adhere and colonize on the TPU surface, which limits its application in fields with antibacterial requirements.

[0003] Currently, the methods for preparing antibacterial TPU mainly include two categories. One category is to blend an antibacterial agent with TPU. For example, Chinese Patent with Publication No. CN 117777397A discloses an antibacterial TPU material for oropharyngeal airway and a preparation method thereof. The TPU material includes the following raw materials in parts by weight: 25-35 parts of polyester diol, 35-45 parts of polyether diol, 28-38 parts of diisocyanate, 5-15 parts of chain extender, 10-15 parts of antibacterial agent, and 1-5 parts of modified inorganic filler. The TPU material provided by this technical solution has good elasticity, antibacterial performance, and lubricating performance, and can be widely used in the field of medical devices such as oropharyngeal airways. However, this technical solution does not pay attention to its long-acting antibacterial property.

[0004] Chinese Patent with Authorization Publication No. CN 115286766B discloses an antibacterial thermoplastic polyurethane elastomer material, a preparation method thereof, and an application thereof in the preparation of wristbands, cutting boards, and mobile phone cases. The preparation method includes: adding a macromolecular diol, a diisocyanate, and a chain extender into a twin-screw extruder through a first pouring port, adding an alcohol and / or an acid containing a mercapto group into the twin-screw extruder through a second pouring port, extruding to obtain a polyurethane elastomer material with terminal mercapto groups, and then mixing with a silver ion antibacterial agent and adding them into the twin-screw extruder for extrusion granulation to obtain the antibacterial thermoplastic polyurethane elastomer material. The antibacterial agent in this technical solution can be evenly distributed throughout the whole body and surface of the product. On the one hand, it keeps the silver ions in a stable state all the time, and it is not easy to undergo a color reaction with oxygen in the air, thereby avoiding color change of the product; on the other hand, the dissolution rate of the silver ions combined with the mercapto groups in the body phase slows down, and the antibacterial timeliness is greatly extended. However, there are silver ions in this technical solution, and the degradation and discoloration of silver ions still cannot be avoided after long-term use.

[0005] Another type is to introduce antibacterial components into the main chain of polyurethane. For example, a Chinese patent with the authorized publication number CN 112679689B discloses an organosilicon quaternary ammonium salt modified polyurethane, its preparation method and application. The organosilicon quaternary ammonium salt modified polyurethane is prepared from an organosilicon quaternary ammonium salt, a polyether polyol or a polyester polyol, a diisocyanate, an organometallic catalyst, a chain extender, an antifoaming agent and a curing agent. In this technical solution, an organosilicon quaternary ammonium salt is first prepared and then grafted onto the polyurethane side chain. Since the side-chain organosilicon is prone to migrate to the material surface, the quaternary ammonium salt connected thereto is also enriched on the surface, increasing the contact with bacteria, improving the antibacterial effect, and reducing the amount of antibacterial agent used, thus saving costs. In addition, the side-chain organosilicon can more effectively improve the hydrophobicity of the material surface than the organosilicon grafted onto the main chain, which is beneficial to keeping the material surface dry, thereby reducing the growth of microorganisms such as bacteria and viruses. However, the antibacterial rate of this technical solution against Escherichia coli and Staphylococcus aureus can only reach about 90%, and the long-term effect is not concerned. Summary of the Invention

[0006] In view of the above problems, the present invention provides a long-acting antibacterial TPU material, its preparation method and application. The TPU material obtained by using carboxyl silicone oil modified inorganic antibacterial agent and quaternary ammonium salt modified polyurethane in the present invention has an inhibition rate of more than 99% against Staphylococcus aureus and Escherichia coli, and has persistent antibacterial properties.

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

[0008] In the first aspect of the present invention, a long-acting antibacterial TPU material is provided, which comprises a carboxyl silicone oil modified inorganic antibacterial agent and a quaternary ammonium salt modified polyurethane in a mass ratio of 3-8:100. The quaternary ammonium salt modified polyurethane, calculated by mass, comprises 45-90 parts of a polyester polyol, 10-20 parts of a diisocyanate, and 3-8 parts of a hydroxyl-containing quaternary ammonium salt modified organosilicon.

[0009] In some preferred embodiments, the polyester polyol comprises a polyester polyol A and a polyester polyol B. The composition of the polyester polyol A is adipic acid, ethylene glycol and 1,4-butanediol. The composition of the polyester polyol B is terephthalic acid, oxalic acid and diethylene glycol.

[0010] Preferably, the mass ratio of the polyester polyol A to the polyester polyol B is 3-5.5:1.

[0011] Preferably, the number average molecular weight of the polyester polyol A is 1000, purchased from Risheng Chemical Industry Co., Ltd., model: P-2710TL.

[0012] Preferably, the number average molecular weight of the polyester polyol B is 1300, purchased from Risheng Chemical Industry Co., Ltd., model: P-7513A.

[0013] In some preferred embodiments, the diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, preferably isophorone diisocyanate.

[0014] In some preferred embodiments, the method for preparing the quaternary ammonium salt-modified organosilicon containing hydroxyl groups comprises the following steps: polyvinyl alcohol, water and a silane coupling agent are subjected to a heating reaction, the temperature is lowered, 2,3-epoxypropyltrimethylammonium chloride is added, the pH is adjusted to be alkaline, and the reaction is continued to obtain the product.

[0015] Preferably, the mass ratio of the polyvinyl alcohol, water and the silane coupling agent is 10:30 - 50:0.4 - 0.6.

[0016] Preferably, the mass ratio of the silane coupling agent and 2,3-epoxypropyltrimethylammonium chloride is 1:1.1 - 1.3.

[0017] Preferably, the silane coupling agent is selected from at least one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane and γ-aminopropyltriethoxysilane, preferably γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0018] More preferably, the method for preparing the quaternary ammonium salt-modified organosilicon containing hydroxyl groups comprises the following steps: polyvinyl alcohol, water and a silane coupling agent are subjected to a heating reaction at 80 - 90 °C for 1 - 2 h, the temperature is lowered to 25 - 30 °C, 2,3-epoxypropyltrimethylammonium chloride is added, the pH is adjusted to 8 - 9, and the reaction is continued for 2 - 3 h to obtain the product.

[0019] In the process of preparing the quaternary ammonium salt-modified organosilicon containing hydroxyl groups in the present invention, first a silane coupling agent is used to form a crosslinked polymer with polyvinyl alcohol, then the quaternary ammonium salt is grafted onto the organosilicon chain, and the obtained quaternary ammonium salt-modified organosilicon containing hydroxyl groups is grafted onto the polyurethane chain segment to form a stable quaternary ammonium salt structure, thereby realizing the antibacterial property of the TPU material.

[0020] The present invention does not specifically limit the reagent capable of adjusting the pH to 8 - 9, for example, it can be sodium hydroxide, sodium bicarbonate, etc.

[0021] In some preferred embodiments, the inorganic antibacterial agent is selected from at least one of silver-loaded glass, zinc-loaded glass, and silver-zinc-loaded glass, preferably silver-zinc-loaded glass.

[0022] Preferably, the carboxyl silicone oil is a side-chain carboxyl silicone oil.

[0023] Preferably, the preparation method of the carboxyl silicone oil modified inorganic antibacterial agent comprises the following steps: mixing an inorganic antibacterial agent, a side-chain carboxyl silicone oil and an ethanol aqueous solution, adding a platinum catalyst under stirring conditions at 60-80 °C, and reacting for 3-5 h to obtain the product.

[0024] Preferably, the mass ratio of the inorganic antibacterial agent, the side-chain carboxyl silicone oil, the ethanol aqueous solution and the platinum catalyst is 1:0.2-0.3:3-6:0.005-0.007.

[0025] Preferably, the mass concentration of the ethanol aqueous solution is 60-70%.

[0026] Glass-supported silver, glass-supported zinc, and glass-supported silver-zinc are selected as inorganic antibacterial agents to act together with quaternary ammonium salts to improve the long-term antibacterial property of the TPU material. In order to enable glass-supported silver, glass-supported zinc, and glass-supported silver-zinc to be evenly distributed in the quaternary ammonium salt modified polyurethane, the present invention first modifies the inorganic antibacterial agent with carboxyl silicone oil. The inorganic antibacterial agent modified by carboxyl silicone oil has good wettability with the quaternary ammonium salt modified polyurethane, which is beneficial to the coating of the quaternary ammonium salt modified polyurethane on the inorganic antibacterial agent. The obtained TPU material not only has long-term antibacterial property at room temperature, but also has good antibacterial property under 90 °C cyclic washing, and no discoloration phenomenon occurs.

[0027] In some preferred embodiments, the long-term antibacterial TPU material may further include 0-0.3 parts of an antioxidant and 0-0.1 parts of an organotin catalyst.

[0028] The present invention does not specifically limit the antioxidant, and examples thereof include antioxidant 1010, antioxidant 168, antioxidant 246, etc.

[0029] The present invention does not specifically limit the organotin catalyst, and examples thereof include dibutyltin dilaurate.

[0030] The second aspect of the present invention provides a preparation method of the above long-term antibacterial TPU material, comprising the following steps: reacting a polyester polyol, a hydroxyl-containing quaternary ammonium salt modified silicone, a diisocyanate, an antioxidant and an organotin catalyst at 70-90 °C for 4-6 h to obtain a quaternary ammonium salt modified polyurethane, adding a carboxyl silicone oil modified inorganic antibacterial agent and mixing evenly, and extruding to obtain the product.

[0031] The third aspect of the present invention provides an application of the above long-term antibacterial TPU material in kitchen utensils, electronic products and sports equipment.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. In the process of preparing the hydroxyl-containing quaternary ammonium salt modified silicone, a cross-linked polymer is first formed by using a silane coupling agent and polyvinyl alcohol, and then the quaternary ammonium salt is grafted onto the silicone chain. The obtained hydroxyl-containing quaternary ammonium salt modified silicone is grafted onto the polyurethane chain segment to form a stable quaternary ammonium salt structure, thereby realizing the antibacterial property of the TPU material.

[0034] 2. The TPU material obtained by using silver-loaded glass, zinc-loaded glass, and silver-zinc-loaded glass as inorganic antibacterial agents and acting together with the quaternary ammonium salt not only has long-term antibacterial property at room temperature but also has good antibacterial property under 90 °C cyclic washing, and no discoloration occurs.

[0035] 3. The cutting boards made of the existing antibacterial TPU materials are often unable to be cleaned by a dishwasher due to temperature limitations. The TPU material obtained by reacting polyester polyol A and polyester polyol B with diisocyanate and acting together with a specific inorganic antibacterial agent still has good antibacterial property, tensile strength retention rate, and no color change after 50 washing cycles at 90 °C. Detailed Embodiments

[0036] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0037] The raw materials used in the following examples and comparative examples are all conventional commercially available raw materials unless otherwise specified.

[0038] Some of the raw materials used in the following examples and comparative examples are as follows:

[0039] The composition of the polyester polyol A is adipic acid, ethylene glycol, and 1,4-butanediol; the functionality is 2, the number average molecular weight is 1000, purchased from Risheng Chemical Co., Ltd., model: P-2710TL.

[0040] The composition of the polyester polyol B is terephthalic acid, oxalic acid, and diethylene glycol, the functionality is 2, the number average molecular weight is 1300, purchased from Risheng Chemical Co., Ltd., model: P-7513A.

[0041] The composition of the polyester polyol C is adipic acid and 1,4-butanediol; the functionality is 2, the number average molecular weight is 1000, purchased from Risheng Chemical Co., Ltd., model: P-2410TL.

[0042] The side-chain carboxyl silicone oil is Shin-Etsu X-22-3701E.

[0043] The terminal carboxyl silicone oil is Shin-Etsu X-22-162C.

[0044] The silver- and zinc-loaded glass is from Guangdong Kepuyin Biotechnology Co., Ltd.

[0045] The zinc-loaded glass is from Guangdong Kepuyin Biotechnology Co., Ltd.

[0046] Example 1

[0047] A long-acting antibacterial TPU material is composed of a carboxyl silicone oil-modified inorganic antibacterial agent and a quaternary ammonium salt-modified polyurethane with a mass ratio of 3:100.

[0048] For the quaternary ammonium salt-modified polyurethane, by mass, the raw materials consist of 40 parts of polyester polyol A, 8 parts of polyester polyol B, 10 parts of isophorone diisocyanate, 3 parts of hydroxyl-containing quaternary ammonium salt-modified silicone, 0.1 part of antioxidant 1010, and 0.03 part of dibutyltin dilaurate.

[0049] The preparation method of the hydroxyl-containing quaternary ammonium salt-modified silicone is as follows: Polyvinyl alcohol, water, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane are heated and reacted at 85 °C for 1.5 h, cooled to 25 °C, 2,3-epoxypropyltrimethylammonium chloride is added, and the pH is adjusted to 8.5 with sodium hydroxide, and the reaction is continued for 2.5 h to obtain it.

[0050] The mass ratio of the polyvinyl alcohol, water, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:40:0.5.

[0051] The mass ratio of the γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 2,3-epoxypropyltrimethylammonium chloride is 1:1.2.

[0052] The preparation method of the carboxyl silicone oil-modified inorganic antibacterial agent is as follows: The silver- and zinc-loaded glass, side-chain carboxyl silicone oil, and ethanol aqueous solution are mixed, and a platinum catalyst is added under stirring at 70 °C, and the stirring reaction is carried out for 4 h to obtain it.

[0053] The mass ratio of the silver- and zinc-loaded glass, side-chain carboxyl silicone oil, ethanol aqueous solution (mass concentration of 70%), and platinum catalyst is 1:0.25:5:0.006.

[0054] The preparation method of the above antibacterial TPU material is as follows: Polyester polyol A, polyester polyol B, hydroxyl-containing quaternary ammonium salt-modified silicone, isophorone diisocyanate, antioxidant 1010, and dibutyltin dilaurate are reacted at 80 °C for 5 h to obtain the quaternary ammonium salt-modified polyurethane, and the carboxyl silicone oil-modified inorganic antibacterial agent is added and mixed evenly, and then extruded to obtain it.

[0055] Example 2

[0056] A long-acting antibacterial TPU material is composed of a carboxyl silicone oil-modified inorganic antibacterial agent and a quaternary ammonium salt-modified polyurethane with a mass ratio of 5:100.

[0057] For the quaternary ammonium salt-modified polyurethane, calculated by mass, the raw materials are composed of 55 parts of polyester polyol A, 12 parts of polyester polyol B, 15 parts of isophorone diisocyanate, 5 parts of hydroxyl-containing quaternary ammonium salt-modified silicone, 0.15 part of antioxidant 1010, and 0.05 part of dibutyltin dilaurate.

[0058] The preparation method of the hydroxyl-containing quaternary ammonium salt-modified silicone is as follows: Polyvinyl alcohol, water, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane are subjected to a heating reaction at 85 °C for 1.5 h, cooled to 25 °C, 2,3-epoxypropyltrimethylammonium chloride is added, and the pH is adjusted to 8.5 with sodium hydroxide, and the reaction is continued for 2.5 h to obtain the product.

[0059] The mass ratio of the polyvinyl alcohol, water, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:40:0.5.

[0060] The mass ratio of the γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 2,3-epoxypropyltrimethylammonium chloride is 1:1.2.

[0061] The preparation method of the carboxyl silicone oil-modified inorganic antibacterial agent is as follows: Glass-supported silver zinc, side-chain carboxyl silicone oil, and an ethanol aqueous solution are mixed, and a platinum catalyst is added under stirring conditions at 70 °C, and the reaction is carried out for 4 h to obtain the product.

[0062] The mass ratio of the glass-supported silver zinc, side-chain carboxyl silicone oil, ethanol aqueous solution (mass concentration of 70%), and platinum catalyst is 1:0.25:5:0.006.

[0063] The preparation method of the above antibacterial TPU material is as follows: Polyester polyol A, polyester polyol B, hydroxyl-containing quaternary ammonium salt-modified silicone, isophorone diisocyanate, antioxidant 1010, and dibutyltin dilaurate are reacted at 80 °C for 5 h to obtain the quaternary ammonium salt-modified polyurethane, and the carboxyl silicone oil-modified inorganic antibacterial agent is added and mixed evenly, and then extruded to obtain the product.

[0064] Example 3

[0065] A long-acting antibacterial TPU material is composed of a carboxyl silicone oil-modified inorganic antibacterial agent and a quaternary ammonium salt-modified polyurethane with a mass ratio of 8:100.

[0066] For the quaternary ammonium salt-modified polyurethane, calculated by mass, the raw materials are composed of 65 parts of polyester polyol A, 20 parts of polyester polyol B, 20 parts of isophorone diisocyanate, 8 parts of hydroxyl-containing quaternary ammonium salt-modified silicone, 0.15 part of antioxidant 1010, and 0.05 part of dibutyltin dilaurate.

[0067] The preparation method of the hydroxyl-containing quaternary ammonium salt modified silicone is as follows: Polyvinyl alcohol, water and γ-(2,3-epoxypropoxy)propyltrimethoxysilane are heated and reacted at 85°C for 1.5 h, cooled to 25°C, 2,3-epoxypropyltrimethylammonium chloride is added, and the pH is adjusted to 8.5 with sodium hydroxide, and the reaction is continued for 2.5 h to obtain the product.

[0068] The mass ratio of the polyvinyl alcohol, water and γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:40:0.5.

[0069] The mass ratio of the γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 2,3-epoxypropyltrimethylammonium chloride is 1:1.2.

[0070] The preparation method of the carboxyl silicone oil modified inorganic antibacterial agent is as follows: Glass supported silver zinc, side chain carboxyl silicone oil and ethanol aqueous solution (mass concentration of 70%) are mixed, and platinum catalyst is added under stirring at 70°C, and the stirring reaction is carried out for 4 h to obtain the product.

[0071] The mass ratio of the glass supported silver zinc, side chain carboxyl silicone oil, ethanol aqueous solution and platinum catalyst is 1:0.25:5:0.006.

[0072] The preparation method of the above antibacterial TPU material is as follows: Polyester polyol A, polyester polyol B, hydroxyl-containing quaternary ammonium salt modified silicone, isophorone diisocyanate, antioxidant 1010 and dibutyltin dilaurate are reacted at 80°C for 5 h to obtain quaternary ammonium salt modified polyurethane, and carboxyl silicone oil modified inorganic antibacterial agent is added and mixed evenly, and then extruded to obtain the product.

[0073] Example 4

[0074] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 2; the difference is that the glass supported silver zinc in the carboxyl silicone oil modified inorganic antibacterial agent is replaced with glass supported zinc of the same mass.

[0075] Comparative Example 1

[0076] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 3; the difference is that polyester polyol B is replaced with polyester polyol A of the same mass; the rest are the same.

[0077] Comparative Example 2

[0078] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 3; the difference is that the antibacterial TPU material is only composed of quaternary ammonium salt modified polyurethane; the rest are the same.

[0079] Comparative Example 3

[0080] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 3; the difference is that the carboxyl silicone oil modified inorganic antibacterial agent is replaced with silver-loaded zinc on glass of the same mass; the rest are the same.

[0081] Comparative Example 4

[0082] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 3; the difference is that the side-chain carboxyl silicone oil is replaced with the same mass of terminal carboxyl silicone oil during the preparation of the carboxyl silicone oil modified inorganic antibacterial agent; the rest are the same.

[0083] Comparative Example 5

[0084] A long-acting antibacterial TPU material, the specific implementation method is the same as that of Example 3; the difference is that the preparation method of the quaternary ammonium salt modified silicone containing hydroxyl groups is as follows: Mix 15 g of dodecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 9 g of toluene diisocyanate, and 0.05 g of dibutyltin dilaurate, and under nitrogen protection, stir and react at 75 °C for 5 h, then add 250 g of bis-terminal hydroxyl polydimethylsiloxane (hydroxyalkyl end-capped, average molecular weight of 5000), and under nitrogen protection, stir and react at 80 °C for 8 h to obtain; the rest are the same.

[0085] The TPU materials of Examples 1-4 and Comparative Examples 1-5 were injection molded at 200 °C to prepare test samples of the same specification (length 50 mm, width 50 mm, thickness 5 mm), and then the following tests were carried out:

[0086] Test Example 1

[0087] The antibacterial performance was tested in accordance with GB / T 31402-2015, and the results are shown in Table 1.

[0088] Table 1

[0089]

[0090]

[0091] Test Example 2

[0092] The test samples were placed in a washing solution at 25 °C (composed of dishwashing liquid and water with a mass ratio of 3:100) for 168 h (7 days), then rinsed with water, dried, and the antibacterial performance was tested in accordance with GB / T 31402-2015, and the results are shown in Table 2.

[0093] Table 2

[0094]

[0095] Test Example 3

[0096] The test sample was placed in a washing solution at 90 °C (composed of dishwashing liquid and water with a mass ratio of 3:100) for 2 h and then rinsed clean with water. This was considered 1 cycle. After 50 cycles: (1) The antibacterial performance was tested in accordance with GB / T 31402-2015; (2) Whether color change occurred was observed; (3) Tensile strength retention rate: (Tensile strength before cycling - Tensile strength after 50 cycles) / 100%, and the tensile strength was tested in accordance with GBT 528-2009; The results are shown in Table 3.

[0097] Table 3

[0098]

[0099]

[0100] As can be seen from Tables 1-3, only the TPU materials of Examples 1-4 have good antibacterial effects, antibacterial effect persistence, small change rate of tensile strength at 90 °C, and no discoloration phenomenon;

[0101] In Comparative Example 1, polyester polyol B was replaced with the same mass of polyester polyol A, resulting in the absence of a rigid aromatic structure in the obtained TPU material, leading to a decrease in thermal stability and a relatively large change rate of tensile strength at 90 °C.

[0102] In Comparative Example 2, the antibacterial TPU material was only composed of quaternary ammonium salt-modified polyurethane, resulting in a decrease in the antibacterial effect and antibacterial effect persistence of the obtained TPU material, and also a relatively large increase in the change rate of tensile strength at 90 °C. It is speculated that the carboxyl silicone oil-modified inorganic antibacterial agent can improve the mechanical strength of the TPU material to a certain extent.

[0103] In Comparative Example 3, the carboxyl silicone oil-modified inorganic antibacterial agent was replaced with the same mass of silver-loaded zinc on glass, which had poor dispersibility in polyurethane, resulting in a decrease in both the antibacterial effect and antibacterial effect persistence of the obtained silicone; and color change occurred, and the change rate of tensile strength increased.

[0104] In Comparative Example 4, the side-chain carboxyl silicone oil was replaced with the same mass of end-carboxyl silicone oil, resulting in a decrease in both the antibacterial effect and antibacterial effect persistence of the obtained silicone; and color change and an increase in the change rate of tensile strength occurred. It is speculated that the single active site and limited spatial distribution of the end-carboxyl silicone oil led to a poor modification effect.

[0105] In Comparative Example 5, the antibacterial effects and antibacterial effect persistence of the silicone prepared by other methods both decreased.

[0106] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than limiting the protection scope of the present invention. Any simple modification or equivalent replacement made by those of ordinary skill in the art to the technical solution of the present invention shall not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A long-lasting antibacterial TPU material, characterized in that: The invention comprises a carboxyl silicone oil modified inorganic antibacterial agent and a quaternary ammonium salt modified polyurethane in a mass ratio of 3-8:100; the quaternary ammonium salt modified polyurethane comprises, by mass, 45-90 parts of polyester polyol, 10-20 parts of diisocyanate and 3-8 parts of quaternary ammonium salt modified silicone containing hydroxyl.

2. The long-lasting antibacterial TPU material according to claim 1, characterized in that: The polyester polyol comprises polyester polyol A and polyester polyol B; the polyester polyol A is composed of adipic acid, ethylene glycol and 1,4-butanediol; the polyester polyol B is composed of terephthalic acid, oxalic acid and diethylene glycol.

3. The long-lasting antibacterial TPU material according to claim 2, characterized in that: The diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

4. The long-lasting antibacterial TPU material according to claim 3, characterized in that: The preparation method of the hydroxyl-containing quaternary ammonium salt-modified organic silicon comprises the following steps: heating polyvinyl alcohol, water and a silane coupling agent for reaction, cooling, adding 2,3-epoxypropyltrimethylammonium chloride, adjusting the pH to alkaline, and continuing the reaction to obtain the organic silicon.

5. The long-lasting antibacterial TPU material according to claim 4, characterized in that: The inorganic antibacterial agent is selected from at least one of glass-supported silver, glass-supported zinc, and glass-supported silver-zinc.

6. The long-lasting antibacterial TPU material according to claim 5, characterized in that: The carboxyl silicone oil is a side chain carboxyl silicone oil.

7. The long-lasting antibacterial TPU material according to claim 6, characterized in that: The preparation method of the carboxyl silicone oil-modified inorganic antibacterial agent comprises the following steps: mixing the inorganic antibacterial agent, the side chain carboxyl silicone oil and an ethanol aqueous solution, adding a platinum catalyst under stirring conditions of 60-80° C., and reacting for 3-5 hours to obtain the antibacterial agent.

8. The long-lasting antibacterial TPU material according to claim 7, characterized in that: The long-acting antibacterial TPU material also includes 0-0.3 parts of antioxidant and 0-0.1 parts of organic tin catalyst.

9. The method for preparing the long-acting antibacterial TPU material according to claim 8, characterized in that: The method comprises the following steps: reacting polyester polyol, hydroxyl-containing quaternary ammonium salt-modified organic silicon, diisocyanate, antioxidant and organic tin catalyst at 70-90° C. for 4-6 hours to obtain quaternary ammonium salt-modified polyurethane, adding carboxyl silicone oil-modified inorganic antibacterial agent, mixing evenly and extruding to obtain the product.

10. Application of the long-acting antibacterial TPU material according to any one of claims 1 to 8 in kitchen utensils, electronic products and sports equipment.

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