A thermoplastic polyurethane elastomer for antibacterial air cushion and its preparation method and application

Abstract

The present invention belongs to the field of C08G technology, and more specifically relates to a thermoplastic polyurethane elastomer for antibacterial air cushions, and a preparation method and application thereof. A thermoplastic polyurethane elastomer for antibacterial air cushions, the raw materials for preparing the thermoplastic polyurethane elastomer include, by weight percentage: 50-60% polyester polyol, 30-40% isocyanate, 5-10% chain extender, and the remainder of the auxiliary agent is supplemented to 100%. The antibacterial rate of the thermoplastic polyurethane elastomer prepared by the present invention can be as high as 99% or more. When it is used in the shoe material air cushion, it can avoid the infection of bacteria and the like caused by the foot movement, sweating, etc. during use; the thermoplastic polyurethane elastomer prepared by the present invention has good processing performance, and has good tear strength and tensile properties. When it is used in the field of air cushions, it can avoid the damage of the finished product caused by external forces such as tearing and stretching, and improve its service life and use value in the field of shoe material air cushions.

Description

Technical Field

[0001] The present invention belongs to the C08G technical field, and more specifically relates to a thermoplastic polyurethane elastomer for an antibacterial air cushion, a preparation method and an application thereof. Background Art

[0002] Thermoplastic polyurethane elastomer is a commonly used material for air cushions. However, with the advancement of technology, the polyurethane materials commonly used for air cushions at this stage are mostly foamed materials. Through the action of polyols and isocyanates, and the synergistic foaming agent, a material with elastic and soft properties is obtained.

[0003] For example, the Chinese invention patent with the patent number CN110698627A discloses a highly breathable polyurethane sheet insole composite material, in which a insole product with different hardness and breathability is prepared by using polyether polyol and carbodiimide modified isocyanate. However, the insole prepared by the foaming method in the patent has a great influence on the mechanical properties of the prepared material in terms of its foaming density and foaming effect. During long-term use, the air cushion may explode, affecting its use value.

[0004] In order to further ensure the application of polyurethane materials in the field of shoe air cushions, it has become an important research to prepare a polyurethane material that has both mechanical properties and antibacterial properties and also has good transparency and processability. Summary of the invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a thermoplastic polyurethane elastomer for antibacterial air cushions. The raw materials for preparation include, by weight percentage: 50-60% polyester polyol, 30-40% isocyanate, 5-10% chain extender, and auxiliary agents to supplement the balance to 100%.

[0006] In some preferred embodiments, the weight average molecular weight of the polyester polyol is 500 to 2000 g / mol.

[0007] In some preferred embodiments, the weight average molecular weight of the polyester polyol is 800 to 1200 g / mol.

[0008] Further preferably, the weight average molecular weight of the polyester polyol is 1000 g / mol.

[0009] In some preferred embodiments, the polyester polyol is an aliphatic polyester polyol and / or an aromatic polyester polyol.

[0010] In some preferred embodiments, the polyester polyol is an aliphatic polyester polyol.

[0011] More preferably, the aliphatic polyester polyol is polybutylene adipate.

[0012] Polybutylene adipate, model: P916124, was purchased from the official website of Shanghai McLean Reagent.

[0013] In some preferred embodiments, the chain extender includes but is not limited to at least one of 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, sorbitol, and ethylenediamine.

[0014] More preferably, the chain extender is 1,4-butanediol.

[0015] In some preferred embodiments, the auxiliary agents include antibacterial agents, antioxidants, lubricants, and stabilizers.

[0016] In some preferred embodiments, the antioxidant is antioxidant 626 and antioxidant 1010.

[0017] In some preferred embodiments, the weight ratio of the antioxidant 626 to the antioxidant 1010 is 1:(1-4);

[0018] Further preferably, the weight ratio of the antioxidant 626 to the antioxidant 1010 is 1:2.

[0019] In some preferred embodiments, the lubricant includes but is not limited to E wax and C wax.

[0020] In some preferred embodiments, the weight ratio of C wax in E wax is (1-3):1.

[0021] Further preferably, the weight ratio of C wax in E wax is 2:1.

[0022] In some preferred embodiments, the stabilizer is carbodiimide.

[0023] In some preferred embodiments, the raw materials for preparation further include 2-methyl-1,3-propanediol, the weight percentage of which is 0.5-1%.

[0024] In some preferred embodiments, the weight ratio of the 2-methyl-1,3-propanediol to the chain extender is 1:(5-20).

[0025] More preferably, the weight ratio of the 2-methyl-1,3-propanediol to the chain extender is 1:(10-20).

[0026] During the experiment, after a large number of creative experimental explorations by the applicant, it was found that in this system, the addition of 2-methyl-1,3-propanediol, especially in synergy with the chain extender, can greatly improve the transparency of the prepared material, especially when the weight ratio of 2-methyl-1,3-propanediol to the chain extender 1,4-butanediol is 1:(10-20), it can be ensured that in the process of preparing the material, the small molecule substances are promoted to play the role of crystal nuclei in the polyurethane system, the number of crystal nuclei in the system is increased, the number of microcrystals is increased, and the strong interaction between the ester group and the active group between the molecules is enhanced, thereby destroying the regularity of the system and improving its transparency, and the transparency reaches more than 5mm.

[0027] The second aspect of the present invention provides a method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion, comprising the following steps:

[0028] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0029] 2) Then, add the auxiliary agent to the pouring head after the initial mixing, mix evenly, and then send it to a twin-screw reaction extruder to further mix evenly and carry out chemical reaction, and then post-process to obtain the product.

[0030] The third aspect of the present invention provides an application of a thermoplastic polyurethane elastomer for antibacterial air cushions, which is used in the field of shoe air cushions.

[0031] Beneficial effects: The thermoplastic polyurethane elastomer for antibacterial air cushion provided by the present invention has the following advantages:

[0032] 1. The antibacterial rate of the thermoplastic polyurethane elastomer prepared by the present invention can be as high as 99% or more. When it is used in a shoe air cushion, it can avoid bacterial infection caused by excessive heat and sweating during foot exercise;

[0033] 2. The thermoplastic polyurethane elastomer provided by the present invention has good transparency, and the transparency result is above 5mm;

[0034] 3. The thermoplastic polyurethane elastomer prepared by the present invention has good processing performance, and has good tear strength and tensile properties. When used in the field of air cushions, it can avoid the damage of the finished product caused by external forces such as tearing and stretching, thereby improving its service life and use value in the field of shoe air cushions. DETAILED DESCRIPTION

[0035] Example

[0036] Example 1

[0037] A thermoplastic polyurethane elastomer for antibacterial air cushion, the raw materials for preparation thereof include, by weight percentage, 55% polyester polyol, 35% isocyanate, 6% chain extender, 0.6% 2-methyl-1,3-propylene glycol, and auxiliary agents to supplement the balance to 100%.

[0038] The polyester polyol is polybutylene adipate, with a weight average molecular weight of 1000 g / mol, model: P916124, purchased from the official website of Shanghai McLean Reagent.

[0039] The isocyanate is diphenylmethane-4,4'-diisocyanate;

[0040] The chain extender is 1,4-butanediol;

[0041] The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer;

[0042] The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%, purchased from Kangye Biotechnology (Dongguan) Co., Ltd.;

[0043] The antioxidants are antioxidant 626 and antioxidant 1010, the weight percentage of antioxidant 626 is 0.3%, and the weight percentage of antioxidant 1010 is 0.6%;

[0044] The stabilizer is carbodiimide, with a weight percentage of 0.4%;

[0045] The lubricant is supplemented to 100% by weight, including E wax and C wax, with a weight ratio of 2:1, purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0046] A method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion comprises the following steps:

[0047] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0048] 2) Adding additives and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mixing evenly, and then transferring to a twin-screw reaction extruder, adding C wax through the twin-screw reaction extruder, further mixing evenly and reacting chemically, and post-processing to obtain the product.

[0049] Example 2

[0050] A thermoplastic polyurethane elastomer for antibacterial air cushion, the raw materials for preparation thereof include, by weight percentage, 55% polyester polyol, 35% isocyanate, 6% chain extender, 0.6% 2-methyl-1,3-propylene glycol, and auxiliary agents to supplement the balance to 100%.

[0051] The polyester polyol is polybutylene adipate, with a weight average molecular weight of 2000 g / mol, model: P916125, purchased from the official website of Shanghai McLean Reagent.

[0052] The isocyanate is diphenylmethane-4,4'-diisocyanate;

[0053] The chain extender is 1,4-butanediol;

[0054] The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer;

[0055] The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%, purchased from Kangye Biotechnology (Dongguan) Co., Ltd.;

[0056] The antioxidants are antioxidant 626 and antioxidant 1010, the weight percentage of antioxidant 626 is 0.3%, and the weight percentage of antioxidant 1010 is 0.6%;

[0057] The stabilizer is carbodiimide, with a weight percentage of 0.4%;

[0058] The lubricant is supplemented to 100% by weight, including E wax and C wax, with a weight ratio of 2:1, purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0059] A method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion comprises the following steps:

[0060] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0061] 2) Adding additives and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mixing evenly, and then transferring to a twin-screw reaction extruder, adding C wax through the twin-screw reaction extruder, further mixing evenly and reacting chemically, and post-processing to obtain the product.

[0062] Example 3

[0063] A thermoplastic polyurethane elastomer for antibacterial air cushions is prepared from raw materials, which include, by weight percentage, 55% polyester polyol, 35% isocyanate, 6% chain extender, and auxiliary agents to supplement the balance to 100%.

[0064] The polyester polyol is polybutylene adipate, with a weight average molecular weight of 1000 g / mol, model: P916124, purchased from the official website of Shanghai McLean Reagent.

[0065] The isocyanate is diphenylmethane-4,4'-diisocyanate;

[0066] The chain extender is 1,4-butanediol;

[0067] The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer;

[0068] The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%, purchased from Kangye Biotechnology (Dongguan) Co., Ltd.;

[0069] The antioxidants are antioxidant 626 and antioxidant 1010, the weight percentage of antioxidant 626 is 0.3%, and the weight percentage of antioxidant 1010 is 0.6%;

[0070] The stabilizer is carbodiimide, with a weight percentage of 0.4%;

[0071] The lubricant is supplemented to 100% by weight, including E wax and C wax, with a weight ratio of 2:1, purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0072] A method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion comprises the following steps:

[0073] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0074] 2) Adding additives and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mixing evenly, and then transferring to a twin-screw reaction extruder, adding C wax through the twin-screw reaction extruder, further mixing evenly and reacting chemically, and post-processing to obtain the product.

[0075] Example 4

[0076] A thermoplastic polyurethane elastomer for antibacterial air cushion, the raw materials for preparation thereof include, by weight percentage, 55% polyester polyol, 35% isocyanate, 6% chain extender, 0.6% 2-methyl-1,3-propylene glycol, and auxiliary agents to supplement the balance to 100%.

[0077] The polyester polyol is polybutylene adipate, with a weight average molecular weight of 1000 g / mol, model: P916124, purchased from the official website of Shanghai McLean Reagent.

[0078] The isocyanate is diphenylmethane-4,4'-diisocyanate;

[0079] The chain extender is 1,4-butanediol;

[0080] The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer;

[0081] The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%, purchased from Kangye Biotechnology (Dongguan) Co., Ltd.;

[0082] The antioxidant is antioxidant 1010, and its weight percentage is 0.9%;

[0083] The stabilizer is carbodiimide, with a weight percentage of 0.4%;

[0084] The lubricant is supplemented to 100% by weight, including E wax and C wax, with a weight ratio of 2:1, purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0085] A method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion comprises the following steps:

[0086] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0087] 2) Adding additives and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mixing evenly, and then transferring to a twin-screw reaction extruder, adding C wax through the twin-screw reaction extruder, further mixing evenly and reacting chemically, and post-processing to obtain the product.

[0088] Example 5

[0089] A thermoplastic polyurethane elastomer for antibacterial air cushion, the raw materials for preparation thereof include, by weight percentage, 55% polyester polyol, 35% isocyanate, 6% chain extender, 0.6% 2-methyl-1,3-propylene glycol, and auxiliary agents to supplement the balance to 100%.

[0090] The polyester polyol is polybutylene adipate, with a weight average molecular weight of 1000 g / mol, model: P916124, purchased from the official website of Shanghai McLean Reagent.

[0091] The isocyanate is diphenylmethane-4,4'-diisocyanate;

[0092] The chain extender is 1,4-butanediol;

[0093] The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer;

[0094] The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%, purchased from Kangye Biotechnology (Dongguan) Co., Ltd.;

[0095] The antioxidants are antioxidant 626 and antioxidant 1010, the weight percentage of antioxidant 626 is 0.3%, and the weight percentage of antioxidant 1010 is 0.6%;

[0096] The stabilizer is carbodiimide, with a weight percentage of 0.4%;

[0097] The weight of the lubricant is supplemented to 100%, and the lubricant is E wax purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0098] A method for preparing a thermoplastic polyurethane elastomer for an antibacterial air cushion comprises the following steps:

[0099] 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring;

[0100] 2) Add the auxiliary agent and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mix them evenly, and then transfer them to a twin-screw reaction extruder to further mix them evenly and carry out chemical reaction, and then post-treat them to obtain the product.

[0101] Performance Testing:

[0102] The thermoplastic polyurethane elastomer prepared in Example 1 of the present application was used for hardness, softening point, tensile strength, tear strength, elongation at break, and antibacterial performance tests, and the test results are recorded in the table below.

[0103] Table 1:

[0104] Test Type Test Standards / Methods Example 1 Shore hardness ASTM D2240 95A Softening point(℃) CFT-500D Rheometer 169.1 Tensile strength(MPa) ASTM D412 47 Elongation at break (%) ASTM D412 500 Tear strength (kN / m) ASTM D624 142 Antibacterial rate (%) GB / T31402-2015 99

[0105] The elastomers prepared in Examples 1-5 were used for transparency testing. The testing method was visual inspection. The prepared materials were made into sheets of different thicknesses, and the maximum thickness that could be seen through was observed. The maximum thickness of transparency was recorded in Table 2 below.

[0106] Table 2:

[0107]

[0108]

Claims

1. A thermoplastic polyurethane elastomer for antibacterial air cushion, the raw materials for preparation thereof, calculated by weight percentage, include: Polyester polyol 55%, isocyanate 35%, chain extender 6%, 2-methyl-1,3-propylene glycol 0.6%, and additives to make up the balance to 100%; The polyester polyol is polybutylene adipate, and the weight average molecular weight is 1000 g / mol; The isocyanate is diphenylmethane-4,4'-diisocyanate; The chain extender is 1,4-butanediol; The auxiliary agents include: antibacterial agent, antioxidant, lubricant, stabilizer; The antibacterial agent is a silver ion antibacterial agent, with a weight percentage of 1.5%; The antioxidants are antioxidant 626 and antioxidant 1010, the weight percentage of antioxidant 626 is 0.3%, and the weight percentage of antioxidant 1010 is 0.6%; The stabilizer is carbodiimide, with a weight percentage of 0.4%; The lubricant is supplemented to 100% by weight, including E wax and C wax, and the weight ratio is 2:1; The method for preparing the thermoplastic polyurethane elastomer for the antibacterial air cushion comprises the following steps: 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring; 2) Add the auxiliary agent and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mix them evenly, and then transfer them to the twin-screw reaction extruder. Add the C wax through the twin-screw reaction extruder to further mix them evenly and react chemically, and then post-treat them to obtain the product.

2. A method for preparing the thermoplastic polyurethane elastomer for antibacterial air cushion according to claim 1, characterized in that: The following steps are involved: 1) The polyester polyol, isocyanate and chain extender are accurately metered into the pouring head by a metering pump and initially mixed under high-speed stirring; 2) Add the auxiliary agent and 2-methyl-1,3-propanediol to the pouring head after the initial mixing, mix them evenly, and then transfer them to the twin-screw reaction extruder. Add the C wax through the twin-screw reaction extruder to further mix them evenly and react chemically, and then post-treat them to obtain the product.

3. An application of the thermoplastic polyurethane elastomer for antibacterial air cushion according to claim 1, characterized in that: Used in the field of shoe air cushions.

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