High density pu material composition for insole and method for preparing the same

Abstract

The application discloses a high-density PU material composition for insoles and a preparation method thereof. The composition is composed of the following components: polyester polyol 80-120 parts; polyether polyol 50-70 parts; polyisocyanate 30-50 parts; physical foaming agent 1-5 parts; first chain extender 3-8 parts; second chain extender 1-4 parts; polyamide short fiber 3-8 parts; and antibacterial agent 0.1-2 parts. The first chain extender is an alcohol chain extender, and the second chain extender is an oxygen-containing heterocyclic chain extender. The composition is prepared by using the compounding effect of the alcohol first chain extender and the oxygen-containing heterocyclic second chain extender. The first chain extender can prolong the molecular chain, improve the molecular weight and mechanical strength of the material, the second chain extender can significantly improve the hydrolysis resistance and dynamic performance of the material, the crosslinking density is optimized, the elasticity and durability are balanced, and the polyamide short fiber, the physical foaming agent and the antibacterial agent and other materials are further used to further improve the shock absorption, antibacterial and air permeability of the material.

Description

Technical Field

[0001] This invention relates to the field of insole technology, and more particularly to a high-density PU material composition for insoles and its preparation method. Background Technology

[0002] Insoles are linings placed inside shoes, directly contacting the soles of the feet. Their main functions include sweat and cold protection, reducing friction, moisture wicking, warmth, and adjusting foot support. They are made from various materials, such as cloth, leather, silicone, and felt, each emphasizing different functions. For example, felt excels at moisture wicking, while silicone effectively relieves pressure on the soles of the feet. In addition, insoles often carry cultural connotations; for instance, traditional hand-embroidered insoles often symbolize wealth and celebration. Modern sports insoles prioritize functionality, such as orthotics, shock absorption, antibacterial properties, and breathability, to meet the needs of professional sports.

[0003] Commonly used materials for insoles include EVA, polyurethane (PU), and silicone. EVA is lightweight and elastic, but has poor breathability and is easily deformed; silicone has excellent shock absorption, but poor breathability and is relatively thick. Currently, the main problems with traditional PU materials for insoles are as follows: (1) Easy deformation and performance degradation: After long-term use, PU materials are prone to collapse and deformation in areas of concentrated pressure (such as the arch and heel), and the cushioning performance is significantly reduced; (2) Poor breathability: Its dense molecular structure leads to poor breathability, making it difficult for foot sweat to evaporate, which easily creates a stuffy and humid environment; (3) Insufficient durability: After 3-6 months of use, the cushioning performance of ordinary PU insoles may decrease by more than 30%, requiring frequent replacement. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, one of the objectives of this invention is to provide a high-density PU material composition for insoles to solve the aforementioned problems of the conventional technology.

[0005] The second objective of this invention is to provide a method for preparing a high-density PU material composition for shoe insoles, which is easy to produce and can be widely promoted.

[0006] One of the objectives of this invention is achieved through the following technical solution: A high-density PU material composition for shoe insoles, comprising the following components in parts by weight: Polyester polyol 80-120 parts; polyether polyol 50-70 parts; polyisocyanate 30-50 parts; physical foaming agent 1-5 parts; first chain extender 3-8 parts; second chain extender 1-4 parts; polyamide short fiber 3-8 parts; antibacterial agent 0.1-2 parts, wherein the first chain extender is an alcohol chain extender and the second chain extender is an oxygen-containing heterocyclic chain extender.

[0007] In this invention, by employing the combined action of an alcohol-based first chain extender and an oxygen-containing heterocyclic second chain extender, the first chain extender, as the basic chain extender, can extend the molecular chain, increase the molecular weight and mechanical strength of the material, and at the same time, its linear structure endows polyurethane with good elasticity, abrasion resistance and tear resistance. The second chain extender enhances the cohesive energy through the hydrogen bond network of the oxygen heterocyclic structure, significantly improves the hydrolysis resistance and dynamic performance of the material, optimizes the crosslinking density, balances elasticity and durability, and meets the high density and high resilience requirements of insoles. In addition, with the combined action of polyamide short fibers, physical foaming agents and antibacterial agents, the shock absorption, antibacterial and breathability properties of the material are further improved.

[0008] Furthermore, the alcohol chain extender is one or more of 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and neopentyl glycol, and the oxygen-containing heterocyclic chain extender is one or more of 3,4-furandicarboxylic acid, 2-methylfuran-3,4-dicarboxylic acid, 2,5-dimethylfuran-3,4-dicarboxylic acid, 2,5-dicarboxylic acid dicarboxylic acid, 2-phenylfuran-3,4-dicarboxylic acid, 2-(4-methoxyphenyl)-3,4-furandicarboxylic acid, 2,5-diphenylfuran-3,4-dicarboxylic acid, and [2,2'-bifuran]-5,5'-dicarboxylic acid.

[0009] Furthermore, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol and castor oil-based polyester polyol in a mass ratio of 1:(0.2-0.4):(0.3-0.6).

[0010] In this invention, a compound system of polycaprolactone polyol, polycarbonate diol and castor oil-based polyester polyol is used to balance the mechanical strength and hydrolysis resistance of the material through the synergistic effect of different molecular structures.

[0011] Furthermore, the polycaprolactone polyol has a weight-average molecular weight of 1000-2000 and an average hydroxyl functionality of 2.5-2.8. Preferably, the polycaprolactone polyol is one or more of the following: ethylene glycol polycaprolactone polyol, 1,4-butanediol polycaprolactone polyol, diethylene glycol polycaprolactone polyol, and neopentyl glycol polycaprolactone polyol.

[0012] Furthermore, the weight-average molecular weight of the castor oil-based polyester polyol is 1500-2200, and the average hydroxyl functionality is 2.5-2.8.

[0013] Furthermore, the polyether polyol is composed of polycaprolactone polyol, polycarbonate diol and castor oil-based polyester polyol in a mass ratio of 1:(0.2-0.3):(0.5-0.6).

[0014] Furthermore, the polyether polyol is composed of polytetrahydrofuran ether and hydroxy disulfide in a mass ratio of 1:(0.5-0.7).

[0015] In this invention, a compound system of polytetrahydrofuran ether and hydroxy disulfide is used to give the material self-healing ability.

[0016] Furthermore, the weight-average molecular weight of polytetrahydrofuran ether is 1000-1500, and the average hydroxyl functionality is 2.5-2.8.

[0017] Furthermore, the hydroxy disulfide is a bis(10-hydroxydecyl) disulfide and / or a bis(11-hydroxyundecyl) disulfide.

[0018] Furthermore, the polyether polyol is composed of polytetrahydrofuran ether and hydroxy disulfide in a mass ratio of 1:(0.5-0.6).

[0019] Furthermore, the polyisocyanate is toluene diisocyanate and / or isophorone diisocyanate.

[0020] Furthermore, the physical foaming agent is CO2, which enables the system to form a microporous structure, optimizing air permeability and lightweight while maintaining high density characteristics.

[0021] Furthermore, the monofilament diameter of polyamide short fibers is 8-15 μm.

[0022] Furthermore, the antibacterial agent is alkyl dimethyl benzyl ammonium chloride and / or dialcyl dimethyl ammonium chloride.

[0023] The second objective of this invention is achieved by the following technical solution: A method for preparing a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Add polyester polyol and polyether polyol to the reactor and stir and mix them under vacuum conditions of 75℃-90℃ to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2-3 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 80℃-95℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants and form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 30-100μm.

[0024] Furthermore, the preparation method also includes the following steps: S6: Inject the composition obtained in step S5 into a mold and mold it at 100-120℃ and 10-15MPa pressure for 5-10 minutes to ensure complete cross-linking reaction. Then, use microwave molding process for secondary foaming. After demolding, place it in an oven at 50-60℃ for 20-24 hours to mature. Cut and surface treat it according to the insole design requirements.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The high-density PU material composition for insoles of the present invention utilizes the combined action of an alcohol-based first chain extender and an oxygen-containing heterocyclic second chain extender. The first chain extender, as a basic chain extender, can extend the molecular chain, increase the molecular weight and mechanical strength of the material, and at the same time, its linear structure endows polyurethane with good elasticity, abrasion resistance and tear resistance. The second chain extender enhances the cohesive energy through the hydrogen bond network of the oxygen heterocyclic structure, significantly improves the hydrolysis resistance and dynamic performance of the material, optimizes the crosslinking density, balances elasticity and durability, and meets the requirements of high density and high resilience for insoles. In addition, the combination of polyamide short fibers, physical foaming agents and antibacterial agents further improves the shock absorption, antibacterial and breathability properties of the material.

[0026] 2. This invention employs a compound system of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol. Through the synergistic effect of different molecular structures, the mechanical strength and hydrolysis resistance of the material are balanced.

[0027] 3. This invention uses a compound system of polytetrahydrofuran ether and hydroxy disulfide to give the material self-healing ability. Detailed Implementation

[0028] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. The raw materials used in the embodiments are all commercially available; unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. Example 1

[0029] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0030] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0031] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.4. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 2

[0032] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0033] The composition comprises the following components in parts by weight: 80 parts polyester polyol; 50 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0034] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 3

[0035] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0036] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 3 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0037] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 4

[0038] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0039] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 3 parts first chain extender; 4 parts second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0040] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.5. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 5

[0041] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0042] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0043] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.4:0.6. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 6

[0044] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0045] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0046] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.7. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride. Example 7

[0047] The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0048] The composition comprises the following components in parts by weight: 100 parts polyester polyol; 60 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 6 parts first chain extender; 2 parts second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,6-hexanediol and the second chain extender is 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid.

[0049] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(11-hydroxyundecyl) disulfide. The polyisocyanate is isophorone diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0050] Comparative Example 1 The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first pre-dispersed chain extender to the prepolymer, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactant; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0051] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 9 parts first chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol.

[0052] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0053] Comparative Example 2 The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the second chain extender to obtain the pre-dispersed second chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the pre-dispersed second chain extender to the prepolymer sequentially, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactant; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0054] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 9 parts second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the second chain extender is 3,4-furandicarboxylic acid.

[0055] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0056] Comparative Example 3 The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0057] The composition comprises the following components in parts by weight: 120 parts polyester polyol; 70 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 15 parts second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0058] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0059] Comparative Example 4 The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0060] The composition comprises the following components in parts by weight: 200 parts polyester polyol; 30 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0061] In the above composition, the polyester polyol is composed of polycaprolactone polyol and castor oil-based polyester polyol in a mass ratio of 1:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is composed of polytetrahydrofuran ether and hydroxyl disulfide in a mass ratio of 1:0.5. The polytetrahydrofuran ether has a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The hydroxyl disulfide is bis(10-hydroxydecyl) disulfide. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0062] Comparative Example 5 The preparation of a high-density PU material composition for shoe insoles includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Polyester polyol and polyether polyol are added to the reactor and stirred and mixed under vacuum at 85°C to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 90℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants to form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 50μm. S6: The composition obtained in step S5 is injected into a mold and molded at 120°C and 12MPa pressure for 8 minutes to ensure complete cross-linking reaction. Then, a second foaming process is carried out using microwave molding. After demolding, it is placed in a 60°C oven for 24 hours to mature. Cutting and surface treatment are performed according to the insole design requirements.

[0063] The composition comprises the following components in parts by weight: 60 parts polyester polyol; 200 parts polyether polyol; 30 parts polyisocyanate; 2 parts physical foaming agent; 8 parts first chain extender; 1 part second chain extender; 3 parts polyamide short fiber; 1 part antibacterial agent, wherein the first chain extender is 1,4-butanediol and the second chain extender is 3,4-furandicarboxylic acid.

[0064] In the above composition, the polyester polyol is composed of polycaprolactone polyol, polycarbonate diol, and castor oil-based polyester polyol in a mass ratio of 1:0.2:0.3. The polycaprolactone polyol is an ethylene glycol-based polycaprolactone polyol with a weight-average molecular weight of 1800 and an average hydroxyl functionality of 2.6. The castor oil-based polyester polyol has a weight-average molecular weight of 2000 and an average hydroxyl functionality of 2.8. The polyether polyol is polytetrahydrofuran ether with a weight-average molecular weight of 1200 and an average hydroxyl functionality of 2.5. The polyisocyanate is toluene diisocyanate. The physical foaming agent is CO2. The monofilament diameter of the polyamide short fiber is 10 μm. The antibacterial agent is alkyl dimethyl benzyl ammonium chloride.

[0065] Performance testing 1. Elongation at break: Refer to GB / T528-2009 The elongation at break at 120℃ was determined by preparing the sample into a dumbbell shape with a length of 10 mm and a thickness of 1 mm. The test was conducted using a tensile testing machine at a tensile speed of 200 mm / min.

[0066] 2. Rebound rate: Refer to GB / T6670-2008 The sample was prepared with dimensions of 100 mm in length, 100 mm in width, and 50 mm in height. After standing for 72 hours, the sample was placed horizontally on the rebound hammer. The height from the bottom of the steel ball to the sample surface was adjusted to 460 mm. A 16.3 g steel ball was released, and the maximum rebound height was recorded as an integer. The ball should not hit the wall during the fall or rebound. Three valid rebound values ​​were obtained within 1 minute. Three sets of measurements were taken, and the average value was recorded.

[0067] 3. Air permeability: Refer to GB / T5453-1997 The sample is clamped on the sample frustum, and air is passed through the sample to bring the pressure close to 50 Pa. After 1 minute, the airflow rate is recorded. The calculation formula is: air permeability R = qv / A × 100%; Where qv is the average gas flow rate (dm³) 3 / min), A is the experimental area (cm²) 2 ).

[0068] 4. Wear resistance The wear was measured using a multifunctional material friction behavior tester. The wear material was GCr15 with a diameter of 5 mm, the load was 400 g, the time was 40 min, and the rotation speed was 250 r / min. The wear amount was calculated.

[0069] 5. Antibacterial properties: The antibacterial effect was evaluated in accordance with GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method"; Escherichia coli was selected as the bacterial species for antibacterial performance testing. The inhibition rate Y = (Wt-Qt) / Wt×100%, where Y is the inhibition rate (%), Wt is the average viable bacterial concentration of the control sample (CFU / ml), and Qt is the average viable bacterial concentration of the insole. After 200 standard washes, the antibacterial durability of the insole was determined.

[0070] 6. The test results are shown in Table 1.

[0071] Table 1 project Elongation at break / % Rebound rate / % Breathability (mm / s) <![CDATA[Wear amount 10 -3 g / N*m]]> Antibacterial rate / % Antibacterial durability rate / % Example 1 413 90.6 95.3 0.78 99.8 99.3 Example 2 402 86.5 97.5 0.98 99.6 95.1 Example 3 393 85.2 98.2 1.35 99.5 94.3 Example 4 428 92.1 92.3 0.89 99.4 96.2 Example 5 419 89.3 94.6 0.72 99.6 98.5 Example 6 409 93.4 94.8 0.82 99.7 99.1 Example 7 405 88.7 92.6 0.86 99.2 93.6 Comparative Example 1 362 76.8 88.3 1.68 99.4 86.5 Comparative Example 2 359 75.1 85.1 1.82 99.6 80.3 Comparative Example 3 328 68.5 70.5 2.11 92.3 82.3 Comparative Example 4 382 80.6 90.3 1.45 96.5 90.5 Comparative Example 5 375 78.6 89.5 1.53 97.2 88.7 The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A high-density PU material composition for shoe insoles, characterized in that, It consists of the following components in parts by weight: Polyester polyol 80-120 parts; polyether polyol 50-70 parts; polyisocyanate 30-50 parts; physical foaming agent 1-5 parts; first chain extender 3-8 parts; second chain extender 1-4 parts; polyamide short fiber 3-8 parts; antibacterial agent 0.1-2 parts, wherein the first chain extender is an alcohol chain extender and the second chain extender is an oxygen-containing heterocyclic chain extender.

2. The high-density PU material composition for insoles according to claim 1, characterized in that, The alcohol chain extender is one or more of 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and neopentyl glycol.

3. The high-density PU material composition for insoles according to claim 1, characterized in that, The oxygen-containing heterocyclic chain extender is one or more of the following: 3,4-furandicarboxylic acid, 2-methylfuran-3,4-dicarboxylic acid, 2,5-dimethylfuran-3,4-dicarboxylic acid, 2,5-dicarboxylic acid acylfuran-3,4-dicarboxylic acid, 2-phenylfuran-3,4-dicarboxylic acid, 2-(4-methoxyphenyl)-3,4-furandicarboxylic acid, 2,5-diphenylfuran-3,4-dicarboxylic acid, and [2,2'-bifuran]-5,5'-dicarboxylic acid.

4. The high-density PU material composition for insoles according to claim 1, characterized in that, The polyester polyol is composed of polycaprolactone polyol, polycarbonate diol and castor oil-based polyester polyol in a mass ratio of 1:(0.2-0.4):(0.3-0.6).

5. The high-density PU material composition for insoles according to claim 4, characterized in that, The polycaprolactone polyol has a weight-average molecular weight of 1000-2000 and an average hydroxyl functionality of 2.5-2.8; the castor oil-based polyester polyol has a weight-average molecular weight of 1500-2200 and an average hydroxyl functionality of 2.5-2.

8.

6. The high-density PU material composition for insoles according to claim 1, characterized in that, The polyether polyol is composed of polytetrahydrofuran ether and hydroxy disulfide in a mass ratio of 1:(0.5-0.7).

7. The high-density PU material composition for insoles according to claim 6, characterized in that, The polytetrahydrofuran ether has a weight-average molecular weight of 1000-1500 and an average hydroxyl functionality of 2.5-2.

8.

8. The high-density PU material composition for insoles according to claim 1, characterized in that, The polyisocyanate is toluene diisocyanate and / or isophorone diisocyanate.

9. The high-density PU material composition for insoles according to claim 1, characterized in that, The physical foaming agent is CO2, the monofilament diameter of the polyamide short fiber is 8-15 μm, and the antibacterial agent is alkyl dimethyl benzyl ammonium chloride and / or dialcyl dimethyl ammonium chloride.

10. A method for preparing a high-density PU material composition for shoe insoles as described in any one of claims 1-9, characterized in that, Includes the following steps: S1: Polyamide short fibers and antibacterial agent are pre-dispersed in the first chain extender to obtain the pre-dispersed first chain extender; S2: Add polyester polyol and polyether polyol to the reactor and stir and mix them under vacuum conditions of 75℃-90℃ to obtain the first mixture; S3: Add polyisocyanate to the first mixture and react for 2-3 hours to obtain the prepolymer; S4: Add the first and second pre-dispersed chain extenders to the prepolymer in sequence, control the temperature at 80℃-95℃, and continue stirring until the reaction is complete to obtain the reactants; S5: Inject a physical foaming agent into the reactants and form a microporous closed-cell structure through a supercritical foaming process. The pore size of the microporous closed-cell structure is 30-100μm.