Rapidly-formed high-wear-resistance transparent polyurethane sole material and preparation method thereof

Abstract

The invention relates to the technical field of sole materials, in particular to a rapidly-formed high-wear-resistance transparent polyurethane sole material and a preparation method thereof. The preparation method comprises the following steps: step 1, uniformly mixing vacuum dehydrated polyester polyol, diphenylmethane diisocyanate, modified silicon dioxide and phosphoric acid under the protection of nitrogen, reacting at 70-80 DEG C for 2-3 hours, cooling and discharging to obtain a component A; 2, uniformly mixing the vacuum dehydrated polyester polyol, bio-based polyol, a chain extender, a catalyst, a foaming agent and a foam stabilizer to obtain a component B; and 3, uniformly mixing the component A and the component B in vacuum, defoaming, pouring into a mold, and demolding after 2-5 minutes to obtain the high-wear-resistance transparent polyurethane sole material which not only has excellent mechanical property, but also has antibacterial property, so that the service life of the high-wear-resistance transparent polyurethane sole material is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of shoe sole materials, specifically a rapid-forming high-wear-resistance transparent polyurethane shoe sole material and its preparation method. BACKGROUND

[0002] With the rapid development of the shoe industry, consumers' demands for shoe sole materials are constantly increasing, especially in terms of wear resistance, transparency, and comfort. Polyurethane (PU) materials have become a popular choice for shoe sole materials due to their excellent physical properties and processing flexibility. Transparent polyurethane shoe soles not only enhance the aesthetic appeal of shoes but also meet the market's demand for fashion and individuality. Furthermore, with the booming development of sports shoes and casual shoes markets, the demand for high-wear-resistance transparent polyurethane shoe soles is increasing.

[0003] Although there are some polyurethane shoe sole materials on the market, their wear resistance often cannot meet the needs of high-strength use, leading to severe wear of the shoe sole in a short period of time and affecting the service life. At the same time, existing transparent polyurethane materials have deficiencies in antibacterial performance, especially in humid environments, where bacteria and fungi are prone to grow, thereby affecting the service life of the shoes and the health of consumers. In addition, existing transparent polyurethane materials often require complex process conditions and a long time in the molding process, resulting in low production efficiency and failing to meet the needs of large-scale production.

[0004] Therefore, we propose a rapid-forming high-wear-resistance transparent polyurethane shoe sole material and its preparation method. SUMMARY

[0005] The purpose of the present application is to provide a rapid-forming high-wear-resistance transparent polyurethane shoe sole material and its preparation method to solve the problems in the prior art.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] A preparation method of a rapid-forming high-wear-resistance transparent polyurethane shoe sole material, comprising the following steps:

[0008] Step one: under nitrogen protection, mix the vacuum-dehydrated polyester polyol, diphenylmethane diisocyanate, modified silica, and phosphoric acid uniformly, and react at 70-80℃ for 2-3h, cool down, discharge, and obtain component A;

[0009] Step two: mix the vacuum-dehydrated polyester polyol, bio-based polyol, chain extender, catalyst, foaming agent, and foam stabilizer uniformly to obtain component B;

[0010] Step three: mix components A and B uniformly under vacuum, degas, and then pour into a mold, remove the mold after 2-5min to obtain the high-wear-resistance transparent polyurethane shoe sole material.

[0011] Further, the A component includes the following weight components: polyester polyol 50-60 parts, diphenylmethane diisocyanate 60-70 parts, modified silica 10-20 parts, phosphoric acid 0.002-0.010 parts.

[0012] Further, the B component includes the following weight components: polyester polyol 50-60 parts, bio-based polyol 30-40 parts, chain extender 3-8 parts, catalyst 1-3 parts, foaming agent 1-3 parts, cell stabilizer 0.5-2.5 parts.

[0013] Further, the preparation method of the modified silica is as follows:

[0014] Step A: Under light-proof conditions, ultrasonic dispersion of nano-silica in a mixed solution of anhydrous ethanol and deionized water, adjust the pH of the system to 4-5, add mercaptopropyl trimethoxysilane, pass nitrogen, stir at room temperature for 22-24 h, after centrifugation, washing and drying, obtain mercapto-nano-silica;

[0015] Step B: Under nitrogen protection, mix triphenylmethane triisocyanate, polymerization inhibitor and acetone uniformly, add double bond containing compound, use dibutyltin dilaurate as catalyst, react at 70-80℃ for 2-3 h, reduce pressure distillation, obtain double bond containing diisocyanate; under nitrogen protection, mix double bond containing diisocyanate, iodomethane and acetone uniformly, react at 50-60℃ for 10-12 h, after reducing pressure distillation and drying, obtain quaternary ammonium isocyanate;

[0016] Step C: Mix mercapto-nano-silica, mercapto-chitosan and quaternary ammonium isocyanate uniformly, add photoinitiator, irradiate with 360-400 nm ultraviolet light for 30-60 min, obtain modified silica.

[0017] Further, in step A, the mass ratio of nano-silica, anhydrous ethanol, deionized water, mercaptopropyl trimethoxysilane is 1:(10-12):(2-4):(0.3-0.5).

[0018] Further, in step B, the triphenylmethane triisocyanate and double bond containing compound are mixed according to the molar ratio of isocyanate and hydroxyl group 3:1.

[0019] Further, the amount of polymerization inhibitor is 0.1-0.3% of the total mass of triphenylmethane triisocyanate and double bond containing compound.

[0020] Further, the amount of dibutyltin dilaurate is 0.3-0.5% of the total mass of triphenylmethane triisocyanate and double bond containing compound.

[0021] Further, the preparation step of the double bond-containing compound is: under nitrogen protection, mixing 4-chloromethylstyrene, diglycolamine and anhydrous ethanol uniformly, adding potassium carbonate, reacting at 40-50℃ for 22-24h, and then filtering and purifying to obtain the double bond-containing compound.

[0022] Further, the mass ratio of the 4-chloromethylstyrene, diglycolamine, anhydrous ethanol and potassium carbonate is 1:(0.30-0.34):(4-6):(0.9-1.0).

[0023] Further, in step B, the mass ratio of the double bond-containing diisocyanate, iodomethane and acetone is 1:(1.5-2.5):(5-10).

[0024] Further, in step C, the mass ratio of the mercapto-modified nanosilica, mercapto-modified chitosan and quaternary ammonium-modified isocyanate is 1:(0.5-1.0):(2-4).

[0025] Further, the preparation step of the mercapto-modified chitosan is: dispersing chitosan in deionized water, adjusting the pH to 6-7 using hydrochloric acid, adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine and mixing uniformly, reacting in the dark for 22-24h, and then dialyzing and drying to obtain the mercapto-modified chitosan.

[0026] Further, the mass ratio of the chitosan, deionized water, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine is 1:100:(7-8):(4.0-4.5):(2-4), and the concentration of the hydrochloric acid is 1 mol / L.

[0027] Further, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the amount thereof is 3-5% of the total mass of the mercapto-modified nanosilica, mercapto-modified chitosan and quaternary ammonium-modified isocyanate.

[0028] Further, the irradiation intensity of the ultraviolet irradiation is 25-35 mW / cm 2 .

[0029] Further, the chain extender is a mixture of one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol and diethylene glycol.

[0030] Further, the foaming agent is pure water.

[0031] Further, the foam stabilizer is dimethyl silicone oil.

[0032] Further, the mass ratio of the A component and the B component is 1:(0.6-0.8).

[0033] Compared with the prior art, the present application has the following advantages:

[0034] The application discloses a kind of rapid prototyping high wear-resistant transparent polyurethane shoe sole material and preparation method thereof, with 4-chloromethyl styrene and diethylene glycol amine as raw material, compound with hydroxyl and styrene type double bond, i.e.

[0035] Finally, under the action of photoinitiator, thiolated nanosilica, thiolated chitosan and the double bond in quaternary ammonium isocyanate are subjected to thiol-ene click reaction, chitosan and quaternary ammonium salt structure are introduced, which significantly improves the antibacterial performance of the material and helps to prevent the growth of bacteria and fungi, thereby improving the hygiene and service life of the shoe; the introduction of isocyanate group enables nanosilica to be uniformly distributed in the long-chain structure of polyurethane macromolecule, significantly enhancing the flexibility and rigidity of polyurethane material and improving the mechanical properties of polyurethane material. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0037] The polyester polyol in the present embodiment is CMA-1044 from Jining Lido Chemical Co., Ltd.; the bio-based polyol is cashew nut shell oil bio-based modified polyol, model FX-9014, from Shandong Mobai Chemical Co., Ltd.; the foam stabilizer is dimethyl silicone oil, model PMX-200; the catalyst is A-33 from Wuhan Jiyesheng Chemical Co., Ltd.; and the nanosilica has a particle size of 20-50 nm.

[0038] The following parts are mass parts unless otherwise specified.

[0039] Example 1: A preparation method of a kind of rapid prototyping high wear-resistant transparent polyurethane shoe sole material, comprising the following processes:

[0040] Step one: under the protection of nitrogen, 50 parts of vacuum dehydrated polyester polyol, 60 parts of diphenyl methane diisocyanate, 10 parts of modified silica and 0.002 parts of phosphoric acid were mixed uniformly, and reacted at 70℃ for 2h, cooled, discharged, and A component was obtained;

[0041] Step two: 50 parts of vacuum dehydrated polyester polyol, 30 parts of bio-based polyol, 3 parts of 1, 4-butanediol, 1 part of catalyst, 1 part of foaming agent and 0.5 parts of foam stabilizer were mixed uniformly to obtain B component;

[0042] Step three: A component and B component were mixed uniformly under vacuum at a mass ratio of 1:0.6, defoamed, and then poured into a mold, demolded after 2min to obtain high wear-resistant transparent polyurethane sole material;

[0043] The preparation method of modified silica is as follows:

[0044] Step A: under the light shielding condition, 10 parts of nano silica was ultrasonically dispersed in a mixed solution of 100 parts of anhydrous ethanol and 20 parts of deionized water, the pH of the system was adjusted to 4, 3 parts of mercaptopropyl trimethoxysilane was added, nitrogen was introduced, and stirring was carried out at room temperature for 22h, and then mercapto nano silica was obtained after centrifugation, washing and drying;

[0045] Step B: under the protection of nitrogen, 4-chloromethyl styrene, diethylene glycol amine and anhydrous ethanol were mixed uniformly, potassium carbonate was added, and the mixture was reacted at 40℃ for 22h to obtain a double bond containing compound; the mass ratio of 4-chloromethyl styrene, diethylene glycol amine, anhydrous ethanol and potassium carbonate was 1:0.3:4:0.9;

[0046] Under the protection of nitrogen, triphenylmethane triisocyanate, hydroquinone and acetone were mixed uniformly, the double bond containing compound was added at a molar ratio of isocyanate group to hydroxyl group of 3:1, and dibutyltin dilaurate was used as a catalyst, and the mixture was reacted at 70℃ for 2h, and then distilled under reduced pressure to obtain a double bond containing diisocyanate; the amount of hydroquinone was 0.1% of the total mass of triphenylmethane triisocyanate and the double bond containing compound, and the amount of dibutyltin dilaurate was 0.3% of the total mass of triphenylmethane triisocyanate and the double bond containing compound; under the protection of nitrogen, 20 parts of double bond containing diisocyanate, 30 parts of iodomethane and 100 parts of acetone were mixed uniformly, and the mixture was reacted at 50℃ for 10h, and then distilled under reduced pressure and dried to obtain a quaternary ammonium isocyanate;

[0047] Step C: 5 parts of chitosan were dispersed in 500 parts of deionized water, 1mol / L hydrochloric acid was used to adjust the pH to 6, and 35 parts of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 20 parts of N-hydroxysuccinimide and 10 parts of L-cysteine were mixed uniformly, and the mixture was reacted in the dark for 22h, and then dialyzed and dried to obtain mercapto chitosan;

[0048] Mix 10 parts of thiolated nanosilica, 5 parts of thiolated chitosan and 20 parts of quaternary ammonium isocyanate uniformly, add 1.05 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, irradiate for 30 min under 360 nm ultraviolet light, the irradiation intensity is 35 mW / cm 2 , to obtain modified silica.

[0049] Example 2: A preparation method of a rapid forming high wear-resistant transparent polyurethane sole material, comprising the following processes:

[0050] Step one: under the protection of nitrogen, mix 55 parts of vacuum dehydrated polyester polyol, 65 parts of diphenyl methane diisocyanate, 15 parts of modified silica and 0.005 parts of phosphoric acid uniformly, react at 75℃ for 2.5h, cool down, discharge, to obtain component A;

[0051] Step two: mix 55 parts of vacuum dehydrated polyester polyol, 35 parts of bio-based polyol, 5 parts of 1,4-butanediol, 2 parts of catalyst, 2 parts of foaming agent and 2 parts of uniform foaming agent uniformly, to obtain component B;

[0052] Step three: mix component A and component B uniformly under vacuum at a mass ratio of 1:0.7, after defoaming, pour into a mold, demold after 4 min, to obtain a high wear-resistant transparent polyurethane sole material;

[0053] The preparation method of the modified silica is as follows:

[0054] Step A: under the light shielding condition, ultrasonically disperse 15 parts of nanosilica in a mixed solution of 165 parts of anhydrous ethanol and 45 parts of deionized water, adjust the pH of the system to 4.5, add 6 parts of mercaptopropyl trimethoxysilane, pass nitrogen, stir at room temperature for 23h, after centrifugation, washing and drying, obtain thiolated nanosilica;

[0055] Step B: under the protection of nitrogen, mix 4-chloromethylstyrene, diglycolamine and anhydrous ethanol uniformly, add potassium carbonate, react at 45℃ for 23h, to obtain a double bond containing compound; the mass ratio of 4-chloromethylstyrene, diglycolamine, anhydrous ethanol and potassium carbonate is 1:0.32:5:0.95;

[0056] Under nitrogen protection, triphenylmethane triisocyanate, hydroquinone and acetone were mixed uniformly, and the compound containing double bond was added in a molar ratio of isocyanate group to hydroxyl group of 3:1, and dibutyltin dilaurate was used as a catalyst to react at 75℃ for 2.5h, and then distilled under reduced pressure to obtain a double-bond-containing diisocyanate; the amount of hydroquinone was 0.2% of the total mass of triphenylmethane triisocyanate and the double-bond-containing compound, and the amount of dibutyltin dilaurate was 0.4% of the total mass of triphenylmethane triisocyanate and the double-bond-containing compound; under nitrogen protection, 45 parts of the double-bond-containing diisocyanate, 90 parts of iodomethane and 450 parts of acetone were mixed uniformly, and reacted at 55℃ for 11h, and then distilled under reduced pressure, dried to obtain a quaternary ammonium isocyanate;

[0057] Step C: 12 parts of chitosan were dispersed in 1200 parts of deionized water, and the pH was adjusted to 6.5 using 1 mol / L hydrochloric acid, and 90 parts of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 50 parts of N-hydroxysuccinimide and 36 parts of L-cysteine were mixed uniformly, and reacted in the dark for 23h, and then dialyzed, dried to obtain thiolated chitosan;

[0058] 15 parts of thiolated nanosilica, 12 parts of thiolated chitosan and 45 parts of quaternary ammonium isocyanate were mixed uniformly, 2.88 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone was added, and irradiated with 380nm ultraviolet light for 40min, and the irradiation intensity was 30mW / cm 2 , to obtain modified silica.

[0059] Example 3: A preparation method of a rapid forming high wear-resistant transparent polyurethane sole material, comprising the following processes:

[0060] Step one: under nitrogen protection, 60 parts of vacuum dehydrated polyester polyol, 60-70 parts of diphenylmethane diisocyanate, 20 parts of modified silica and 0.010 parts of phosphoric acid were mixed uniformly, and reacted at 70-80℃ for 2-3h, cooled, discharged to obtain component A;

[0061] Step two: 60 parts of vacuum dehydrated polyester polyol, 40 parts of bio-based polyol, 8 parts of 1,4-butanediol, 3 parts of catalyst, 3 parts of blowing agent and 2.5 parts of foam stabilizer were mixed uniformly to obtain component B;

[0062] Step three: component A and component B were mixed uniformly in a mass ratio of 1:0.8 under vacuum, defoamed, and then poured into a mold, demolded after 5min to obtain a high wear-resistant transparent polyurethane sole material;

[0063] The preparation method of the modified silica is as follows:

[0064] Step A: Under light protection, 20 parts of nanometer silica was ultrasonically dispersed in a mixed solution of 240 parts of anhydrous ethanol and 80 parts of deionized water, the pH of the system was adjusted to 5, 10 parts of mercaptopropyltrimethoxysilane was added, nitrogen was introduced, and stirring was carried out at room temperature for 24 hours. After centrifugation, washing and drying, mercapto-nanometer silica was obtained;

[0065] Step B: Under nitrogen protection, 4-chloromethylstyrene, diglycolamine and anhydrous ethanol were uniformly mixed, potassium carbonate was added, and the mixture was reacted at 50°C for 24 hours to obtain a double bond-containing compound; the mass ratio of 4-chloromethylstyrene, diglycolamine, anhydrous ethanol and potassium carbonate was 1:0.34:6:1;

[0066] Under nitrogen protection, triphenylmethane triisocyanate, hydroquinone and acetone were uniformly mixed, the double bond-containing compound was added according to a molar ratio of isocyanate group to hydroxyl group of 3:1, and dibutyltin dilaurate was used as a catalyst to react at 80°C for 3 hours. After vacuum distillation, a double bond-containing diisocyanate was obtained; the amount of hydroquinone was 0.3% of the total mass of triphenylmethane triisocyanate and the double bond-containing compound, and the amount of dibutyltin dilaurate was 0.5% of the total mass of triphenylmethane triisocyanate and the double bond-containing compound; under nitrogen protection, 80 parts of the double bond-containing diisocyanate, 200 parts of iodomethane and 800 parts of acetone were uniformly mixed, and the mixture was reacted at 60°C for 12 hours. After vacuum distillation and drying, a quaternary ammonium isocyanate was obtained;

[0067] Step C: Chitosan was dispersed in deionized water, the pH was adjusted to 7 using 1 mol / L hydrochloric acid, and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine were uniformly mixed. The mixture was reacted in the dark for 24 hours. After dialysis and drying, mercapto-chitosan was obtained;

[0068] 20 parts of mercapto-nanometer silica, 20 parts of mercapto-chitosan and 80 parts of quaternary ammonium isocyanate were uniformly mixed, 6 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone was added, and the mixture was irradiated with 400 nm ultraviolet light for 60 minutes at an irradiation intensity of 25 mW / cm 2 , to obtain modified silica.

[0069] Comparative Example 1: A preparation method of a rapid forming high wear-resistant transparent polyurethane sole material, comprising the following processes:

[0070] Compared with Example 2, 5 parts of modified silica was added in the A component of Comparative Example 1, and the other steps were the same as those of Example 2.

[0071] Comparative Example 2: A preparation method of a rapid forming high wear-resistant transparent polyurethane sole material, comprising the following processes:

[0072] The preparation method of the modified silica is as follows:

[0073] Step A: under light-proof conditions, 15 parts of nano-silica are ultrasonically dispersed in a mixed solution of 165 parts of anhydrous ethanol and 45 parts of deionized water, the pH of the system is adjusted to 4.5, 6 parts of mercaptopropyltrimethoxysilane are added, nitrogen is introduced, and stirring is performed at room temperature for 23 hours; after centrifugation, washing and drying, mercapto-nano-silica is obtained;

[0074] Step B: under nitrogen protection, 4-chloromethylstyrene, diglycolamine and anhydrous ethanol are uniformly mixed, potassium carbonate is added, and reaction is performed at 45°C for 23 hours to obtain a double bond-containing compound; the mass ratio of 4-chloromethylstyrene, diglycolamine, anhydrous ethanol and potassium carbonate is 1:0.32:5:0.95;

[0075] Under nitrogen protection, triphenylmethane triisocyanate, hydroquinone and acetone are uniformly mixed, the double bond-containing compound is added in a molar ratio of isocyanate group to hydroxyl group of 3:1, dibutyltin dilaurate is used as a catalyst, and reaction is performed at 75°C for 2.5 hours; after distillation under reduced pressure, a double bond-containing diisocyanate is obtained; the amount of hydroquinone is 0.2% of the total mass of triphenylmethane triisocyanate and the double bond-containing compound, and the amount of dibutyltin dilaurate is 0.4% of the total mass of triphenylmethane triisocyanate and the double bond-containing compound; under nitrogen protection, 45 parts of the double bond-containing diisocyanate, 90 parts of iodomethane and 450 parts of acetone are uniformly mixed, and reaction is performed at 55°C for 11 hours; after distillation under reduced pressure and drying, a quaternary ammonium isocyanate is obtained;

[0076] Step C: 15 parts of mercapto-nano-silica and 45 parts of the quaternary ammonium isocyanate are uniformly mixed, 2.88 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone is added, and irradiation is performed under 380 nm ultraviolet light for 40 minutes at an irradiation intensity of 30 mW / cm2 to obtain modified silica;

[0077] Compared with Example 2, Comparative Example 2 does not introduce mercapto-chitosan, and other steps are the same as those of Example 2.

[0078] Comparative Example 3: a preparation method of a rapid forming high-wear-resistant transparent polyurethane sole material, comprising the following processes:

[0079] The preparation method of the modified silica is as follows:

[0080] Step A: under light-proof conditions, 15 parts of nano-silica are ultrasonically dispersed in a mixed solution of 165 parts of anhydrous ethanol and 45 parts of deionized water, the pH of the system is adjusted to 4.5, 6 parts of mercaptopropyltrimethoxysilane are added, nitrogen is introduced, and stirring is performed at room temperature for 23 hours; after centrifugation, washing and drying, mercapto-nano-silica is obtained;

[0081] Step B: 12 parts of chitosan was dispersed in 1200 parts of deionized water, using 1 mol / L hydrochloric acid to adjust the pH to 6.5, 90 parts of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 50 parts of N-hydroxysuccinimide and 36 parts of L-cysteine were added and mixed uniformly, and reacted in the dark for 23 h, and then subjected to dialysis and drying to obtain thiolated chitosan;

[0082] 15 parts of thiolated nanosilica and 12 parts of thiolated chitosan were mixed uniformly to obtain modified silica;

[0083] Compared with Example 2, Comparative Example 3 does not introduce quaternary ammonium isocyanate, and the other steps are the same as those of Example 2.

[0084] Experiment: The high-wear-resistant transparent polyurethane sole material obtained in Examples 1-3 and Comparative Examples 1-3 was taken to prepare a sample, and the performance of the sample was detected and the detection results were recorded:

[0085] Wear resistance test: The wear resistance test was performed according to GB / T 9867-2008 "Determination of abrasion resistance of vulcanized or thermoplastic rubber (rotary drum abrasion machine method)", the experimental steps were as follows: the sample was in the shape of a cylinder with a diameter of 16 mm and a height of 6 mm, and a vertical force of 10 N was used to press the sample tightly on the roller, the test was started, and the sample moved along the transverse direction of the roller, when the wear distance reached 40 m, the machine was automatically stopped, the mass difference before and after abrasion was measured, and the sample density was measured by the drainage method; the abrasion volume (unit: mm 3 ) was calculated according to the mass loss and the density.

[0086] Antibacterial performance test: the sample size was 5 mm x 5 mm, and the sterilized sample was placed in a triangular flask containing E. coli and S. aureus bacterial solution, respectively, and oscillated at 24℃ and 180 r / min for 24 h, the viable bacterial concentration of the bacterial solution before and after oscillation was measured, and the antibacterial rate was calculated.

[0087] The test results are shown in Table 1.

[0088] Table 1 Performance test results of high-wear-resistant transparent polyurethane sole material

[0089]

[0090] According to the data in the above table, the following conclusions can be clearly obtained:

[0091] From Examples 1-3 and Comparative Examples 1-3, it can be seen that the polyurethane sole material prepared by the present application not only has excellent wear resistance, but also has excellent antibacterial performance.

[0092] It will be apparent to those skilled in the art that the application is not limited to the details of the above-exemplified embodiments and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. The embodiments should therefore be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the above description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A method for the preparation of a rapid prototyping high abrasion transparent polyurethane sole material, characterized by: Comprising the following steps: Step one: under the protection of nitrogen, the vacuum dehydrated polyester polyol, diphenyl methane diisocyanate, modified silica and phosphoric acid are mixed uniformly, and reacted at 70-80 DEG C for 2-3h, cooled, discharged, to obtain A component; Step two: the vacuum dehydrated polyester polyol, bio-based polyol, chain extender, catalyst, foaming agent and foam stabilizer are mixed uniformly to obtain B component; Step three: A component and B component are mixed uniformly under vacuum, defoamed, and then poured into a mold, demolded after 2-5 min, to obtain high wear-resistant transparent polyurethane sole material.

2. The method for preparing a rapid prototyping high-wear-resistant transparent polyurethane shoe sole material according to claim 1, characterized in that: The A component comprises the following components by weight: polyester polyol 50-60 parts, diphenyl methane diisocyanate 60-70 parts, modified silica 10-20 parts, and phosphoric acid 0.002-0.010 parts.

3. The method for preparing a rapid prototyping high-wear-resistant transparent polyurethane shoe sole material according to claim 2, characterized in that: The preparation method of the modified silica is as follows: Step A: under light-proof conditions, the nano-silica is ultrasonically dispersed in a mixed solution of anhydrous ethanol and deionized water, the pH of the system is adjusted to 4-5, mercaptopropyl trimethoxysilane is added, nitrogen is introduced, and stirring is carried out at room temperature for 22-24h, after centrifugation, washing and drying, mercapto-nano-silica is obtained; Step B: under the protection of nitrogen, triphenylmethane triisocyanate, polymerization inhibitor and acetone are mixed uniformly, a double bond-containing compound is added, dibutyltin dilaurate is used as a catalyst, and reaction is carried out at 70-80 DEG C for 2-3h, and then vacuum distillation is carried out to obtain a double bond-containing diisocyanate; under the protection of nitrogen, the double bond-containing diisocyanate, iodomethane and acetone are mixed uniformly, and reaction is carried out at 50-60 DEG C for 10-12h, and then vacuum distillation and drying are carried out to obtain a quaternary ammonium isocyanate; Step C: the mercapto-nano-silica, mercapto-chitosan and quaternary ammonium isocyanate are mixed uniformly, a photoinitiator is added, and then ultraviolet irradiation is carried out at 360-400nm for 30-60min to obtain modified silica.

4. The method for preparing a rapid prototyping high wear-resistant transparent polyurethane shoe sole material according to claim 3, characterized in that: In step A, the mass ratio of the nano-silica to anhydrous ethanol, deionized water and mercaptopropyl trimethoxysilane is 1:(10-12):(2-4):(0.3-0.5).

5. The method for preparing a rapid prototyping high wear-resistant transparent polyurethane shoe sole material according to claim 3, characterized in that: In step B, the triphenylmethane triisocyanate and the double bond-containing compound are mixed according to an isocyanate to hydroxyl molar ratio of 3:

1.

6. The method for preparing a rapid prototyping high-wear-resistant transparent polyurethane shoe sole material according to claim 5, characterized in that: The preparation steps of the double bond-containing compound are as follows: under the protection of nitrogen, 4-chloromethyl styrene, diethylene glycol amine and anhydrous ethanol are mixed uniformly, potassium carbonate is added, and reaction is carried out at 40-50 DEG C for 22-24h, and then filtration and purification are carried out to obtain the double bond-containing compound.

7. The method for preparing a rapid prototyping high-wear-resistant transparent polyurethane shoe sole material according to claim 3, characterized in that: In step C, the mass ratio of the mercapto-nano-silica, mercapto-chitosan and quaternary ammonium isocyanate is 1:(0.5-1.0):(2-4).

8. The method for preparing a rapid prototyping high wear-resistant transparent polyurethane shoe sole material according to claim 7, characterized in that: The preparation steps of the mercapto-chitosan are as follows: chitosan is dispersed in deionized water, hydrochloric acid is used to adjust the pH to 6-7, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine are added and mixed uniformly, and then reaction is carried out in the dark for 22-24h, and then dialysis and drying are carried out to obtain mercapto-chitosan.

9. The method for preparing a rapid prototyping high wear-resistant transparent polyurethane shoe sole material according to claim 1, characterized in that: The B component includes the following weight components: polyester polyol 50 60 parts, bio-based polyol 30-40 parts, chain extender 3-8 parts, catalyst 1-3 parts, foaming agent 1-3 parts, cell stabilizer 0.5-2.5 parts.

10. A rapid prototyping high wear resistant transparent polyurethane sole material prepared according to the preparation method in any one of claims 1-9.

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