Environment-friendly plastic special boots and preparation method thereof

Abstract

The invention discloses an environment-friendly plastic special boot and a preparation method thereof, and belongs to the technical field of special boot production. The environment-friendly plastic special boot takes waterborne polyurethane as a raw material, and water is used as a solvent in the manufacturing process of the waterborne polyurethane, so that the use of a large amount of chemical organic solvents is reduced, and the pollution of the chemical organic solvents to the environment is avoided; in addition, in the raw materials of the waterborne polyurethane, castor oil polyol is used for replacing part of polyether polyol, so that the waterborne polyurethane has the characteristic of degradability; the environment-friendly flame retardant is introduced into the waterborne polyurethane, and the flame retardant belongs to a high-molecular flame retardant, is small in mobility, belongs to an organic phosphorus-nitrogen synergistic flame retardant, is excellent in flame retardant property, and can improve the toughness and aging resistance of the waterborne polyurethane. Therefore, the water-based polyurethane for the special boots provided by the invention is environment-friendly and easy to degrade, and the special boots are excellent in mechanical property, flame retardant property, corrosion resistance, acid and alkali resistance and waterproof property.

Description

Technical Field

[0001] The invention belongs to the technical field of special boot production, and in particular, relates to an environmentally friendly plastic special boot and a preparation method thereof. Background Art

[0002] In general, special boots include soles, uppers and midsoles, and are suitable for special sites such as factories, typhoons, and earthquakes. In these special situations, there are high temperatures, humidity, uneven surfaces, which requires special boots to integrate anti-slip, wear-resistant, puncture-resistant, impact-resistant, waterproof and other protective functions, so that they can be suitable for wearing in emergencies and special environments, and can provide safety protection for our feet in special environments.

[0003] The upper material of special boots is generally artificial leather, because it is more economical, waterproof and durable than real leather. However, a large amount of chemical raw materials are often used in its preparation process, which is easy to cause environmental pollution. Among them, polyurethane artificial leather belongs to the category of polyurethane elastomers, with a soft and natural luster, soft feel, and a strong leather feel. It has excellent mechanical properties such as excellent adhesion to the substrate, wear resistance, flex resistance, and aging resistance.

[0004] Therefore, the present invention provides an environmentally friendly plastic special boot and a preparation method thereof. Summary of the invention

[0005] The purpose of the present invention is to provide an environmentally friendly plastic special boot and a preparation method thereof, so as to solve the technical problem of environmental pollution caused by the use of a large amount of chemical raw materials in the manufacturing process of existing special boots.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] The invention discloses an environmentally friendly plastic special boot comprising a boot sole, a boot midsole and a boot shaft. The boot sole and the boot midsole are made of water-based polyurethane through foaming, and the boot shaft is made of water-based polyurethane artificial leather.

[0008] The preparation method of the environmentally friendly plastic special boots comprises the following steps:

[0009] Step 1, preparation of the sole: After the components of the waterborne polyurethane are evenly mixed, they are injected into the sole mold with a gun tip, preheated at 0.08MPa and 78°C for 20s, and then foamed for 5min to obtain a molded sole, with a gun tip flow rate of 900-1000g / s;

[0010] Step 2, preparation of the boot shaft: cutting and shaping the waterborne polyurethane artificial leather to obtain a shaped boot shaft;

[0011] Step 3, preparation of finished boots: inject the mixed water-based polyurethane raw material between the boot shaft and the boot sole into the boot-shaped mold, preheat for 30 seconds at 0.07MPa and 83°C, and then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

[0012] Furthermore, the waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on its surface, and is manufactured by the following method: coating a waterborne polyurethane slurry prepared and mixed by weight on a woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110-130° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0013] Furthermore, the waterborne polyurethane comprises the following raw materials in parts by weight: 20-40 parts of polyether polyol, 15-30 parts of castor oil polyol, 12-22 parts of hydroxypropyl acrylate, 20-45 parts of hexamethylene diisocyanate, 3.5-6.5 parts of kenaf fiber, 1.5-4.5 parts of crosslinking agent, 1-2.5 parts of chain extender, 2-6 parts of foaming agent, 0.5-3.5 parts of stabilizer, 3.5-9.5 parts of environmentally friendly flame retardant, and 50-90 parts of deionized water.

[0014] Furthermore, the hydroxyl value of the polyether polyol is 400-500 mgKOH / g.

[0015] Furthermore, the hydroxyl value of the castor oil polyol is 290 mgKOH / g.

[0016] Furthermore, the cross-linking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 2-5:1-3.

[0017] Furthermore, the chain extender is a mixture of hexanediol and diethylenetriamine in a mass ratio of 1-4:3-5.

[0018] Furthermore, the foaming agent is one or a mixture of several AC foaming agents in any ratio.

[0019] Furthermore, the stabilizer is one or a combination of several succinate water foam stabilizers in any ratio.

[0020] Furthermore, the environmentally friendly flame retardant is prepared by the following steps:

[0021] Step A, stirring and mixing crystalline hypophosphorous acid and trimethyl orthoformate at -2-0°C, heating to room temperature, stirring and reacting for 3 hours, and then distilling under vacuum conditions until a light yellow solid powder is formed to obtain intermediate 1, wherein the molar ratio of hypophosphorous acid to trimethyl orthoformate is 1:1; uniformly mixing intermediate 1, acrylonitrile and triethylamine at -2-0°C, heating to 52°C, stirring and reacting for 3 hours to obtain intermediate 2, using Michael addition reaction of intermediate 1 and acrylonitrile, wherein the amount ratio of intermediate 1, acrylonitrile and triethylamine is 0.1-0.13 mol: 0.1 mol: 0.1-0.15 mol; adding concentrated hydrochloric acid to intermediate 2 at -2-0°C and stirring, and heating to 90°C, stirring and reacting for 3 hours, cooling, filtering, dissolving and recrystallizing with acetone to obtain intermediate 3, wherein the amount ratio of intermediate 2 to concentrated hydrochloric acid is 0.1 mol l: 3-4g, and the mass concentration of concentrated hydrochloric acid is 36%, the reaction formula is as follows;

[0022]

[0023] Step B, using a constant pressure dropping funnel to slowly add benzyl chloride to p-hydroxymethylbenzaldehyde, heat the reaction system to 102°C, and react at a constant temperature for 3.5 hours. When the reaction system is cooled to 35°C, potassium carbonate and dichloromethane are added, and the reaction is continued at a constant temperature for 4 hours. Cooling obtains intermediate 4, and the reaction formula is shown below, wherein the amount ratio of p-hydroxymethylbenzaldehyde, benzyl chloride, potassium carbonate and dichloromethane is 1 mol: 1 mol: 5-10 g: 60-150 mL; intermediate 4, aniline, and aniline hydrochloride are added to a four-necked flask with a stirring magnet and a nitrogen flow device, and after stirring evenly, the reaction system is heated to 113°C in an oil bath, and the reaction is continued at a constant temperature for 2 hours, and then the reaction system is heated to 152°C, and the reaction is continued at a constant temperature for 1.5 hours. After the reaction is completed, when the system drops to 55°C, it is distilled under reduced pressure for 30 minutes, and then 2 mol / L of dilute hydrochloric acid is added to dissolve the remaining substance, filtered, and the filtrate is taken and 2 mol / L of dilute hydrochloric acid is added. l / L of dilute sodium hydroxide solution to pH 7-8, at which time a precipitate is generated. After the precipitation is complete, it is filtered, and the filter cake is washed repeatedly for 3-5 times to obtain a crude product, which is recrystallized twice with ethanol / water, and finally dried in vacuo at 60°C for 24h to obtain intermediate 5, wherein the amount ratio of intermediate 4, aniline, and aniline hydrochloride is 0.1mol:0.11-0.13mol:4-6mL; intermediate 5, p-toluenesulfonyl chloride, triethylamine and dichloromethane are added to a three-necked flask with a stirrer and a condenser, and the reaction temperature is controlled to 63°C under a nitrogen atmosphere. The reaction is stirred for 8h, and the solvent is removed by vacuum rotary evaporation to obtain intermediate 6, wherein the amount ratio of intermediate 5, p-toluenesulfonyl chloride, triethylamine and dichloromethane is 0.01mol:0.02-0.023mol:0.02mol:50-100mL, and the reaction formula is shown below;

[0024]

[0025]

[0026] Step C, adding intermediate 6 and pyridine into a three-necked flask with a stirrer and a reflux device, passing high-purity nitrogen for 30 min, then adding a 10% volume fraction Pd / C catalyst, passing hydrogen, and stirring at room temperature for 24 hours under hydrogen protection. After the reaction is completed, filtering, washing with methanol for 3 times, combining the filtrate, and distilling the filtrate under reduced pressure at room temperature to obtain intermediate 7, and removing the benzyl group by catalytic hydrogenation of benzyl ether to generate an alcohol reaction, wherein the amount ratio of intermediate 6, pyridine, and Pd / C catalyst is 0.1 mmol: 30-80 mL: 0.1-0.3 g, and the reaction formula is shown below;

[0027]

[0028] Step D: add intermediate 7, benzene and p-toluenesulfonic acid into a three-necked flask with a condenser reflux tube and a stirring magnet, stir evenly, heat the reaction system to 61°C with an oil bath, add perfluoropentanoic acid with a dropping funnel under stirring at a dropping speed of 1 drop / second, reflux for 10 hours, separate the reaction solution through a column (the volume ratio of methanol: chloroform is 2:5), and obtain intermediate 8, wherein the esterification reaction of perfluoropentanoic acid and alkyl alcohol is utilized, wherein the usage ratio of intermediate 7, benzene, p-toluenesulfonic acid and perfluoropentanoic acid is 0.1 mol:40-70 mL:0.4-0.7 mL:0.15-0.18 mol l; After stirring the glacial acetic acid solution of hydrogen bromide, intermediate 8 and phenol evenly, seal the reaction system, control the temperature of the reaction system at 73°C, react at a constant temperature for 2 hours, cool, add anhydrous ether, shake well, place at 0°C for 12 hours, filter under reduced pressure, wash with anhydrous ethanol, and vacuum dry to constant weight to obtain intermediate 9, which utilizes the deprotection reaction of benzenesulfonyl, wherein the amount ratio of the glacial acetic acid solution of hydrogen bromide, intermediate 8 and phenol is 30-80mL:3-7g:6-15mL, and the volume ratio of hydrogen bromide to glacial acetic acid in the glacial acetic acid solution of hydrogen bromide is 1:2-3. The reaction formula is shown below;

[0029]

[0030] Step E, add intermediate 3, EDC, NHS and deionized water into a three-necked flask with a stirrer and a condenser, stir at room temperature for 1 hour, then add intermediate 9, and adjust the pH of the reaction solution to 5-6 with dilute hydrochloric acid, stir and react at 35°C for 12 hours, filter the reactant, and wash it repeatedly with deionized water for 3 times, and vacuum dry it to constant weight to obtain an environmentally friendly flame retardant, wherein the amount ratio of intermediate 3, EDC, NHS, deionized water and intermediate 9 is 0.01 mol: 0.5-1g: 0.4-0.9g: 80-160mL: 0.01 mol, and the reaction formula is shown below.

[0031]

[0032] Beneficial effects of the present invention:

[0033] 1. The present invention uses water-based polyurethane as the raw material of special boots. Water-based polyurethane uses water as solvent in the manufacturing process, which reduces the use of a large amount of chemical organic solvents and avoids the pollution of the environment by chemical organic solvents. In addition, the water-based polyurethane used in the present invention replaces part of the polyether polyol with castor oil polyol, so that the water-based polyurethane has the characteristics of being degradable and its environmental performance is improved. Kenaf fiber is introduced into the raw material to enhance the mechanical properties of the water-based polyurethane.

[0034] 2. In order to improve the application of the special boots in high temperature environments, the present invention introduces an environmentally friendly flame retardant into the raw materials of the waterborne polyurethane used, and the flame retardant belongs to a polymer flame retardant with low mobility. In addition, it can also increase the toughness and anti-aging properties of the waterborne polyurethane. The environmentally friendly flame retardant is an organic phosphorus-nitrogen synergistic flame retardant mainly with hypophosphorous acid as the phosphorus source and aniline as the nitrogen source, and has good compatibility with the waterborne polyurethane system. Its preparation mainly involves the following process: using hypophosphorous acid, trimethyl orthoformate, acrylonitrile and concentrated hydrochloric acid to gradually react to produce intermediate 3, and then using p-hydroxymethylbenzaldehyde, benzyl chloride, aniline, perfluoropentanoic acid, p-toluenesulfonyl chloride to gradually react to obtain intermediate 9, and then using the polycondensation reaction of intermediate 3 and intermediate 9 to obtain the environmentally friendly flame retardant. In the above process, perfluoropentanoic acid provides a fluorinated alkyl chain for the environmentally friendly flame retardant, giving the environmentally friendly flame retardant corrosion resistance, acid and alkali resistance, and waterproof effects.

[0035] In summary, the aqueous polyurethane used in the special boots provided by the present invention is environmentally friendly and easily degradable, and the special boots have excellent mechanical properties, flame retardant properties, corrosion resistance, acid and alkali resistance, and waterproof properties. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Embodiment 1:

[0038] Environmentally friendly flame retardants are made through the following steps:

[0039] Step A, stirring and mixing 1 mol of crystalline hypophosphorous acid and 1 mol of trimethyl orthoformate at 0°C, heating to room temperature, stirring and reacting for 3 hours, and then distilling under vacuum conditions until a light yellow solid powder is formed to obtain intermediate 1; uniformly mixing 0.13 mol of intermediate 1, 0.1 mol of acrylonitrile and 0.15 mol of triethylamine at 0°C, heating to 52°C, stirring and reacting for 3 hours to obtain intermediate 2; adding 4 g of 36% concentrated hydrochloric acid to 0.1 mol of intermediate 2 at 0°C and stirring, and heating to 90°C, stirring and reacting for 3 hours, cooling, filtering, dissolving and recrystallizing with acetone to obtain intermediate 3;

[0040] Step B, slowly add 1 mol of benzyl chloride to 1 mol of p-hydroxymethylbenzaldehyde using a constant pressure dropping funnel, heat the reaction system to 102°C, and react at a constant temperature for 3.5 hours. When the reaction system is cooled to 35°C, add 5g of potassium carbonate and 60mL of dichloromethane, react at a constant temperature for 4 hours, and cool to obtain intermediate 4; add 0.1 mol of intermediate 4, 0.11 mol of aniline, and 4mL of aniline hydrochloride into a four-necked flask with a stirring magnet and a nitrogen flow device, stir evenly, heat the reaction system to 113°C with an oil bath, and react at a constant temperature for 2 hours, then heat the reaction system to 152°C, continue to react at a constant temperature for 1.5 hours, and when the reaction is completed, when the system drops to 55°C, distill under reduced pressure for 30 minutes, then add 2 mol / L of dilute hydrochloric acid to dissolve the remaining substance, filter, and take the filtrate with 2 mol l / L of dilute sodium hydroxide solution was neutralized to pH 7, at which time a precipitate was generated. After the precipitation was complete, it was filtered, and the filter cake was taken and washed repeatedly for 3-5 times to obtain a crude product, which was recrystallized twice with ethanol / water, and finally dried under vacuum at 60°C for 24h to obtain intermediate 5; 0.01mol intermediate 5, 0.02mol p-toluenesulfonyl chloride, 0.02mol triethylamine and 50mL dichloromethane were added to a three-necked flask with a stirrer and a condenser, and the reaction temperature was controlled to 63°C under a nitrogen atmosphere. The reaction was stirred for 8h, and the solvent was removed by vacuum rotary evaporation to obtain intermediate 6;

[0041] Step C, add 0.1 mmol of intermediate 6 and 30 mL of pyridine into a three-necked flask with a stirrer and a reflux device, pass high-purity nitrogen for 30 minutes, then add 0.1 g of 10% Pd / C catalyst by volume, pass hydrogen, and stir at room temperature for 24 hours under hydrogen protection. After the reaction is completed, filter, wash with methanol 3 times, combine the filtrate, and evaporate the filtrate under reduced pressure at room temperature to obtain intermediate 7;

[0042] Step D, add 0.1 mol intermediate 7, 40 mL benzene, and 0.4 mL p-toluenesulfonic acid into a three-necked flask with a condenser reflux tube and a stirring magnet, stir evenly, heat the reaction system to 61°C with an oil bath, and add 0.15 mol perfluoropentanoic acid with a dropping funnel under stirring at a dropping speed of 1 drop / second, reflux reaction for 10 hours, and separate the reaction solution through a column (the volume ratio of methanol: chloroform is 2:5) to obtain intermediate 8; stir evenly 30 mL of hydrogen bromide glacial acetic acid solution, 3 g of intermediate 8 and 6 mL of phenol, seal the reaction system, control the temperature of the reaction system at 73°C, react at a constant temperature for 2 hours, cool, add anhydrous ether, shake well, place at 0°C for 12 hours, filter under reduced pressure, wash with anhydrous ethanol, and vacuum dry to constant weight to obtain intermediate 9, the volume ratio of hydrogen bromide to glacial acetic acid in the hydrogen bromide glacial acetic acid solution is 1:2;

[0043] Step E, add 0.01 mol intermediate 3, 0.5 g EDC, 0.4 g NHS and 80 mL deionized water into a three-necked flask with a stirrer and a condenser, stir at room temperature for 1 hour, then add 0.01 mol intermediate 9, and adjust the pH of the reaction solution to 5 with dilute hydrochloric acid, stir the reaction at 35°C for 12 hours, filter the reactants, wash them repeatedly with deionized water for 3 times, and vacuum dry them to constant weight to obtain an environmentally friendly flame retardant.

[0044] Embodiment 2:

[0045] Environmentally friendly flame retardants are made through the following steps:

[0046] Step A, stirring and mixing 1 mol of crystalline hypophosphorous acid and 1 mol of trimethyl orthoformate at -2°C, heating to room temperature, stirring and reacting for 3 hours, and then distilling under vacuum conditions until a light yellow solid powder is formed to obtain intermediate 1; uniformly mixing 0.13 mol of intermediate 1, 0.1 mol of acrylonitrile and 0.1 mol of triethylamine at 0°C, heating to 52°C, stirring and reacting for 3 hours to obtain intermediate 2; adding 4 g of 36% concentrated hydrochloric acid to 0.1 mol of intermediate 2 at -2°C and stirring, and heating to 90°C, stirring and reacting for 3 hours, cooling, filtering, dissolving with acetone and recrystallizing, to obtain intermediate 3;

[0047] Step B, slowly add 1 mol of benzyl chloride to 1 mol of p-hydroxymethylbenzaldehyde using a constant pressure dropping funnel, heat the reaction system to 102°C, and react at a constant temperature for 3.5 hours. When the reaction system is cooled to 35°C, add 10g of potassium carbonate and 150mL of dichloromethane, react at a constant temperature for 4 hours, and cool to obtain intermediate 4; 0.1 mol of intermediate 4, 0.13 mol of aniline, and 6mL of aniline hydrochloride are added to a four-necked flask with a stirring magnet and a nitrogen flow device, and after stirring evenly, the reaction system is heated to 113°C in an oil bath and reacted at a constant temperature for 2 hours, and then the reaction system is heated to 152°C and the constant temperature reaction is continued for 1.5 hours. After the reaction is completed, when the system drops to 55°C, it is distilled under reduced pressure for 30 minutes, and then 2 mol of 1 / L of dilute hydrochloric acid was used to dissolve the remaining material, and the mixture was filtered. The filtrate was neutralized with a 2 mol / L dilute sodium hydroxide solution to a pH of 7, at which time a precipitate was generated. After the precipitation was complete, the filter cake was washed repeatedly for 3-5 times to obtain a crude product, which was recrystallized twice with ethanol / water and finally dried under vacuum at 60°C for 24 h to obtain intermediate 5. 0.01 mol of intermediate 5, 0.023 mol of p-toluenesulfonyl chloride, 0.02 mol of triethylamine and 100 mL of dichloromethane were added to a three-necked flask equipped with a stirrer and a condenser. Under a nitrogen atmosphere, the reaction temperature was controlled to 63°C, and the reaction was stirred for 8 h. The solvent was removed by rotary evaporation under reduced pressure to obtain intermediate 6.

[0048] Step C, add 0.1 mmol of intermediate 6 and 80 mL of pyridine into a three-necked flask with a stirrer and a reflux device, pass high-purity nitrogen for 30 minutes, then add 0.2 g of 10% Pd / C catalyst by volume, pass hydrogen, and stir at room temperature for 24 hours under hydrogen protection. After the reaction is completed, filter, wash with methanol three times, combine the filtrate, and evaporate the filtrate under reduced pressure at room temperature to obtain intermediate 7;

[0049] Step D, add 0.1 mol intermediate 7, 70 mL benzene, and 0.7 mL p-toluenesulfonic acid into a three-necked flask with a condenser reflux tube and a stirring magnet, stir evenly, heat the reaction system to 61°C with an oil bath, and add 0.16 mol perfluoropentanoic acid with a dropping funnel under stirring at a dropping speed of 1 drop / second, reflux reaction for 10 hours, and separate the reaction solution through a column (the volume ratio of methanol: chloroform is 2:5) to obtain intermediate 8; stir evenly 80 mL of hydrogen bromide glacial acetic acid solution, 7 g of intermediate 8 and 15 mL of phenol, seal the reaction system, control the temperature of the reaction system at 73°C, react at a constant temperature for 2 hours, cool, add anhydrous ether, shake well, place at 0°C for 12 hours, filter under reduced pressure, wash with anhydrous ethanol, and vacuum dry to constant weight to obtain intermediate 9, the volume ratio of hydrogen bromide to glacial acetic acid in the hydrogen bromide glacial acetic acid solution is 1:3;

[0050] Step E, add 0.01 mol intermediate 3, 1 g EDC, 0.9 g NHS and 160 mL deionized water into a three-necked flask with a stirrer and a condenser, stir at room temperature for 1 h, then add 0.01 mol intermediate 9, and adjust the pH of the reaction solution to 6 with dilute hydrochloric acid, stir the reaction at 35 ° C for 12 h, filter the reactant, and wash it repeatedly with deionized water for 3 times, and vacuum dry it to constant weight to obtain an environmentally friendly flame retardant.

[0051] Embodiment 3:

[0052] The waterborne polyurethane comprises the following raw materials in parts by weight: 20 parts of polyether polyol, 15 parts of castor oil polyol, 12 parts of hydroxypropyl acrylate, 20 parts of hexamethylene diisocyanate, 3.5 parts of kenaf fiber, 1.5 parts of crosslinking agent, 1 part of chain extender, 2 parts of foaming agent, 0.5 parts of stabilizer, 3.5 parts of environmentally friendly flame retardant prepared in Example 1, and 50 parts of deionized water; the hydroxyl value of the polyether polyol is 400 mgKOH / g; the hydroxyl value of the castor oil polyol is 290 mgKOH / g; the crosslinking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 2:1; the chain extender is a mixture of hexanediol and diethylenetriamine mixed in a mass ratio of 1:3; the foaming agent is SA1000; and the stabilizer is sodium salt of dioctyl sulfosuccinate.

[0053] Embodiment 4:

[0054] The waterborne polyurethane comprises the following raw materials in parts by weight: 30 parts of polyether polyol, 22 parts of castor oil polyol, 18 parts of hydroxypropyl acrylate, 30 parts of hexamethylene diisocyanate, 4 parts of kenaf fiber, 2 parts of cross-linking agent, 2 parts of chain extender, 3 parts of foaming agent, 2 parts of stabilizer, 6 parts of environmentally friendly flame retardant prepared in Example 2, and 70 parts of deionized water; the hydroxyl value of the polyether polyol is 500 mgKOH / g; the hydroxyl value of the castor oil polyol is 290 mgKOH / g; the cross-linking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 3:2; the chain extender is a mixture of hexanediol and diethylenetriamine mixed in a mass ratio of 3:4; the foaming agent SA3000; and the stabilizer is sodium salt of dioctyl sulfosuccinate.

[0055] Embodiment 5:

[0056] The waterborne polyurethane comprises the following raw materials in parts by weight: 40 parts of polyether polyol, 30 parts of castor oil polyol, 22 parts of hydroxypropyl acrylate, 45 parts of hexamethylene diisocyanate, 6.5 parts of kenaf fiber, 4.5 parts of crosslinking agent, 2.5 parts of chain extender, 6 parts of foaming agent, 3.5 parts of stabilizer, 9.5 parts of environmentally friendly flame retardant prepared in Example 1, and 90 parts of deionized water; the hydroxyl value of the polyether polyol is 500 mgKOH / g; the hydroxyl value of the castor oil polyol is 290 mgKOH / g; the crosslinking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 5:3; the chain extender is a mixture of hexanediol and diethylenetriamine mixed in a mass ratio of 4:5; the foaming agent is a combination of SA1000 and SA3000 mixed in a mass ratio of 1:1; the stabilizer is disodium alcohol ether sulfosuccinate.

[0057] Embodiment 6:

[0058] The waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating the waterborne polyurethane slurry in parts by weight in Example 3 on the woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0059] Embodiment 7:

[0060] The waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating the waterborne polyurethane slurry in parts by weight in Example 4 on the woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0061] Embodiment 8:

[0062] The waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating 3 parts by weight of the waterborne polyurethane slurry of the embodiment on the woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 117° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0063] Embodiment 9:

[0064] An environmentally friendly plastic special boot is made by the following steps:

[0065] Step 1, preparation of the sole: taking the waterborne polyurethane according to the weight portion in Example 3, and then mixing it evenly, injecting it into the sole mold with a gun tip, preheating it at 0.08 MPa and 78°C for 20 seconds, and then foaming it for 5 minutes to obtain a molded sole, and the flow rate of the gun tip is 900 g / s;

[0066] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Example 6 to obtain a shaped boot shaft;

[0067] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in Example 3) into the boot-shaped mold for forming the boot shaft and the sole between the boot shaft and the sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

[0068] Embodiment 10:

[0069] An environmentally friendly plastic special boot is made by the following steps:

[0070] Step 1, preparation of the sole: taking the waterborne polyurethane according to the weight portion in Example 4, and then mixing it evenly, injecting it into the sole mold with a gun tip, preheating at 0.08 MPa and 78°C for 20 seconds, and then foaming for 5 minutes to obtain a molded sole, and the flow rate of the gun tip is 900 g / s;

[0071] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Example 7 to obtain a shaped boot shaft;

[0072] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in Example 4) between the boot shaft and the boot sole into the boot-shaped mold for forming the boot shaft and the boot sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

[0073] Embodiment 11:

[0074] An environmentally friendly plastic special boot is made by the following steps:

[0075] Step 1, preparation of the sole: taking the waterborne polyurethane according to the weight portion in Example 5, and then mixing it evenly, injecting it into the sole mold with a gun tip, preheating at 0.08 MPa and 78°C for 20 seconds, and then foaming for 5 minutes to obtain a molded sole, and the flow rate of the gun tip is 900 g / s;

[0076] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Example 8 to obtain a shaped boot shaft;

[0077] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in Example 5) into the boot-shaped mold for forming the boot shaft and the sole between the boot shaft and the sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

[0078] Comparative Example 1:

[0079] The waterborne polyurethane comprises the following raw materials in parts by weight: 20 parts of polyether polyol, 12 parts of hydroxypropyl acrylate, 20 parts of hexamethylene diisocyanate, 3.5 parts of kenaf fiber, 1.5 parts of crosslinking agent, 1 part of chain extender, 2 parts of foaming agent, 0.5 parts of stabilizer, 3.5 parts of environmentally friendly flame retardant prepared in Example 1, and 50 parts of deionized water; the hydroxyl value of the polyether polyol is 400 mgKOH / g; the crosslinking agent is a composition in which maleic anhydride and epichlorohydrin are mixed in a mass ratio of 2:1; the chain extender is a mixture in which hexanediol and diethylenetriamine are mixed in a mass ratio of 4:3; the foaming agent is SA1000; and the stabilizer is alcohol ether sulfosuccinate monoester.

[0080] Comparative Example 2:

[0081] The waterborne polyurethane comprises the following raw materials in parts by weight: 30 parts of polyether polyol, 22 parts of castor oil polyol, 18 parts of hydroxypropyl acrylate, 30 parts of hexamethylene diisocyanate, 2 parts of crosslinking agent, 2 parts of chain extender, 3 parts of foaming agent, 2 parts of stabilizer, 6 parts of environmentally friendly flame retardant prepared in Example 2, and 70 parts of deionized water; the hydroxyl value of the polyether polyol is 500 mgKOH / g; the hydroxyl value of the castor oil polyol is 290 mgKOH / g; the crosslinking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 3:2; the chain extender is a mixture of hexanediol and diethylenetriamine mixed in a mass ratio of 3:4; the foaming agent is SA3000; and the stabilizer is sodium salt of dioctyl sulfosuccinate.

[0082] Comparative Example 3:

[0083] The waterborne polyurethane comprises the following raw materials in parts by weight: 40 parts of polyether polyol, 30 parts of castor oil polyol, 22 parts of hydroxypropyl acrylate, 45 parts of hexamethylene diisocyanate, 6.5 parts of kenaf fiber, 4.5 parts of crosslinking agent, 2.5 parts of chain extender, 6 parts of foaming agent, 3.5 parts of stabilizer, 9.5 parts of commercially available flame retardant and 90 parts of deionized water; the hydroxyl value of the polyether polyol is 500 mgKOH / g; the hydroxyl value of the castor oil polyol is 290 mgKOH / g; the crosslinking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 5:3; the chain extender is a mixture of hexanediol and diethylenetriamine mixed in a mass ratio of 4:5; the foaming agent is a combination of SA1000 and SA3000 mixed in a mass ratio of 1:1; the stabilizer is disodium alcohol ether sulfosuccinate.

[0084] Comparative Example 4:

[0085] The waterborne polyurethane artificial leather comprises a base fabric layer and waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating 1 weight portion of waterborne polyurethane slurry of a comparative example on a woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0086] Comparative Example 5:

[0087] The waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating 2 parts by weight of a waterborne polyurethane slurry of a comparative example on a woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0088] Comparative Example 6:

[0089] The waterborne polyurethane artificial leather comprises a base fabric layer and a waterborne polyurethane coated on the surface thereof, and is prepared by the following method: coating 3 parts by weight of a waterborne polyurethane slurry of a comparative example on a woven base fabric by dipping or roller coating; scraping and leveling the coated product surface by a scraper; and drying and shaping the product at 110° C. by a drying and shaping machine to obtain a waterborne polyurethane artificial leather.

[0090] Comparative Example 7:

[0091] A special boot is made by the following steps:

[0092] Step 1, preparation of the sole: taking the waterborne polyurethane according to the weight portion in comparative example 1, and then mixing evenly, injecting into the sole mold with a gun tip, preheating at 0.08 MPa and 78°C for 20 seconds, and then foaming for 5 minutes to obtain a molded sole, and the flow rate of the gun tip is 900 g / s;

[0093] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Comparative Example 4 to obtain a shaped boot shaft;

[0094] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in comparative example 1) between the boot shaft and the boot sole into the boot-shaped mold for forming the boot shaft and the boot sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain a special boot.

[0095] Comparative Example 8:

[0096] A special boot is made by the following steps:

[0097] Step 1, preparation of the sole: take the waterborne polyurethane according to the weight portion in comparative example 2, mix them evenly, inject them into the sole mold with a gun tip, preheat them at 0.08 MPa and 78°C for 20 seconds, and then foam them for 5 minutes to obtain the molded sole, and the flow rate of the gun tip is 900 g / s;

[0098] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Comparative Example 5 to obtain a shaped boot shaft;

[0099] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in Comparative Example 2) between the boot shaft and the boot sole into the boot-shaped mold for forming the boot shaft and the boot sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

[0100] Comparative Example 9:

[0101] A special boot is made by the following steps:

[0102] Step 1, preparation of the sole: take the waterborne polyurethane according to the weight portion in comparative example 3, mix them evenly, inject them into the sole mold with a gun tip, preheat them at 0.08 MPa and 78°C for 20 seconds, and then foam them for 5 minutes to obtain the molded sole, and the flow rate of the gun tip is 900 g / s;

[0103] Step 2, preparation of a boot shaft: cutting and shaping the waterborne polyurethane artificial leather prepared in Comparative Example 6 to obtain a shaped boot shaft;

[0104] Step 3, preparation of finished boots: inject the mixed aqueous polyurethane raw material (take the material according to the weight proportion in Comparative Example 3) between the boot shaft and the boot sole into the boot-shaped mold for forming the boot shaft and the boot sole, preheat for 30 seconds at 0.07MPa and 83°C, then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain a special boot.

[0105] Embodiment 12:

[0106] The special boots obtained from Examples 9-11 and Comparative Examples 7-9 were subjected to the following performance tests:

[0107] Flame retardant properties: The limiting oxygen index (LOI) test is carried out in accordance with GB / T2406-93 "Plastic Combustion Performance Test Method - Oxygen Index Method", the sample size is 100mm×10mm×3mm, each group of specimens is repeated 5 times, and the average value is taken. Vertical combustion is carried out in accordance with GB / T2508-1996 or the US UL-94 test standard, the molded standard specimens (specimen size is 120mm×13mm×3mm) are tested on a horizontal vertical combustion test machine, each group of specimens is repeated at least 5 times, and the average value is taken; the test data are shown in Table 1;

[0108] Acid and alkali resistance: Cut the test sample into small squares of 1.5cm×1.5cm, immerse them in 10% diluted HCl and 10% diluted NaOH solutions for 20 days, and observe the changes in the morphology of the small squares; the test data are shown in Table 1;

[0109] Tensile properties: tensile strength and elongation at break are tested according to GB / T528-2009, and the test data are shown in Table 2;

[0110] The degradation performance test adopts the soil burial degradation method. First, the obtained special boots are made into the same standard specimens. Five standard specimens are used in each case, and the sample size is 100mm×10mm×3mm. Then they are buried in the soil of the test area for soil burial degradation experiments. The test time is six months. Five standard specimens are taken in each case to test their tensile strength, elongation at break and thermal weight loss rate. Among them, the thermal stability is characterized and analyzed by a thermogravimetric analyzer on the flame retardant samples after vacuum oven drying for 8 hours. The test environment is N2 environment, the N2 flow rate is 60mL / min, the heating rate is 10℃ / min, and the temperature range is 25℃-800℃; the result is the average value of 5 standard samples; the test data is shown in Table 2;

[0111] Table 1

[0112]

[0113] It can be seen from the data in Table 1 that the flame retardant properties and acid and alkali resistance of the special boots obtained in Examples 9-11 are better than the corresponding properties of the special boots obtained in Comparative Example 3.

[0114] Table 2

[0115]

[0116]

[0117] It can be seen from the data in Table 2 that the tensile properties of the special boots obtained in Examples 9-11 are better than the corresponding properties of the special boots obtained in Comparative Example 8, and the degradation properties of the special boots obtained in Examples 9-11 are better than the corresponding properties of the special boots obtained in Comparative Example 7.

[0118] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0119] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An environmentally friendly plastic special boot, comprising a sole, a midsole and a boot shaft, wherein the sole and the midsole are made of waterborne polyurethane foamed, and the boot shaft is made of waterborne polyurethane artificial leather, characterized in that: The waterborne polyurethane comprises the following raw materials in parts by weight: 20-40 parts of polyether polyol, 15-30 parts of castor oil polyol, 12-22 parts of hydroxypropyl acrylate, 20-45 parts of hexamethylene diisocyanate, 1.5-4.5 parts of crosslinking agent, 1-2.5 parts of chain extender, 2-6 parts of foaming agent, 0.5-3.5 parts of stabilizer, 3.5-9.5 parts of environmentally friendly flame retardant, and 50-90 parts of deionized water; The waterborne polyurethane artificial leather comprises a base fabric layer and waterborne polyurethane coated on the surface thereof.

2. The environmentally friendly plastic special boots according to claim 1, characterized in that: The environmentally friendly flame retardant is prepared by the following steps: Step A, stirring and mixing crystalline hypophosphorous acid and trimethyl orthoformate at -2-0°C, heating to room temperature, stirring and reacting for 3 hours, and then distilling under vacuum conditions until a light yellow solid powder is formed to obtain intermediate 1; uniformly mixing intermediate 1, acrylonitrile and triethylamine at -2-0°C, heating to 52°C, stirring and reacting for 3 hours to obtain intermediate 2; adding concentrated hydrochloric acid to intermediate 2 at -2-0°C with stirring, heating to 90°C, stirring and reacting for 3 hours, cooling, filtering, and recrystallizing to obtain intermediate 3; Step B, benzyl chloride was added dropwise to p-hydroxymethylbenzaldehyde, and the mixture was reacted at 102°C for 3.5 hours. When the reaction system was cooled to 35°C, potassium carbonate and dichloromethane were added, and the mixture was reacted at a constant temperature for 4 hours, and then cooled to obtain intermediate 4; intermediate 4, aniline and aniline hydrochloride were mixed evenly, and the mixture was reacted at 113°C for 2 hours, and the mixture was further reacted at 152°C for 1.5 hours, and post-treated to obtain intermediate 5; intermediate 5, p-toluenesulfonyl chloride, triethylamine and dichloromethane were mixed, and the mixture was stirred and reacted at 63°C in a nitrogen atmosphere for 8 hours, and the mixture was evaporated under reduced pressure to obtain intermediate 6; Step C, adding intermediate 6 and pyridine into a three-necked flask, passing high-purity nitrogen for 30 minutes, then adding 10% by volume Pd / C catalyst, passing hydrogen, and stirring at room temperature for 24 hours under hydrogen protection, filtering, washing, combining the filtrate, and vacuum distilling the filtrate to obtain intermediate 7; Step D, after mixing intermediate 7, benzene and p-toluenesulfonic acid evenly, add perfluoropentanoic acid dropwise at 61° C. with stirring, reflux for 10 hours, separate through a column to obtain intermediate 8; after mixing hydrogen bromide glacial acetic acid solution, intermediate 8 and phenol evenly, seal the reaction system, react at 73° C. for 2 hours, cool, add anhydrous ether, shake well, place at 0° C. for 12 hours, filter under reduced pressure, wash, and vacuum dry to obtain intermediate 9; Step E: After mixing intermediate 3, EDC, NHS and deionized water evenly, add intermediate 9, stir and react at pH 5-6 and 35° C. for 12 hours, filter the reactant, wash, and vacuum dry to obtain an environmentally friendly flame retardant.

3. The environmentally friendly plastic special boots according to claim 1, characterized in that: The hydroxyl value of the polyether polyol is 400-500 mgKOH / g.

4. The environmentally friendly plastic special boots according to claim 1, characterized in that: The hydroxyl value of the castor oil polyol is 290 mgKOH / g.

5. The environmentally friendly plastic special boots according to claim 1, characterized in that: The cross-linking agent is a composition of maleic anhydride and epichlorohydrin mixed in a mass ratio of 2-5:1-3.

6. The environmentally friendly plastic special boots according to claim 1, characterized in that: The chain extender is a mixture of hexanediol and diethylenetriamine in a mass ratio of 1-4:3-5.

7. The environmentally friendly plastic special boots according to claim 1, characterized in that: The foaming agent is one of AC foaming agents or a mixture of several of them in any ratio.

8. The environmentally friendly plastic special boots according to claim 1, characterized in that: The stabilizer is one or a combination of several succinate water foam stabilizers in any ratio.

9. The method for preparing an environmentally friendly plastic special boot according to claim 1, characterized in that: The following steps are involved: Step 1, preparation of the boot sole: after the components of the waterborne polyurethane are evenly mixed, they are injected into the sole mold with a gun head to foam and form the boot sole; Step 2, preparation of the boot shaft: cutting and shaping the waterborne polyurethane artificial leather to obtain a shaped boot shaft; Step 3, preparation of finished boots: inject the mixed water-based polyurethane raw material between the boot shaft and the boot sole into the boot-shaped mold, preheat for 30 seconds at 0.07MPa and 83°C, and then foam for 5 minutes to obtain the boot midsole, cool, and demold to obtain an environmentally friendly plastic special boot.

10. The method for preparing an environmentally friendly plastic special boot according to claim 9, characterized in that: In step 1, the foaming conditions are 0.08 MPa, 78° C., preheating for 20 seconds, and then foaming for 5 minutes.

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