Anti-smashing and anti-puncturing special plastic boot

Abstract

The invention discloses an anti-smashing and anti-puncture special plastic boot, and belongs to the technical field of special plastic boots. The plastic boot comprises a sole material and a vamp material, raw materials of the sole material contain mineral powder and carbon fibers as inorganic materials besides polymers such as butadiene rubber and modified polystyrene resin, and the organic-inorganic materials are compounded, so that the puncture resistance of the sole is enhanced, and the plastic boot can be worn for a long time in special environments such as earthquakes, fire disasters and rugged mountain roads, and has a good anti-puncture effect. And the modified polystyrene resin enhances the aging resistance of the sole. In addition, the vamp material is further improved, the glass fiber cloth has good mechanical property and high strength, the impact resistance is greatly enhanced, the phenomenon that toes are kicked by foreign objects or crushed and crushed by falling foreign objects in the walking process is effectively avoided, the safety is high, the glass fiber cloth is coated with the modified coating, and the service life of the vamp is prolonged. And therefore, the corrosion-resistant, acid-resistant, alkali-resistant and the like are realized, and the service life is greatly prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of special plastic boots and relates to a special plastic boot that is resistant to smashing and puncture. Background Art

[0002] Special boots generally refer to shoes worn in special working situations that protect the feet and legs from foreseeable injuries. Special boots have very high requirements for raw materials, auxiliary materials and production processes. Special boots must have functions such as anti-smashing, anti-puncture, anti-static, oil-resistant, anti-slip, and insulation.

[0003] Referring to a puncture-proof and wear-resistant safety shoe sole and its manufacturing method disclosed in Chinese patent CN110483978A, the weight proportions of each component in its formula are as follows: 20-30 parts of composite fiber, 100 parts of polycarbonate polyol, 1.5-2 parts of catalyst, 0.6-1.2 parts of foaming agent, 0.5-1 parts of foaming agent, 0.05 parts of foaming aid, 6-8 parts of wear-resistant agent, 100 parts of isocyanate, 1-1.5 parts of chain extender, 10-15 parts of puncture-proof glue. The composite fiber of the invention is evenly dispersed in the polyurethane matrix to form a high-strength fiber net. When the sole is subjected to puncture external force, the fiber net plays a good hindering role and enhances the puncture-proof performance of the sole; the wear-resistant agent enhances the wear resistance of the sole; the puncture-proof glue enhances the high temperature resistance and electric shock resistance of the sole, so that the comprehensive safety performance of the safety shoe is improved. However, in special and complex environments such as construction sites or laboratories, special plastic boots are often exposed to acid and alkali substances, and are easily corroded by acids and alkalis, becoming brittle and reducing their service life. Summary of the invention

[0004] The purpose of the present invention is to provide a special plastic boot that is resistant to smashing and puncture to solve the problems mentioned in the background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A special plastic boot that is resistant to smashing and puncture, comprising a sole material and an upper material;

[0007] The sole material is prepared by the following steps:

[0008] Step A11, taking 20-35 parts of butadiene rubber, 10-18 parts of modified polystyrene resin, 3-5 parts of hot melt adhesive, 3-5 parts of ore powder, 1-2 parts of sulfur, and 2-4 parts of carbon fiber in parts by weight, and mixing them to synthesize a raw rubber sheet;

[0009] Step A12, loading the raw rubber sheet into the sole mold, applying 80-90 kg pressure to the rubber sheet using a hydraulic press, and vulcanizing it at a temperature of 100-115° C. for 8-12 minutes to obtain the sole.

[0010] Furthermore, the ore powder in step A11 is one or more of phosphotyrite, pyrite, lapis lazuli, copper ore, dolomite, and medical stone mixed in any proportion.

[0011] Wherein the modified polystyrene resin is prepared by the following steps:

[0012] Step S11, add 4-hydroxybenzaldehyde, K2CO3, and acetone to a three-necked flask, stir evenly, then dropwise add a solution of 1,5-dibromopentane in acetone, reflux at room temperature for 16-17 hours, remove the solvent by rotary evaporation, wash the product with dichloromethane 2-3 times, dry with magnesium sulfate, and purify by silica gel column chromatography to obtain intermediate 1;

[0013] The reaction process is as follows:

[0014]

[0015] Step S12, add intermediate 1, K2CO3, and acetonitrile to a three-necked flask, stir evenly, then dropwise add 2,2,6,6-tetramethylpiperidinylbutylamine, heat to 100-110°C and reflux for 13-14h, cool to room temperature, filter, and remove the solvent from the filtrate by rotary evaporation to obtain intermediate 2;

[0016] The reaction process is as follows:

[0017]

[0018] Step S13, adding ethyltriphenylphosphonium bromide into a three-necked flask, introducing nitrogen, adding anhydrous tetrahydrofuran, adding dropwise 1.3 mol / L n-butyllithium solution at -78°C, stirring at room temperature for 1 hour, then lowering the temperature to -78°C, adding dropwise a tetrahydrofuran solution of intermediate 2, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, standing for 2 hours, filtering to remove the precipitate, rotating the filtrate to dryness, and then recrystallizing with n-propanol to obtain intermediate 3;

[0019] The reaction process is as follows:

[0020]

[0021] Step S14, polystyrene, intermediate 3, and azobisisobutyronitrile are melted at 200-240° C., a plasticizer is added thereto, melt blending is continued, and then extrusion granulation is performed to obtain a modified polystyrene resin.

[0022] The reaction process is as follows:

[0023]

[0024] Furthermore, in step S11, the dosage ratio of 4-hydroxybenzaldehyde, K2CO3, acetone, and 1,5-dibromopentane in the acetone solution is 16.4-16.8 mmol: 28.9-29.1 mmol: 20.1-20.3 mL: 5.3-5.4 mL, and the dosage ratio of 1,5-dibromopentane and acetone in the acetone solution of 1,5-dibromopentane is 49.5-49.6 mmol: 5-6 mL.

[0025] Furthermore, in step S12, the usage ratio of the intermediate 1, K2CO3, acetonitrile and 2,2,6,6-tetramethylpiperidinylbutylamine is 15.2-15.6 mmol: 45.4-45.8 mmol: 50.3-50.6 mL: 4.8-4.86 g.

[0026] Furthermore, in step S13, the dosage ratio of ethyltriphenylphosphonium bromide, anhydrous tetrahydrofuran, n-butyllithium solution, and tetrahydrofuran solution of intermediate 2 is 10.2-10.5 mmol: 40.2-40.8 mL: 7.5-7.8 mL: 19.8-20.5 mL, and the dosage ratio of tetrahydrofuran and intermediate 2 in the tetrahydrofuran solution of intermediate 2 is 20 mL: 7.1-7.4 mmol.

[0027] Furthermore, the weight proportions of the polystyrene, intermediate 3, initiator and plasticizer in step S14 are: 20.5-28.6 parts of polystyrene, 35.4-8.7 parts of intermediate, 0.08-0.2 parts of azobisisobutyronitrile and 2.5-3.1 parts of plasticizer, wherein the plasticizer is any one of propylene glycol adipate polyester, propylene glycol sebacate polyester and phthalate polyester.

[0028] The upper material is made by the following steps:

[0029] Step A21, coating the modified coating on the glass fiber cloth, and then affixing polyethylene films on the upper surface and the lower surface of the glass fiber cloth respectively, and compacting them;

[0030] Step A22, drying the compacted glass fiber cloth to form a felt sheet;

[0031] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to obtain the upper material.

[0032] The modified coating is prepared by the following steps:

[0033] Step S21, add 2,2-bis-(4-hydroxyphenyl)hexafluoropropane, 2-chloro-5-nitrotrifluorotoluene and DMF into a three-necked flask, stir and dissolve, add potassium carbonate, heat to 110-120°C for reaction for 5-6h, filter while hot, pour the filtrate into a 70% by mass methanol solution for precipitation, filter, wash the filter cake with methanol, and then dry at 60-70°C for 3-4h to obtain intermediate 4;

[0034] The reaction process is as follows:

[0035]

[0036] Step S22, add intermediate 4, anhydrous ethanol, and Pd / C catalyst into a three-necked flask, perform ultrasonic dispersion at a frequency of 30-40kHz for 20-30min, raise the temperature to 105-110°C, add hydrazine hydrate, control the addition to be completed within 30min, continue the reflux reaction for 3-4h, filter while hot, pour the filtrate into deionized water to precipitate, and dry at 60-70°C for 3-4h to obtain intermediate 5;

[0037] The reaction process is as follows:

[0038]

[0039] Step S23, add intermediate 5, dimethylacetamide, and xylene to a three-necked flask, heat to 80-85° C., stir evenly, add 1,2,4-trimellitic anhydride chloride, heat to 120-140° C., react for 5-6 hours, and obtain a prepolymer;

[0040] The reaction process is as follows:

[0041]

[0042] Step S24, dissolving the prepolymer in N-methylpyrrolidone, adding a mixed solvent thereto, adding dispersant BYK-163, MoS2, and graphite under high-speed stirring, dispersing at high speed for 30 minutes, adding to a ball mill and grinding for 5-6 hours, passing through a 300-mesh sieve, and obtaining a modified coating.

[0043] Furthermore, in step S21, the usage ratio of 2,2-bis-(4-hydroxyphenyl)hexafluoropropane, 2-chloro-5-nitrotrifluorotoluene, DMF, and potassium carbonate is 0.02-0.03 mol: 0.04-0.045 mol: 25-28 mL: 0.035-0.037 mol.

[0044] Furthermore, in step S22, the usage ratio of the intermediate 4, anhydrous ethanol, Pd / C catalyst and hydrazine hydrate is 0.010-0.012 mol:40-45 mL:0.10-0.14 g:2.2-2.5 mL.

[0045] Furthermore, in step S23, the usage ratio of the intermediate 5, dimethylacetamide, xylene, and 1,2,4-trimellitic anhydride chloride is 34.5-38.7 g: 104-110 mL: 45.6-48.7 mL: 68.5-77.4 g.

[0046] Furthermore, in step S24, the dosage ratio of the prepolymer, N-methylpyrrolidone, mixed solvent, dispersant BYK-163, MoS2, and graphite is 35.4-36.5 g: 101.3-102.5 mL: 134.3-142.8 mL: 0.5-0.6 g: 10.2-10.8 g: 3.4-3.8 g, and the mixed solvent is NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0047] Beneficial effects of the present invention: The purpose of the present invention is to provide a special plastic boot that is resistant to smashing and puncture, and the special plastic boot includes a sole material and an upper material. The raw materials of the sole material contain inorganic materials such as mineral powder and carbon fiber in addition to high molecular polymers such as butadiene rubber and modified polystyrene resin. The organic-inorganic materials are compounded to enhance the puncture resistance of the sole, and the sole can be worn for a long time under special environments such as earthquakes, fires, and rugged mountain roads. The modified polystyrene resin enhances the anti-aging ability of the sole and prolongs the service life. The synthetic route of the modified polystyrene resin is as follows: 4-hydroxybenzaldehyde reacts with 1,5-dibromopentane to remove water to generate intermediate 1, intermediate 1 reacts with 2,2,6,6-tetramethylpiperidin butylamine to remove HBr to generate intermediate 2, and intermediate 2 reacts with ethyltriphenylphosphonium bromide under the action of n-butyl lithium to react with ethyltriphenylphosphonium bromide. ng reaction generates intermediate 3. Under the action of initiator azobisisobutyronitrile, intermediate 3 is grafted onto the polystyrene molecular chain, so that the chain segment is connected with hindered amine, which exhibits excellent light stability. Because polymer materials will produce free radicals or hydroperoxides under the action of light, oxygen, etc., hydroperoxides will promote the generation of free radicals, and free radicals will induce polymer degradation, thereby causing aging. In the process of protecting the polymer, the hindered amine itself will be transformed into a highly stable nitroxide free radical. This nitroxide free radical can be combined with the alkyl free radical or alkoxy free radical generated by the polymer to achieve the purpose of capturing free radicals. At the same time, after structural conversion, the nitroxide free radical can be regenerated to continue to capture new free radicals. This cyclic working mechanism allows the hindered amine to effectively and permanently cut off the chain reaction of polymer degradation, thereby preventing the aging of the sole material and extending the service life.

[0048] In addition, further improvements have been made to the upper material. The glass fiber cloth has good mechanical properties and high strength, which greatly enhances the impact resistance, effectively avoiding the phenomenon of kicking foreign objects or being crushed or hit by falling foreign objects during walking, and has high safety. The modified coating is coated on the glass fiber cloth, which makes it corrosion-resistant, acid-resistant, and alkali-resistant, greatly extending its service life. First, the main component of the modified coating is polyamide-amic acid prepolymer, and the diamine monomer is improved by introducing trifluoromethyl. The introduction of trifluoromethyl improves the hydrophobicity of the substrate and reduces its hygroscopicity. The CF bond energy is as high as 485 kJ / mol, and the covalent bond energy is high. The photon energy of ultraviolet light is about 544 kJ / mol, indicating that the CF bond is very stable under light and has a strong shielding effect. The introduction of trifluoromethyl into the polymer main chain can effectively protect the CC main chain from damage by ultraviolet light and chemicals, so that it has good chemical corrosion resistance and weather resistance, so that the prepared special plastic boots are not only resistant to smashing and puncture, but also corrosion-resistant and highly safe. DETAILED DESCRIPTION

[0049] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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.

[0050] Example 1

[0051] The modified polystyrene resin is prepared by the following steps:

[0052] Step S11, add 16.4 mmol 4-hydroxybenzaldehyde, 28.9 mmol K2CO3, and 20.1 mL acetone to a three-necked flask, stir evenly, then dropwise add 5.3 mL 1,5-dibromopentane acetone solution thereto, reflux at room temperature for 16 hours, remove the solvent by rotary evaporation, wash the product twice with dichloromethane, dry with magnesium sulfate, and purify by silica gel column chromatography to obtain intermediate 1, wherein the amount ratio of 1,5-dibromopentane to acetone in the 1,5-dibromopentane acetone solution is 49.5 mmol:5 mL;

[0053] Step S12, add 15.2 mmol of intermediate 1, 45.4 mmol of K2CO3, and 50.3 mL of acetonitrile into a three-necked flask, stir evenly, then dropwise add 4.8 g of 2,2,6,6-tetramethylpiperidinylbutylamine, heat to 100° C. and reflux for 13 h, cool to room temperature, filter, and remove the solvent from the filtrate by rotary evaporation to obtain intermediate 2;

[0054] Step S13, adding 10.2 mmol ethyltriphenylphosphonium bromide into a three-necked flask, introducing nitrogen, adding 40.2 mL anhydrous tetrahydrofuran, adding dropwise 7.5 mL 1.3 mol / L n-butyl lithium solution at -78 ° C, stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C, adding dropwise 19.8 mL tetrahydrofuran solution of intermediate 2, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, standing for 2 hours, filtering to remove the precipitate, rotating the filtrate to dryness, and then recrystallizing with n-propanol to obtain intermediate 3, wherein the amount ratio of tetrahydrofuran to intermediate 2 in the tetrahydrofuran solution of intermediate 2 is 20 mL:7.1 mmol;

[0055] Step S14, 20.5 parts of polystyrene, 5.4 parts of intermediate 3, and 0.08 parts of azobisisobutyronitrile are melted at 200° C., 2.5 parts of propylene glycol adipate polyester are added thereto, melt blending is continued, and then extrusion granulation is performed to obtain a modified polystyrene resin.

[0056] Example 2

[0057] The modified polystyrene resin is prepared by the following steps:

[0058] Step S11, add 16.6 mmol 4-hydroxybenzaldehyde, 29 mmol K2CO3, and 20.2 mL acetone to a three-necked flask, stir evenly, then dropwise add 5.3 mL 1,5-dibromopentane acetone solution thereto, reflux at room temperature for 16 hours, remove the solvent by rotary evaporation, wash the product twice with dichloromethane, dry with magnesium sulfate, and purify by silica gel column chromatography to obtain intermediate 1, wherein the amount ratio of 1,5-dibromopentane to acetone in the 1,5-dibromopentane acetone solution is 49.5 mmol:5 mL;

[0059] Step S12, add 15.4 mmol of intermediate 1, 45.6 mmol of K2CO3, and 50.4 mL of acetonitrile into a three-necked flask, stir evenly, then dropwise add 4.83 g of 2,2,6,6-tetramethylpiperidinylbutylamine, heat to 105° C., reflux for 13 h, cool to room temperature, filter, and remove the solvent from the filtrate by rotary evaporation to obtain intermediate 2;

[0060] Step S13, adding 10.4 mmol ethyltriphenylphosphonium bromide into a three-necked flask, introducing nitrogen, adding 40.5 mL anhydrous tetrahydrofuran, adding dropwise 7.6 mL 1.3 mol / L n-butyl lithium solution at -78 ° C, stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C, adding dropwise 20.2 mL tetrahydrofuran solution of intermediate 2, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, standing for 2 hours, filtering to remove the precipitate, rotating the filtrate to dryness, and then recrystallizing with n-propanol to obtain intermediate 3, wherein the amount ratio of tetrahydrofuran to intermediate 2 in the tetrahydrofuran solution of intermediate 2 is 20 mL:7.2 mmol;

[0061] Step S14, 25.2 parts of polystyrene, 6.9 parts of intermediate 3, and 0.12 parts of azobisisobutyronitrile are melted at 220° C., 2.8 parts of propylene glycol sebacate polyester are added thereto, melt blending is continued, and then extrusion granulation is performed to obtain a modified polystyrene resin.

[0062] Example 3

[0063] The modified polystyrene resin is prepared by the following steps:

[0064] Step S11, add 16.8 mmol 4-hydroxybenzaldehyde, 29.1 mmol K2CO3, and 20.3 mL acetone to a three-necked flask, stir evenly, then dropwise add 5.4 mL 1,5-dibromopentane acetone solution thereto, reflux at room temperature for 17 hours, remove the solvent by rotary evaporation, wash the product with dichloromethane three times, dry with magnesium sulfate, and purify by silica gel column chromatography to obtain intermediate 1, wherein the amount ratio of 1,5-dibromopentane to acetone in the 1,5-dibromopentane acetone solution is 49.6 mmol:6 mL;

[0065] Step S12, add 15.6 mmol of intermediate 1, 45.8 mmol of K2CO3, and 50.6 mL of acetonitrile into a three-necked flask, stir evenly, then dropwise add 4.86 g of 2,2,6,6-tetramethylpiperidinylbutylamine, heat to 110° C., reflux for 14 h, cool to room temperature, filter, and remove the solvent from the filtrate by rotary evaporation to obtain intermediate 2;

[0066] Step S13, adding 10.5 mmol ethyltriphenylphosphonium bromide into a three-necked flask, introducing nitrogen, adding 40.8 mL anhydrous tetrahydrofuran, adding dropwise 7.8 mL 1.3 mol / L n-butyl lithium solution at -78 ° C, stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C, adding dropwise 20.5 mL tetrahydrofuran solution of intermediate 2, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, standing for 2 hours, filtering to remove the precipitate, rotating the filtrate to dryness, and then recrystallizing with n-propanol to obtain intermediate 3, wherein the amount ratio of tetrahydrofuran to intermediate 2 in the tetrahydrofuran solution of intermediate 2 is 20 mL:7.4 mmol;

[0067] Step S14, 28.6 parts of polystyrene, 8.7 parts of intermediate 3, and 0.2 parts of azobisisobutyronitrile are melted at 240° C., 3.1 parts of phthalic acid polyester are added thereto, and melt blending is continued, followed by extrusion granulation to obtain a modified polystyrene resin.

[0068] Example 4

[0069] The modified coating is prepared by the following steps:

[0070] Step S21, add 0.02 mol 2,2-bis-(4-hydroxyphenyl)hexafluoropropane, 0.04 mol 2-chloro-5-nitrotrifluorotoluene and 25 mL DMF into a three-necked flask, stir and dissolve, add 0.035 mol potassium carbonate, heat to 110°C and react for 5 hours, filter while hot, pour the filtrate into a 70% methanol solution for precipitation, filter, wash the filter cake with methanol, and then dry at 60°C for 3 hours to obtain intermediate 4;

[0071] Step S22, add 0.010 mol intermediate 4, 40 mL anhydrous ethanol, and 0.10 g Pd / C catalyst into a three-necked flask, and ultrasonically disperse at a frequency of 30 kHz for 20 min, heat to 105° C., add 2.2 mL hydrazine hydrate, control the addition to be completed within 30 min, continue reflux reaction for 3 h, filter while hot, pour the filtrate into deionized water to precipitate, and dry at 60° C. for 3 h to obtain intermediate 5;

[0072] Step S23, add 34.5 g of intermediate 5, 104 mL of dimethylacetamide, and 45.6 mL of xylene into a three-necked flask, heat to 80° C., stir evenly, add 68.5 g of 1,2,4-trimellitic anhydride chloride, heat to 120° C. and react for 5 h to obtain a prepolymer;

[0073] Step S24, dissolve 35.4g of prepolymer in 101.3mL of N-methylpyrrolidone, add 134.3mL of mixed solvent thereto, add 0.5g of dispersant BYK-163, 10.2g of MoS2, and 3.4g of graphite under high-speed stirring, disperse at high speed for 30min, add to a ball mill and grind for 5h, pass through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent is NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0074] Example 5

[0075] The modified coating is prepared by the following steps:

[0076] Step S21, add 0.025 mol 2,2-bis-(4-hydroxyphenyl)hexafluoropropane, 0.042 mol 2-chloro-5-nitrotrifluorotoluene and 26 mL DMF into a three-necked flask, stir and dissolve, add 0.036 mol potassium carbonate, heat to 115°C and react for 5 hours, filter while hot, pour the filtrate into a 70% methanol solution for precipitation, filter, wash the filter cake with methanol, and then dry at 65°C for 3 hours to obtain intermediate 4;

[0077] Step S22, add 0.011 mol intermediate 4, 43 mL anhydrous ethanol, and 0.12 g Pd / C catalyst into a three-necked flask, and ultrasonically disperse at a frequency of 35 kHz for 25 min, heat to 108°C, add 2.3 mL hydrazine hydrate, control the addition to be completed within 30 min, continue reflux reaction for 3 h, filter while hot, pour the filtrate into deionized water to precipitate, and dry at 65°C for 3 h to obtain intermediate 5;

[0078] Step S23, add 36.5 g of intermediate 5, 108 mL of dimethylacetamide, and 46.9 mL of xylene into a three-necked flask, heat to 83° C., stir evenly, add 72.5 g of 1,2,4-trimellitic anhydride chloride, heat to 130° C., react for 5 h, and obtain a prepolymer;

[0079] Step S24, dissolve 35.9g of prepolymer in 101.9mL of N-methylpyrrolidone, add 138.2mL of mixed solvent thereto, add 0.55g of dispersant BYK-163, 10.4g of MoS2, and 3.6g of graphite under high-speed stirring, disperse at high speed for 30min, add to a ball mill and grind for 5h, pass through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent is NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0080] Example 6

[0081] The modified coating is prepared by the following steps:

[0082] Step S21, add 0.03 mol 2,2-bis-(4-hydroxyphenyl)hexafluoropropane, 0.045 mol 2-chloro-5-nitrotrifluorotoluene and 28 mL DMF into a three-necked flask, stir and dissolve, add 0.037 mol potassium carbonate, heat to 120°C and react for 6 hours, filter while hot, pour the filtrate into a 70% methanol solution for precipitation, filter, wash the filter cake with methanol, and then dry at 70°C for 4 hours to obtain intermediate 4;

[0083] Step S22, add 0.012 mol intermediate 4, 45 mL anhydrous ethanol, and 0.14 g Pd / C catalyst into a three-necked flask, and ultrasonically disperse at a frequency of 40 kHz for 30 min, heat to 110° C., add 2.5 mL hydrazine hydrate, control the addition to be completed within 30 min, continue reflux reaction for 4 h, filter while hot, pour the filtrate into deionized water to precipitate, and dry at 70° C. for 4 h to obtain intermediate 5;

[0084] Step S23, add 38.7 g of intermediate 5, 110 mL of dimethylacetamide, and 48.7 mL of xylene into a three-necked flask, heat to 85° C., stir evenly, add 77.4 g of 1,2,4-trimellitic anhydride chloride, heat to 140° C., react for 6 hours, and obtain a prepolymer;

[0085] Step S24, dissolve 36.5g of prepolymer in 102.5mL of N-methylpyrrolidone, add 142.8mL of mixed solvent thereto, add 0.6g of dispersant BYK-163, 10.8g of MoS2, and 3.8g of graphite under high-speed stirring, disperse at high speed for 30min, add to a ball mill and grind for 6h, pass through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent is NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0086] Example 7

[0087] A special plastic boot that is resistant to smashing and puncture, comprising a sole material and an upper material;

[0088] The sole material is prepared by the following steps:

[0089] Step A11, taking 20 parts of butadiene rubber, 10 parts of the modified polystyrene resin prepared in Example 1, 3 parts of hot melt adhesive, 3 parts of phosphotyrite, 1 part of sulfur, and 2 parts of carbon fiber in parts by weight, and mixing them to synthesize a raw rubber sheet;

[0090] Step A12, loading the raw rubber sheet into the sole mold, applying 80 kg pressure to the rubber sheet using a hydraulic press, and vulcanizing it at 100° C. for 8 minutes to obtain the sole.

[0091] The upper material is made by the following steps:

[0092] Step A21, coating the modified coating prepared in Example 4 on a glass fiber cloth, and then affixing polyethylene films on the upper and lower surfaces of the glass fiber cloth respectively, and compacting them;

[0093] Step A22, drying the compacted glass fiber cloth to form a felt sheet;

[0094] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to obtain the upper material.

[0095] Example 8

[0096] A special plastic boot that is resistant to smashing and puncture, comprising a sole material and an upper material;

[0097] The sole material is prepared by the following steps:

[0098] Step A11, taking 28 parts of butadiene rubber, 14 parts of the modified polystyrene resin prepared in Example 2, 4 parts of hot melt adhesive, 4 parts of pyrite, 1 part of sulfur, and 3 parts of carbon fiber in parts by weight, and mixing them to synthesize a raw rubber sheet;

[0099] Step A12, loading the raw rubber sheet into the sole mold, applying 85 kg pressure to the rubber sheet using a hydraulic press, and vulcanizing it at a temperature of 110° C. for 10 minutes to obtain the sole.

[0100] The upper material is made by the following steps:

[0101] Step A21, coating the modified coating prepared in Example 5 on a glass fiber cloth, and then affixing polyethylene films on the upper and lower surfaces of the glass fiber cloth respectively, and compacting them;

[0102] Step A22, drying the compacted glass fiber cloth to form a felt sheet;

[0103] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to obtain the upper material.

[0104] Example 9

[0105] A special plastic boot that is resistant to smashing and puncture, comprising a sole material and an upper material;

[0106] The sole material is prepared by the following steps:

[0107] Step A11, taking 35 parts of butadiene rubber, 18 parts of the modified polystyrene resin prepared in Example 3, 5 parts of hot melt adhesive, 5 parts of copper ore, 2 parts of sulfur, and 4 parts of carbon fiber in parts by weight, and mixing them to synthesize a raw rubber sheet;

[0108] Step A12, loading the raw rubber sheet into the sole mold, applying 90 kg pressure to the rubber sheet using a hydraulic press, and vulcanizing it at a temperature of 115° C. for 12 minutes to obtain the sole.

[0109] The upper material is made by the following steps:

[0110] Step A21, coating the modified coating prepared in Example 6 on a glass fiber cloth, and then affixing polyethylene films on the upper and lower surfaces of the glass fiber cloth respectively, and compacting them;

[0111] Step A22, drying the compacted glass fiber cloth to form a felt sheet;

[0112] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to obtain the upper material.

[0113] Comparative Example 1

[0114] Oil-resistant, acid-resistant and alkali-resistant special boots produced by Guangzhou Yihuashang Trading Co., Ltd.

[0115] Comparative Example 2

[0116] The special plastic boots of Comparative Example 2 refer to Example 7, except that no modified polystyrene resin is added.

[0117] Comparative Example 3

[0118] The special plastic boots of Comparative Example 3 refer to Example 7, except that the modified coating is not applied.

[0119] The following performance tests were conducted on the special boots of Examples 7-9 and Comparative Examples 1-3: (1) Anti-smashing performance: GB16756-5.4.3 (An1 type: impact hammer mass 23 kg, drop height 900 mm, after inspection, the deformation gap in the toe box is greater than 15 mm and is qualified) was used to test the anti-smashing performance of the sole and the upper; (2) Corrosion resistance: the upper was immersed in 5.3 mol / L sulfuric acid or sodium hydroxide solution at 23°C for 36 h, taken out and dried, cracks were observed and the tear strength was calculated. The test data are shown in Table 1:

[0120] Table 1

[0121]

[0122] It can be seen from Table 1 that, compared with Comparative Examples 1-3, the plastic boots prepared in Examples 7-9 have excellent anti-smashing, anti-puncture and corrosion resistance.

[0123] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A special plastic boot that is resistant to smashing and puncture, characterized in that: Including sole materials and upper materials; The sole material is prepared by the following steps: Step A11, taking 20-35 parts of butadiene rubber, 10-18 parts of modified polystyrene resin, 3-5 parts of hot melt adhesive, 3-5 parts of ore powder, 1-2 parts of sulfur, and 2-4 parts of carbon fiber in parts by weight, and mixing them to synthesize a raw rubber sheet; Step A12, loading the raw rubber sheet into a sole mold, applying 80-90 kg of pressure to the rubber sheet using a hydraulic press, and vulcanizing the rubber sheet at a temperature of 100-115° C. for 8-12 minutes to obtain a sole; The modified polystyrene resin is prepared by the following steps: Step S11, after 4-hydroxybenzaldehyde, K2CO3 and acetone are uniformly stirred, an acetone solution of 1,5-dibromopentane is added dropwise thereto, and the mixture is refluxed at room temperature for 16-17 hours, and the solvent is removed by rotary evaporation. The product is washed, dried and purified to obtain intermediate 1; Step S12, after the intermediate 1, K2CO3 and acetonitrile are uniformly stirred, 2,2,6,6-tetramethylpiperidin butylamine is added dropwise thereto, the temperature is raised to 100-110°C and refluxed for reaction for 13-14 hours, the mixture is cooled to room temperature, filtered, and the solvent is removed from the filtrate by rotary evaporation to obtain the intermediate 2; Step S13, adding ethyltriphenylphosphonium bromide into a three-necked flask, introducing nitrogen, adding anhydrous tetrahydrofuran, adding n-butyl lithium solution dropwise at -78°C, stirring at room temperature for 1 hour, lowering the temperature to -78°C, adding tetrahydrofuran solution of intermediate 2 dropwise, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, standing for 2 hours, filtering to remove the precipitate, rotating the filtrate to dryness, and recrystallizing to obtain intermediate 3; Step S14, polystyrene, intermediate 3, and azobisisobutyronitrile are melted at 200-240° C., a plasticizer is added thereto, melt blending is continued, and then extrusion granulation is performed to obtain a modified polystyrene resin.

2. The anti-smashing and anti-puncture special plastic boots according to claim 1, characterized in that: In step S11, the dosage ratio of 4-hydroxybenzaldehyde, K2CO3, acetone, and 1,5-dibromopentane in acetone solution is 16.4-16.8 mmol: 28.9-29.1 mmol: 20.1-20.3 mL: 5.3-5.4 mL, and the dosage ratio of 1,5-dibromopentane to acetone in the 1,5-dibromopentane in acetone solution is 49.5-49.6 mmol: 5-6 mL.

3. The anti-smashing and anti-puncture special plastic boots according to claim 1, characterized in that: The usage ratio of the intermediate 1, K2CO3, acetonitrile and 2,2,6,6-tetramethylpiperidinylbutylamine in step S12 is 15.2-15.6 mmol: 45.4-45.8 mmol: 50.3-50.6 mL: 4.8-4.86 g.

4. The anti-smashing and anti-puncture special plastic boots according to claim 1, characterized in that: In step S13, the usage ratio of ethyltriphenylphosphonium bromide, anhydrous tetrahydrofuran, n-butyllithium solution, and tetrahydrofuran solution of intermediate 2 is 10.2-10.5 mmol: 40.2-40.8 mL: 7.5-7.8 mL: 19.8-20.5 mL, and the usage ratio of tetrahydrofuran and intermediate 2 in the tetrahydrofuran solution of intermediate 2 is 20 mL: 7.1-7.4 mmol.

5. The anti-smashing and anti-puncture special plastic boots according to claim 1, characterized in that: The weight proportions of the polystyrene, intermediate 3, initiator and plasticizer in step S14 are: 20.5-28.6 parts of polystyrene, 35.4-8.7 parts of intermediate, 0.08-0.2 parts of azobisisobutyronitrile and 2.5-3.1 parts of plasticizer, wherein the plasticizer is any one of propylene glycol adipate polyester, propylene glycol sebacate polyester and phthalate polyester.

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