1. The preparation method of the antibacterial sole material is characterized by comprising the following steps:

step A, cleaning oyster shells, soaking the oyster shells in water for 12-24 hours, drying the oyster shells in an oven at 50-70 ℃ for 24-72 hours, crushing the oyster shells, and sieving the crushed oyster shells with a 100-mesh sieve to obtain oyster shell powder;

b, putting the oyster shell powder obtained in the step A into a muffle furnace, calcining for 2-6 hours at 600-1000 ℃, partially decomposing the oyster shell powder into calcium oxide, and sieving the calcined powder with a 100-mesh sieve to obtain calcined oyster shell powder;

step C, uniformly mixing 100 parts by weight of a mixture of styrene-butadiene rubber and butadiene rubber on an open mill, wherein the mixing temperature is 30-45 ℃, the mixing time is 10-15 minutes, adding 10-40 parts by weight of calcined oyster shell powder, uniformly mixing, adding 1.5-3 parts by weight of sulfur, 2-4 parts by weight of zinc oxide, 0.8-1.2 parts by weight of stearic acid, 0.5-2.5 parts by weight of coupling agent and 1.2-2.0 parts by weight of tetramethyl thiuram disulfide, mixing, wherein the mixing temperature is 45-55 ℃, the mixing time is 20-30 minutes, and standing for more than 2 hours after mixing is completed;

and D, pressing and vulcanizing the material obtained in the step C in a flat vulcanizing machine to obtain the sole material.

2. The method of claim 1, wherein the coupling agent is a titanate coupling agent, a silane coupling agent, or an aluminate coupling agent.

3. The method for preparing the antibacterial sole material according to claim 2, wherein the titanate coupling agent is isopropyl triisostearate, the silane coupling agent is gamma-mercaptopropyltrimethoxysilane, and the aluminate coupling agent is isopropyl distearoyloxy aluminate.

Background

The fillers commonly used for the shoe sole at present are calcium carbonate, silicon dioxide, talcum powder, pottery clay and the like. Most of the fillers come from mineral exploitation, and with the continuous increase of demand, excessive exploitation of minerals brings considerable influence on the natural ecological environment, and a series of environmental problems such as water and soil loss, landslide, water body air pollution and the like are caused. In addition, the compatibility of inorganic fillers such as calcium carbonate with materials such as styrene butadiene rubber and butadiene rubber needs to be improved. In addition, most of the existing sole antibacterial materials are artificially synthesized antibacterial materials, so that the cost is relatively high, and the application of the sole antibacterial materials in soles is limited.

Accordingly, the present inventors have made extensive studies to solve the above problems and have made the present invention.

Disclosure of Invention

The invention aims to provide a preparation method of a sole material which is more environment-friendly, has certain antibacterial performance and is simple in process.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of an antibacterial sole material comprises the following steps:

step A, cleaning oyster shells, soaking the oyster shells in water for 12-24 hours, drying the oyster shells in an oven at 50-70 ℃ for 24-72 hours, crushing the oyster shells, and sieving the crushed oyster shells with a 100-mesh sieve to obtain oyster shell powder;

b, putting the oyster shell powder obtained in the step A into a muffle furnace, calcining for 2-6 hours at 600-1000 ℃, partially decomposing the oyster shell powder into calcium oxide, and sieving the calcined powder with a 100-mesh sieve to obtain calcined oyster shell powder;

step C, uniformly mixing 100 parts by weight of a mixture of styrene-butadiene rubber and butadiene rubber on an open mill, wherein the mixing temperature is 30-45 ℃, the mixing time is 10-15 minutes, adding 10-40 parts by weight of calcined oyster shell powder, uniformly mixing, adding 1.5-3 parts by weight of sulfur, 2-4 parts by weight of zinc oxide, 0.8-1.2 parts by weight of stearic acid, 0.5-2.5 parts by weight of coupling agent and 1.2-2.0 parts by weight of tetramethyl thiuram disulfide, mixing, wherein the mixing temperature is 45-55 ℃, the mixing time is 20-30 minutes, and standing for more than 2 hours after mixing is completed;

and D, pressing and vulcanizing the material obtained in the step C in a flat vulcanizing machine to obtain the sole material.

In a preferred embodiment of the present invention, the coupling agent is a titanate coupling agent, a silane coupling agent, or an aluminate coupling agent.

By adopting the technical scheme of the invention, the waste oyster shells are calcined and modified, and are compounded with the styrene butadiene rubber and the butadiene rubber, so that the high-value application of the waste oyster shells is realized, the waste is turned into wealth, the application of natural biological calcium carbonate is promoted, the influence of the waste oyster shells on the natural environment is reduced, a new direction is developed for the application of natural biomass materials in shoe materials, and the whole process is simple and suitable for industrial popularization. Meanwhile, the calcining degree of the oyster shell is controlled to partially decompose the oyster shell into calcium oxide, so that the oyster shell composite material has certain antibacterial performance, the compatibility between the oyster shell powder and rubber is improved by utilizing a surfactant, and the antibacterial performance of the filler is kept while the comprehensive performance of the composite material is improved.

Detailed Description

In order to further explain the technical solution of the present invention, the following detailed description is made with reference to the embodiments.

And (3) oyster shell treatment: washing collected oyster shells, soaking in distilled water for 12-24 hr to remove attachments and dirt on the surfaces of the oyster shells, and drying in an oven at 50-70 deg.C for 24-72 hr. After the oyster shells are fully dried, the oyster shells are broken and sieved by a 100-mesh sieve for standby.

And (3) putting the sieved oyster shell powder into a muffle furnace, calcining the oyster shell powder for 2 to 6 hours at the temperature of between 600 and 1000 ℃, and partially decomposing the oyster shell powder into calcium oxide by controlling the calcining temperature and the calcining time. Sieving the calcined powder with a 100-mesh sieve to obtain the calcined oyster shell powder.

The manufacturing method of the sole comprises the following steps:

the formula comprises the following components in parts by weight: 100 parts of styrene butadiene rubber and butadiene rubber blend, 10-40 parts of calcined oyster shell powder, and sulfur: 1.5-3 parts, zinc oxide (ZnO): 2-4 parts, stearic acid: 0.8-1.2 parts of coupling agent, 0.5-2.5 parts of tetramethyl thiuram disulfide (namely accelerator TMTD): 1.2 to 2.0 portions. The styrene butadiene rubber and the butadiene rubber are used as base materials, the calcined oyster shell powder is used as a filler, meanwhile, the oyster shell powder suitable for calcination can also play a role of an antibacterial agent, the sulfur is used as a vulcanizing agent, the zinc oxide and the stearic acid are used as active agents, the coupling agent can improve the compatibility between the calcined oyster shell powder and the rubber base materials, and the tetramethyl thiuram disulfide is used as an accelerator, so that the utilization rate of the sulfur can be improved.

The process comprises the following steps:

(1) the calcined oyster shell powder is prepared by the method.

(2) Weighing calcined oyster shell powder, butadiene styrene rubber, butadiene rubber, sulfur, zinc oxide, stearic acid, a coupling agent, TMTD and other raw materials according to a formula.

(3) Firstly, uniformly mixing styrene-butadiene rubber and butadiene rubber on an open mill, adding calcined oyster shell powder, and sequentially adding a coupling agent, stearic acid, zinc oxide, sulfur and TMTD after uniformly mixing. Standing for more than 2 hours after the mixing is finished.

(4) And (3) performing compression molding on the parked rubber material in a flat vulcanizing machine at 160 ℃ to obtain the composite material.

Example 1:

(1) after oyster shell is soaked for 24 hours, the oyster shell is dried in an oven at 60 ℃ for 48 hours and calcined at 600 ℃ for 6 hours, and the obtained oyster shell powder is sieved by a 100-mesh sieve for later use.

(2) 70 parts of styrene butadiene rubber and 30 parts of butadiene rubber are plasticated uniformly on an open mill at the mixing temperature of 35 ℃ for 12 minutes. Weighing 10 parts of the oyster shell powder calcined in the step (1), uniformly mixing the oyster shell powder with the rubber, sequentially adding 1 part of titanate coupling agent (specifically isopropyl triisostearate), 1 part of stearic acid, 2 parts of zinc oxide, 2 parts of sulfur and 1.2 parts of TMTD, mixing at the temperature of 50 ℃ for 25 minutes, uniformly mixing, taking out, and standing for 8 hours. (3) And (3) pressing and vulcanizing the rubber sheet in a flat vulcanizing machine to obtain the sole material. The resulting vulcanizate had a tensile strength of 12.4MPa, an elongation at break of 610% and a tear strength of 22.6 kN/m.

Example 2:

(1) after oyster shell is soaked for 12 hours, the oyster shell is dried in an oven at 70 ℃ for 24 hours and calcined at 800 ℃ for 4 hours, and the obtained oyster shell powder is sieved by a 100-mesh sieve for later use.

(2) 60 parts of styrene butadiene rubber and 40 parts of butadiene rubber are plasticated uniformly on an open mill at the mixing temperature of 35 ℃ for 12 minutes. Weighing 20 parts of the oyster shell powder calcined in the step (1), uniformly mixing the oyster shell powder with the rubber, sequentially adding 1.5 parts of silane coupling agent (specifically gamma-mercaptopropyltrimethoxysilane), 1.2 parts of stearic acid, 3 parts of zinc oxide, 2.5 parts of sulfur and 1.5 parts of TMTD, mixing at the temperature of 50 ℃ for 25 minutes, and taking out and standing for 8 hours after uniform mixing.

(3) And (3) pressing and vulcanizing the rubber sheet in a flat vulcanizing machine to obtain the sole material. The obtained vulcanized rubber has the tensile strength of 13.1Mpa, the elongation at break of 630 percent and the tear strength of 24.1 kN/m.

Example 3:

(1) after oyster shell is soaked for 24 hours, the oyster shell is dried in a 50 ℃ oven for 72 hours and calcined at 1000 ℃ for 2 hours, and the obtained oyster shell powder is sieved by a 100-mesh sieve for standby.

(2) 50 parts of styrene butadiene rubber and 50 parts of butadiene rubber are plasticated on an open mill uniformly at the mixing temperature of 35 ℃ for 12 minutes. Weighing 10 parts of the oyster shell powder calcined in the step (1), uniformly mixing the oyster shell powder with the rubber, sequentially adding 2 parts of an aluminate coupling agent (specifically isopropyl distearoyloxy aluminate), 1.0 part of stearic acid, 2 parts of zinc oxide, 1.75 parts of sulfur and 1.2 parts of TMTD, mixing at the temperature of 50 ℃ for 25 minutes, and taking out and standing for 8 hours after uniform mixing.

(3) And (3) pressing and vulcanizing the rubber sheet in a flat vulcanizing machine to obtain the sole material. The obtained vulcanized rubber has the tensile strength of 12.9Mpa, the elongation at break of 660 percent and the tear strength of 23.6kN/m, and has certain inhibiting capacity on staphylococcus aureus.

Example 4

(1) After oyster shell is soaked for 24 hours, the oyster shell is dried in an oven at 60 ℃ for 48 hours and is crushed by a mechanical method, and the obtained oyster shell powder is sieved by a 100-mesh sieve for standby.

(2) 70 parts of styrene butadiene rubber and 30 parts of butadiene rubber are plasticated uniformly on an open mill at the mixing temperature of 35 ℃ for 12 minutes. Weighing 10 parts of oyster shell powder obtained in the step (1), uniformly mixing with the rubber, sequentially adding 1 part of titanate coupling agent, 1 part of stearic acid, 2 parts of zinc oxide, 2 parts of sulfur and 1.2 parts of TMTD, mixing at 50 ℃ for 25 minutes, uniformly mixing, taking out, and standing for 8 hours.

(3) And (3) pressing and vulcanizing the rubber sheet in a flat vulcanizing machine to obtain the sole material. The resulting vulcanizate had a tensile strength of 11.9MPa, an elongation at break of 580% and a tear strength of 22.3 kN/m.

The sole materials obtained in the 4 examples are tested according to the technical conditions of QB-T2881-2013 footwear and footwear component antibacterial performance, the test strain is staphylococcus aureus, and the results are shown in the following table:

serial number	Oyster shell treatment mode	Staphylococcus aureus antibacterial ratio (%)
			Example 1	Calcining at 600 ℃ for 6 hours	Antibacterial rate of 2.0
Example 2	Calcining at 800 ℃ for 4 hours	Antibacterial rate of 4.2
			Example 3	Calcining at 1000 ℃ for 2 hours	Antibacterial rate 64
Example 4	Without calcination, mechanically comminuted	No antibacterial effect

The antibacterial property of the material obtained by the invention is that the oyster shell powder contains calcium oxide in a calcination product at a higher temperature (1000 ℃ in the experiment), and the product can cause the conformational change of charge molecules of bacterial cell membranes and disturb the normal physiological activities of cells, thereby playing the roles of sterilization and bacteriostasis.

The product form of the present invention is not limited to the embodiments, and any suitable changes or modifications of the similar ideas by anyone should be considered as not departing from the patent scope of the present invention.