CN111109760A

CN111109760A - High-toughness multi-layer repressing anti-skid rubber sole and preparation process thereof

Info

Publication number: CN111109760A
Application number: CN201911362730.5A
Authority: CN
Inventors: 马成龙
Original assignee: Anhui Mingjiexun Network Technology Co Ltd
Current assignee: Anhui Mingjiexun Network Technology Co Ltd
Priority date: 2019-12-26
Filing date: 2019-12-26
Publication date: 2020-05-08

Abstract

The invention provides a high-toughness multi-layer repressing anti-skidding rubber sole and a preparation process thereof, the rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises the following components: carboxyl nitrile rubber, agricultural and forestry waste, sponge iron, nano-scale metal oxide, composite emulsion and an additive; the middle layer comprises the following components: carboxyl butyl rubber, tetrapropylene fluoride rubber, agricultural and forestry waste, composite emulsion, nano-scale metal oxide and an additive; the inner layer comprises the following components: the invention has the advantages of high functional pertinence, high integral comfort, wear-resisting and skid-proof bottom, light and high-elasticity middle layer, comfortable and antibacterial inside and remarkably improved comprehensive quality and suitability for the requirements of most people.

Description

High-toughness multi-layer repressing anti-skid rubber sole and preparation process thereof

Technical Field

The invention relates to the technical field of rubber sole materials and preparation, in particular to a high-toughness multi-layer composite-pressing anti-skidding rubber sole and a preparation process thereof.

Background

China is the biggest shoe production country and export country in the world at present, the main materials for producing the soles comprise rubber, PU, PVC, MD, TPR, TPU, EVA and the like, the rubber soles occupy a large proportion in shoe products due to the advantages of skid resistance, high elasticity, good wear resistance, difficult fracture, good extensibility, stable contraction and the like, and the finished shoes of the first-line brand in China are mostly made of rubber soles. However, rubber also has many disadvantages, such as: heavy, easy to bloom, not easy to decompose and recycle; not hard and easy to be pricked; the rubber sole has poor air permeability and hygroscopicity, is afraid of oil immersion, is not suitable for being worn in places such as automobile gas stations and the like which are in contact with oil, and the like, and greatly influences the application of the rubber sole. For shoe rubber, good anti-skid performance is one of basic functions of a rubber product for a sole, and is an important index for measuring the quality of shoes, when shoes are selected, the problem that the sole is easy to skid is generally considered, particularly, the problem that the sole is wet and slippery is particularly prominent in rainy days and other conditions, and the easy-to-skid sole can always slip down in the walking process to cause personal injury.

The anti-skid performance of the sole refers to the anti-skid effect or the grip of the sole on the ground, and the quality of the anti-skid performance is directly related to the safety of the shoe when the shoe is worn. The sole has poor anti-skid performance, is easy to skid and tumble when walking on a wet and slippery and icy road surface, has low temperature in winter in most northern areas of China, is easy to accumulate water and ice on the road surface, and is easy to skid when people walk on the road surface. In addition, along with the flourishing development of economy and the continuous progress of society, people build the road surface and the indoor ground more and more smoothly, which leads to the frequent occurrence of falling injury accidents, so that the anti-skid performance of the sole material is effectively improved.

The sole is a general term for an outsole, a midsole, and an insole, because the sole is divided into an outsole, a midsole, and an insole, depending on the ease of construction of the sole, as a main component of vulcanized rubber shoes. Since the outsole is in direct contact with the ground, bears the entire weight of the human body while running, jumping and walking, is subject to frequent bending and wear, and cracks and even breaks are generated due to fatigue of the outsole due to multiple flexions and aging, relatively speaking, the performance requirements of the outsole are a little higher. Therefore, in addition to the demand for their anti-slip properties, the demand for their mechanical properties is also increasing.

At present, soles produced by various shoe factories are difficult to have high elasticity and high wear resistance, and have poor aging resistance, or have certain elasticity and wear resistance, but the effect is not good. These three properties, if not very effective, detract from the consumer experience and greatly reduce the life of the shoe.

For example, CN201810127566.9 published in China proposes a formula of a novel rubber shoe sole and a preparation method thereof, and the elasticity of the prepared sole is increased by reasonably improving the formula, so that the sole is not easy to break and the comfortable feeling of feet is improved. Also, as the Chinese published CN201611045111.X provides a sole antiskid rubber composite material and a preparation method thereof, the prepared sole antiskid rubber composite material has the advantages of large friction coefficient, good wear resistance, improved walking stability, improved comfort and the like through reasonable formula improvement and proportioning; the preparation method has simple process and convenient operation.

Therefore, with the diversity and high demand of modern life style, the performance requirement of the sole is continuously improved, and the design of the sole with better performance following the market demand is a way of no end exploration.

Disclosure of Invention

Aiming at the existing problems, the invention provides the high-toughness multi-layer repressing anti-skidding rubber sole and the preparation process thereof, through reasonable raw material selection and adoption of multi-layer structure repressing, the high-toughness multi-layer repressing anti-skidding rubber sole has strong function pertinence, high integral comfort level, wear resistance and skid resistance of the bottom, light weight and high elasticity of the middle layer, comfort and antibiosis of the inner layer, obviously improved comprehensive quality and suitability for the requirements of most people.

In order to achieve the above object, the present invention adopts the following technical solutions:

a high-toughness multi-layer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises the following components: carboxyl nitrile rubber, agricultural and forestry waste, sponge iron, nano-scale metal oxide, composite emulsion and an additive; the middle layer comprises the following components: carboxyl butyl rubber, tetrapropylene fluoride rubber, agricultural and forestry waste, composite emulsion, nano-scale metal oxide and an additive; the inner layer comprises the following components: carboxyl butyl rubber, polyurethane resin, modified plant fiber, composite emulsion, nano metal oxide and an additive.

Preferably, the outer layer comprises, by weight, 50-60 parts of carboxylated nitrile rubber, 12-15 parts of agricultural and forestry waste, 5-9 parts of sponge iron, 1-3 parts of nano-scale metal oxide, 3-10 parts of composite emulsion and 5-15 parts of an additive.

Preferably, the middle layer comprises, by weight, 50-60 parts of carboxybutyl rubber, 25-40 parts of tetrapropylene fluoride rubber, 15-20 parts of agricultural and forestry waste, 6-10 parts of composite emulsion, 4-7 parts of nano-scale metal oxide and 10-25 parts of an additive.

Preferably, the inner layer comprises, by weight, 50-60 parts of carboxybutyl rubber, 10-16 parts of polyurethane resin, 5-10 parts of modified plant fiber, 6-13 parts of composite emulsion, 1-3 parts of nano-scale metal oxide and 5-15 parts of an additive.

Preferably, the agricultural and forestry waste comprises sawdust, crushed straws and rice hulls in a mass ratio of 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, soaking the rice hulls in warm water containing starch for 1-2 hours (the content of starch is 10-15 wt% of the mass of the warm water), taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, blending the wood chips and the crushed straws, performing heat treatment on the mixture for 30-60min in superheated vapor containing nitrogen (the content of nitrogen is 20 vt%, the temperature of the superheated vapor is 180 DEG and 200 ℃) for later use, uniformly blending the treated rice hulls, wood chips and crushed straws, adding a proper amount of phenolic resin adhesive, stirring the mixture for 10-15min, performing vacuum drying at 50 ℃ until the water content is.

Preferably, the nanoscale metal oxide is present in a molar ratio of 1: 0.5:2 of magnesium oxide, zirconium oxide and zinc oxide.

Preferably, the volume ratio of the composite emulsion is 1: 0.2-1: 0.5-1 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion.

Preferably, the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 15-20 mg/g.

Preferably, the addition auxiliary agent comprises a lubricant, an accelerator, a reinforcing agent, a dispersant and a crosslinking agent. Wherein, the additive is added into the outer layer according to the following components: accelerator (b): reinforcing agent: dispersing agent: crosslinker: 3:1:6:1: 1; the additive is added into the middle layer, and the proportion of each component is as follows: accelerator (b): reinforcing agent: dispersing agent: crosslinker 3:1.5:5:2: 1.5; the additive is added into the inner layer, and the proportions of the components are as follows: accelerator (b): reinforcing agent: dispersing agent: the crosslinker was 3:1:5:1: 1.5.

Preferably, the preparation method of the high-toughness multi-layer composite anti-skid rubber sole comprises the following steps:

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spraying manner, uniformly mixing, stirring for 20-40min at 65-70 ℃, adding nano-scale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining for 3-5min at 50 +/-2 ℃, respectively and uniformly dividing at least 2 parts of the added auxiliary agent and the mixed material, and alternately adding the auxiliary agent and the mixed material, mixing for 120s after each addition, wherein the mixing temperature is 135-150 ℃, thinly pressing into sheets, and putting the sheets on a vulcanizing machine for vulcanization after sheet discharge to obtain outer-layer sheets;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending the nanoscale metal oxide and the composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 20-60min at 65-70 ℃ to obtain a mixed material for later use, feeding the carboxyl butyl rubber and the tetrapropylene fluoride rubber into a mixing roll, refining for 3-5min at 50-60 ℃, respectively and equally dividing at least 2 parts of the added auxiliary agent and the mixed material, and alternately adding the auxiliary agent and the mixed material into the mixing roll, mixing for 100 and 120 seconds after each addition, mixing at the temperature of 135 and 150 ℃, thinly pressing the mixed material into sheets, and putting the sheets on a vulcanizing machine for vulcanization after the sheets are taken out to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending nano metal oxide and composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending polyurethane resin and modified plant fiber, stirring and mixing at 70-80 ℃ and 0.7-0.9MPa for 30-60min to obtain a second mixed material for later use, sending carboxyl nitrile rubber into a mixing roll to be refined at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 115 ℃ and 120 ℃ for mixing for 3-5min, respectively and uniformly dividing at least 2 parts of the first mixed material and the auxiliary agent, alternately adding the first mixed material and the auxiliary agent, mixing for 100 seconds after each addition, mixing at the mixing temperature of 135 ℃ and 150 ℃, thinly tabletting, taking out tablets, and placing the tablets on a vulcanizing machine for vulcanization to obtain inner-layer tablets;

4) preparing the anti-skid rubber sole: and taking the outer layer sheet material, the middle layer sheet material and the inner layer sheet material, and carrying out hot pressing and integral molding by adopting a multi-layer hot press to obtain the high-toughness multi-layer re-pressed anti-skid rubber sole.

Due to the adoption of the technical scheme, the invention has the beneficial effects that: the invention adopts a multilayer structure to perform repression through reasonable raw material selection and matching, has strong function pertinence, high integral comfort level, wear-resisting and skid-proof bottom, light middle layer, high elasticity, comfortable inner layer and antibacterial property, obviously improves the comprehensive quality and is suitable for the requirements of most people.

The invention adopts the carboxyl nitrile rubber as the main material and is matched with agricultural and forestry wastes, nano-scale metal oxide and composite emulsion, has excellent foaming and toughening effects, effectively reduces the weight of the material, ensures the rapid dispersion reaction of the metal oxide by the embedding connection of wood fibers, forms a balanced and stable network structure, and has obvious reinforcing effect on the crosslinking sites of the rubber structure by metal divalent ions.

The sponge iron is added in the outer layer material, the high-specific surface area is provided, the reinforcing pressure resistance is good, the looseness is strong, the sponge iron is blended with agricultural wastes and nanoscale metal oxides in the preparation process, the carrying effect on metal oxide particles is strong in the activation crosslinking of the composite emulsion, the good slow release performance is provided, the sponge iron is matched with the emulsion, is cured and crosslinked on the surface layer of agricultural waste particles, the bridging transmissibility is good, the efficient contact and combination of reaction sites are facilitated during the later mixing with a rubber base, the rubber network structure forming stability is good, the toughness and the wear resistance are remarkably improved, and the excellent waterproof low-permeability effect is provided.

The middle layer uses carboxyl butyl rubber to match with tetrafluoroethylene-propylene rubber, so as to bear the force, reduce the deformation rate, improve the contents of agricultural and forestry wastes and nano metal oxides, improve the stability and strength of spatial connection under the action of a compound rubber base, improve the rapid compatible combination during hot melting and pressurization, and have good bonding effect. The inner layer is added with polyurethane resin and modified plant fiber, so that the elasticity, the ventilation and antibacterial effects are improved, the film forming effect is good, the acting range of the inner layer is strong, and the durability is good.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.

Example 1:

a high-toughness multilayer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises 50 parts by weight of carboxyl nitrile rubber, 12 parts by weight of agricultural and forestry waste, 6 parts by weight of sponge iron, 3 parts by weight of nanoscale metal oxide, 10 parts by weight of composite emulsion and 10 parts by weight of additive;

the middle layer comprises 50 parts of carboxyl butyl rubber, 30 parts of tetrapropylene fluororubber, 20 parts of agricultural and forestry waste, 10 parts of composite emulsion, 6 parts of nano metal oxide and 20 parts of additive in parts by weight;

the inner layer comprises 50 parts by weight of carboxyl butyl rubber, 10 parts by weight of polyurethane resin, 10 parts by weight of modified plant fiber, 13 parts by weight of composite emulsion, 2 parts by weight of nano-scale metal oxide and 15 parts by weight of additive.

The agricultural and forestry wastes comprise wood chips, crushed straws and rice hulls, and the mass ratio of the wood chips, the crushed straws and the rice hulls is 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, soaking the rice hulls in warm water containing starch for 2 hours, taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, mixing the crushed wood chips and the crushed straws together, performing heat treatment on the mixture for 60min in superheated steam containing nitrogen for later use, uniformly mixing the treated rice hulls, the wood chips and the crushed straws together, adding a proper amount of phenolic resin glue, stirring for 10-15min, performing vacuum drying at 50 ℃ until the water content is smaller than 10 wt%, and crushing the.

The nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of a combination of magnesium oxide, zirconium oxide, zinc oxide; the volume ratio of the composite emulsion is 1: 0.5: 0.5 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion mixture; the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 17.6 mg/g.

The addition auxiliary agent comprises a lubricant, an accelerator, a reinforcing agent, a dispersant and a cross-linking agent. Wherein, the additive is added into the outer layer according to the following components: accelerator (b): reinforcing agent: dispersing agent: crosslinker: 3:1:6:1: 1; the additive is added into the middle layer, and the proportion of each component is as follows: accelerator (b): reinforcing agent: dispersing agent: crosslinker 3:1.5:5:2: 1.5; the additive is added into the inner layer, and the proportions of the components are as follows: accelerator (b): reinforcing agent: dispersing agent: the crosslinker was 3:1:5:1: 1.5.

The preparation method of the high-toughness multi-layer composite-pressure anti-skid rubber sole comprises the following steps:

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spraying manner, uniformly mixing, stirring for 40min at 65-70 ℃, adding nanoscale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining for 3-5min at 50 +/-2 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 100s after each addition, wherein the mixing temperature is 140 ℃, thinly pressing sheets, and putting the sheets on a vulcanizing machine for vulcanization after sheet discharge to obtain outer-layer sheets;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 40min at 65-70 ℃ to obtain a mixed material for later use, sending carboxyl butyl rubber and tetrafluoroethylene-propylene rubber into a mixing roll, refining for 3-5min at 55 ℃, then respectively and equally dividing at least 2 parts of an additive and the mixed material, and alternately adding the additive and the mixed material, mixing for 100s after each addition, wherein the mixing temperature is 140 ℃, thinly pressing the mixed material into sheets, and putting the sheets on a vulcanizing machine for vulcanization treatment after the sheets are taken out to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending a polyurethane resin and a modified plant fiber, stirring and mixing at 70 ℃ and 0.8MPa for 30min to obtain a second mixed material for later use, feeding carboxyl nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 120 ℃ for mixing for 3-5min, adding an auxiliary agent, and respectively uniformly dividing the first mixed material into 2 parts and alternately adding the first mixed material, mixing for 100s after each addition, performing thin-pass tabletting at a mixing temperature of 140 ℃, discharging the tablets, and placing the tablets on a vulcanizing machine for vulcanization to obtain inner-layer tablets;

Example 2:

a high-toughness multilayer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises 55 parts by weight of carboxyl nitrile rubber, 15 parts by weight of agricultural and forestry waste, 5 parts by weight of sponge iron, 3 parts by weight of nanoscale metal oxide, 6 parts by weight of composite emulsion and 10 parts by weight of additive;

the middle layer comprises 50 parts of carboxyl butyl rubber, 25 parts of tetrapropylene fluororubber, 15 parts of agricultural and forestry waste, 8 parts of composite emulsion, 5 parts of nano metal oxide and 15 parts of additive in parts by weight;

the inner layer comprises 60 parts of carboxyl butyl rubber, 10 parts of polyurethane resin, 8 parts of modified plant fiber, 10 parts of composite emulsion, 2 parts of nano metal oxide and 10 parts of additive.

The nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of a combination of magnesium oxide, zirconium oxide, zinc oxide; the volume ratio of the composite emulsion is 1: 0.2: 0.5 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion mixture; the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 18.1 mg/g.

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spray manner, uniformly mixing, stirring at 65-70 ℃ for 30min, adding nanoscale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 120s after each addition, wherein the mixing temperature is 135 ℃, thinly pressing sheets, taking out the sheets, and placing the sheets on a vulcanizing machine for vulcanization to obtain outer-layer sheets;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 30min at 65-70 ℃ to obtain a mixed material for later use, sending carboxyl butyl rubber and tetrafluoroethylene-propylene rubber into a mixing roll, refining for 3-5min at 60 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 120s after each addition, wherein the mixing temperature is 135 ℃, thinly pressing the mixed material into sheets, and putting the sheets on a vulcanizing machine for vulcanization after sheet discharge to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending a polyurethane resin and a modified plant fiber, stirring and mixing at 80 ℃ and 0.7MPa for 60min to obtain a second mixed material for later use, feeding carboxyl nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 115 ℃ for 3-5min, finally, adding an additive, respectively uniformly dividing the first mixed material into 2 parts, alternately adding the first mixed material, mixing for 120s after each addition, performing thin-pass tabletting at the mixing temperature of 135 ℃, discharging the tablets, and placing the tablets on a vulcanizing machine for vulcanization to obtain inner-layer tablets;

Example 3:

a high-toughness multilayer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises, by weight, 60 parts of carboxyl nitrile rubber, 12 parts of agricultural and forestry waste, 5 parts of sponge iron, 2 parts of nanoscale metal oxide, 8 parts of composite emulsion and 10 parts of additive;

the middle layer comprises 50 parts of carboxyl butyl rubber, 30 parts of tetrapropylene fluororubber, 15 parts of agricultural and forestry waste, 6 parts of composite emulsion, 4 parts of nano metal oxide and 25 parts of additive in parts by weight;

the inner layer comprises 50 parts by weight of carboxyl butyl rubber, 16 parts by weight of polyurethane resin, 6 parts by weight of modified plant fiber, 6 parts by weight of composite emulsion, 3 parts by weight of nano-scale metal oxide and 15 parts by weight of additive.

The agricultural and forestry wastes comprise wood chips, crushed straws and rice hulls, and the mass ratio of the wood chips, the crushed straws and the rice hulls is 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, soaking the rice hulls in warm water containing starch for 2 hours, taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, mixing the crushed wood chips and the crushed straws together, performing heat treatment on the mixture for 30min in superheated steam containing nitrogen for later use, uniformly mixing the treated rice hulls, the wood chips and the crushed straws together, adding a proper amount of phenolic resin glue, stirring for 10-15min, performing vacuum drying at 50 ℃ until the water content is smaller than 10 wt%, and crushing the.

The nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of a combination of magnesium oxide, zirconium oxide, zinc oxide; the volume ratio of the composite emulsion is 1:1 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion; the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 15.9 mg/g.

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spray manner, uniformly mixing, stirring for 30min at 65-70 ℃, adding nanoscale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining for 3-5min at 50 +/-2 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 100s after each addition, wherein the mixing temperature is 150 ℃, thinly pressing sheets, taking out the sheets, and placing the sheets on a vulcanizing machine for vulcanization to obtain outer-layer sheets;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 30min at 65-70 ℃ to obtain a mixed material for later use, sending carboxyl butyl rubber and tetrafluoroethylene-propylene rubber into a mixing roll, refining for 3-5min at 60 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 100s after each addition, mixing at the temperature of 150 ℃, thinly pressing into sheets, and putting the sheets on a vulcanizing machine for vulcanization treatment after sheet discharge to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending a polyurethane resin and a modified plant fiber, stirring and mixing at 80 ℃ and 0.7MPa for 30min to obtain a second mixed material for later use, feeding carboxyl nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 120 ℃ for mixing for 3-5min, adding an additive, respectively dividing the first mixed material into at least 2 parts, alternately adding the first mixed material, mixing for 100s after each addition, performing thin pass tabletting at the mixing temperature of 150 ℃, discharging the tablets, and placing the tablets on a vulcanizing machine for vulcanization to obtain inner-layer tablets;

Example 4:

a high-toughness multilayer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises 50 parts by weight of carboxyl nitrile rubber, 12 parts by weight of agricultural and forestry waste, 9 parts by weight of sponge iron, 1 part by weight of nanoscale metal oxide, 10 parts by weight of composite emulsion and 5 parts by weight of additive;

the middle layer comprises 50 parts of carboxyl butyl rubber, 25 parts of tetrapropylene fluororubber, 20 parts of agricultural and forestry waste, 10 parts of composite emulsion, 4 parts of nano metal oxide and 15 parts of additive in parts by weight;

the inner layer comprises 60 parts of carboxyl butyl rubber, 16 parts of polyurethane resin, 5 parts of modified plant fiber, 6 parts of composite emulsion, 1 part of nano metal oxide and 10 parts of additive.

The agricultural and forestry wastes comprise wood chips, crushed straws and rice hulls, and the mass ratio of the wood chips, the crushed straws and the rice hulls is 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, soaking the rice hulls in warm water containing starch for 1h, taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, mixing the crushed wood chips and the crushed straws together, performing heat treatment on the mixture for 40min in superheated steam containing nitrogen for later use, uniformly mixing the treated rice hulls, the wood chips and the crushed straws together, adding a proper amount of phenolic resin glue, stirring for 10-15min, performing vacuum drying at 50 ℃ until the water content is smaller than 10 wt%, and crushing the.

The nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of a combination of magnesium oxide, zirconium oxide, zinc oxide; the volume ratio of the composite emulsion is 1: 0.2: 1 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion; the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 17.4 mg/g.

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spraying manner, uniformly mixing, stirring for 20min at 65-70 ℃, adding nanoscale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining for 3-5min at 50 +/-2 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 110s after each addition, wherein the mixing temperature is 140 ℃, thinly pressing sheets, and putting the sheets on a vulcanizing machine for vulcanization after sheet discharge to obtain outer-layer sheets;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 40min at 65-70 ℃ to obtain a mixed material for later use, sending carboxyl butyl rubber and tetrafluoroethylene-propylene rubber into a mixing roll, refining for 3-5min at 60 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 110s after each addition, mixing at the mixing temperature of 140 ℃, thinly pressing into sheets, and putting the sheets on a vulcanizing machine for vulcanization treatment after sheet discharge to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending a polyurethane resin and a modified plant fiber, stirring and mixing at 80 ℃ and 0.9MPa for 30min to obtain a second mixed material for later use, feeding carboxyl nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 115 ℃ for 3-5min, finally, adding an additive, and alternately adding the first mixed material in 2 parts respectively, mixing for 110s after each addition, performing thin-pass tabletting at the mixing temperature of 140 ℃, and putting the obtained slices on a vulcanizing machine for vulcanization to obtain inner-layer slices;

Example 5:

a high-toughness multilayer repressing anti-skid rubber sole comprises an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises, by weight, 60 parts of carboxyl nitrile rubber, 15 parts of agricultural and forestry waste, 5 parts of sponge iron, 1 part of nanoscale metal oxide, 3 parts of composite emulsion and 15 parts of additive;

the middle layer comprises 50 parts of carboxyl butyl rubber, 25 parts of tetrapropylene fluororubber, 15 parts of agricultural and forestry waste, 8 parts of composite emulsion, 4 parts of nano metal oxide and 25 parts of additive in parts by weight;

the inner layer comprises 50 parts by weight of carboxyl butyl rubber, 16 parts by weight of polyurethane resin, 10 parts by weight of modified plant fiber, 6 parts by weight of composite emulsion, 1 part by weight of nano-scale metal oxide and 15 parts by weight of additive.

The agricultural and forestry wastes comprise wood chips, crushed straws and rice hulls, and the mass ratio of the wood chips, the crushed straws and the rice hulls is 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, soaking the rice hulls in warm water containing starch for 1h, taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, mixing the crushed wood chips and the crushed straws together, performing heat treatment on the mixture for 60min in superheated steam containing nitrogen for later use, uniformly mixing the treated rice hulls, the wood chips and the crushed straws together, adding a proper amount of phenolic resin glue, stirring for 10-15min, performing vacuum drying at 50 ℃ until the water content is smaller than 10 wt%, and crushing the.

The nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of a combination of magnesium oxide, zirconium oxide, zinc oxide; the volume ratio of the composite emulsion is 1: 0.5: 1 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion; the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 19.3 mg/g.

1) preparing outer layer sheet materials: taking materials according to parts by weight, blending sponge iron and agricultural wastes, adding the composite emulsion in a spraying manner, uniformly mixing, stirring for 40min at 65-70 ℃, adding nanoscale metal oxide, uniformly stirring to obtain a mixed material for later use, feeding the carboxylated nitrile rubber into a mixing roll, refining for 3-5min at 50 +/-2 ℃, respectively and uniformly dividing at least 2 parts of the added auxiliary agent and the mixed material, and alternately adding the auxiliary agent and the mixed material, mixing for 120s after each addition, wherein the mixing temperature is 140 ℃, performing thin-pass tabletting, and putting the mixture on a vulcanizing machine for vulcanization treatment to obtain outer-layer sheet materials;

2) preparing a middle layer sheet material: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, adding the mixture into agricultural and forestry waste, stirring and mixing for 20min at 65-70 ℃ to obtain a mixed material for later use, sending carboxyl butyl rubber and tetrafluoroethylene-propylene rubber into a mixing roll, refining for 3-5min at 60 ℃, respectively and uniformly dividing the added auxiliary agent and the mixed material into 2 parts, alternately adding the auxiliary agent and the mixed material, mixing for 120s after each addition, mixing at the mixing temperature of 140 ℃, thinly pressing into sheets, and putting the sheets on a vulcanizing machine for vulcanization treatment after sheet discharge to obtain middle-layer sheets;

3) preparing inner layer sheet materials: taking materials according to parts by weight, blending a nanoscale metal oxide and a composite emulsion, shaking at a constant temperature of 50 ℃ for 30min to obtain a first mixed material for later use, blending a polyurethane resin and a modified plant fiber, stirring and mixing at 75 ℃ and 0.9MPa for 30min to obtain a second mixed material for later use, feeding carboxyl nitrile rubber into a mixing roll, refining at 50 +/-2 ℃ for 3-5min, adding the second mixed material, heating to 120 ℃ for mixing for 3-5min, adding an auxiliary agent, and respectively uniformly dividing the first mixed material into 2 parts and alternately adding the first mixed material, mixing for 120s after each addition, performing thin-pass tabletting at a mixing temperature of 140 ℃, discharging the tablets, and placing the tablets on a vulcanizing machine for vulcanization to obtain inner-layer tablets;

The performance test of the anti-skid rubber sole prepared by the embodiment of the invention is carried out, and the data is as follows:

the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. The high-toughness multi-layer repressing anti-skidding rubber sole is characterized by comprising an outer layer, a middle layer and an inner layer which are integrally formed by hot pressing, wherein the thickness ratio of the outer layer to the middle layer to the inner layer is 2:1:1, and the outer layer comprises the following components: carboxyl nitrile rubber, agricultural and forestry waste, sponge iron, nano-scale metal oxide, composite emulsion and an additive; the middle layer comprises the following components: carboxyl butyl rubber, tetrapropylene fluoride rubber, agricultural and forestry waste, composite emulsion, nano-scale metal oxide and an additive; the inner layer comprises the following components: carboxyl butyl rubber, polyurethane resin, modified plant fiber, composite emulsion, nano metal oxide and an additive.

2. The high-toughness multilayer repressing anti-slip rubber sole according to claim 1, wherein the outer layer comprises, by weight, 50-60 parts of carboxylated nitrile rubber, 12-15 parts of agricultural and forestry waste, 5-9 parts of sponge iron, 1-3 parts of nano-scale metal oxide, 3-10 parts of composite emulsion, and 5-15 parts of an additive.

3. The high-toughness multi-layer repressing anti-slip rubber sole as recited in claim 1, wherein said middle layer comprises 50-60 parts by weight of carboxybutyl rubber, 25-40 parts by weight of tetrapropylene fluororubber, 15-20 parts by weight of agricultural and forestry waste, 6-10 parts by weight of composite emulsion, 4-7 parts by weight of nano-scale metal oxide, and 10-25 parts by weight of additive.

4. The high-toughness multilayer repressing anti-slip rubber sole as recited in claim 1, wherein said inner layer comprises 50-60 parts by weight of carboxybutyl rubber, 10-16 parts by weight of polyurethane resin, 5-10 parts by weight of modified plant fiber, 6-13 parts by weight of composite emulsion, 1-3 parts by weight of nano-scale metal oxide, and 5-15 parts by weight of additive.

5. The high toughness multi-layer repressing anti-slip rubber shoe sole according to claim 1, wherein: the agricultural and forestry waste comprises sawdust, crushed straws and rice hulls in a mass ratio of 2:2: 1; the preparation method of the agricultural and forestry waste comprises the steps of taking materials according to the mass ratio, crushing rice hulls to be smaller than 1mm, then soaking the rice hulls in warm water containing starch for 1-2 hours, taking the rice hulls out, drying the rice hulls and the crushed straws by hot air at 60 ℃ until the water content is 35-45 wt% for later use, crushing the wood chips and the crushed straws to be smaller than 1mm, blending the crushed wood chips and the crushed straws, then performing heat treatment on the mixture for 30-60min in superheated vapor containing nitrogen for later use, uniformly blending the treated rice hulls, the treated wood chips and the crushed straws, adding a proper amount of phenolic resin adhesive, stirring the mixture for 10-15min, drying the mixture in vacuum at 50 ℃ until the water content is smaller than 10.

6. The high toughness multi-layer repressing anti-slip rubber shoe sole according to claim 1, wherein: the nano-scale metal oxide is prepared from the following components in a molar ratio of 1: 0.5:2 of magnesium oxide, zirconium oxide and zinc oxide.

7. The high toughness multi-layer repressing anti-slip rubber shoe sole according to claim 1, wherein: the composite emulsion is prepared by mixing the following components in a volume ratio of 1: 0.2-1: 0.5-1 of ethylene-vinyl acetate copolymer, polyvinyl acetate emulsion and pure acrylic emulsion.

8. The high toughness multi-layer repressing anti-slip rubber shoe sole according to claim 1, wherein: the modified plant fiber is titanium dioxide loaded bamboo cotton fiber, wherein the loading amount of the titanium dioxide is 15-20 mg/g.

9. The high toughness multi-layer repressing anti-slip rubber shoe sole according to claim 1, wherein: the addition auxiliary agent comprises a lubricant, an accelerator, a reinforcing agent, a dispersant and a cross-linking agent.

10. The high toughness multi-layer repressing anti-slip rubber shoe sole according to any of claims 1 to 9, characterized in that it is prepared by the following steps: