A modified rubber composite nylon elastomer material and a method of making the same

Abstract

The application belongs to the field of rubber material preparation, and particularly relates to a modified rubber composite nylon elastomer material and a preparation method thereof. The modified rubber composite nylon elastomer material comprises the following raw materials: bio-based plastic, bio-based nylon elastomer, EVA, modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, foaming agent, hydroxyl silicone oil and zinc methacrylate. The application limits the raw material composition of the modified rubber composite nylon elastomer material, takes bio-based plastic, bio-based nylon elastomer and EVA as main raw materials, adds modified rubber powder and other raw materials, so that the prepared rubber sole material has good crack resistance and tensile resistance, the reusability of waste rubber is increased, the recycling problem of waste rubber soles is solved, resource recycling and utilization are realized, and the raw material cost is effectively reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of rubber sole material preparation, and particularly relates to a modified rubber composite nylon elastomer material and a preparation method thereof. BACKGROUND

[0002] With the improvement of living standards, people have higher and higher material requirements. In order to wear comfortable, beautiful and atmospheric shoes, most of the sports shoes, casual shoes and the like worn by people are made of rubber materials. However, with the discarding of the shoes, a large amount of rubber sole material is also wasted. If the rubber sole material is naturally aged, a long time is required, and garbage landfill is easily caused. If the waste is incinerated, air pollution is caused. Therefore, the introduction of modified rubber powder into the rubber sole formula to realize the low-carbon design of vulcanized rubber soles becomes an important development direction in the field. However, the product made of the recycled rubber sole material is easy to break, has low fatigue flexing resistance, and has poor ductility, so that the quality cannot be improved, and improvement is urgently needed. SUMMARY

[0003] The application aims to overcome the defects of the prior art and provide a modified rubber composite nylon elastomer material and a preparation method thereof.

[0004] The application adopts the following technical scheme:

[0005] A modified rubber composite nylon elastomer material comprises the following raw materials in parts by weight:

[0006] Bio-based plastic 40-50 parts

[0007] Bio-based nylon elastomer 15-25 parts

[0008] EVA 10-20 parts

[0009] Modified rubber powder 15-20 parts

[0010] SEBS grafting compatibilizer 5-10 parts

[0011] Crosslinking agent 4-6 parts

[0012] Zinc oxide 1-2 parts

[0013] Stearic acid 0.3-1 part

[0014] Zinc stearate 0.3-1 part

[0015] Foaming agent 3-10 parts

[0016] Hydroxyl silicone oil 1-2 parts

[0017] Zinc methacrylate 0.5-1 part.

[0018] Preferably, the modified rubber powder is obtained by modifying the recycled rubber with a modifier, the modifier including polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil, wherein the proportions of the recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil are 100:4-6:5-10:20-30:1-2 by weight.

[0019] Preferably, the modification method of the modified rubber powder specifically includes the following steps:

[0020] (1) The recycled waste rubber soles are washed and sent into a crusher to be broken into 10-20 mesh, and the iron filings impurities are removed by an iron removing machine to obtain recycled rubber particles;

[0021] (2) The obtained recycled rubber particles are dried to control the water content to be less than 5%;

[0022] (3) The recycled rubber particles obtained in step (2) are sent into an internal mixer, and the required weight portions of maleic anhydride grafted polyethylene are added, pre-mixed for 8-12 min, and then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are added and mixed and kneaded, and the material is discharged at 112℃, and then sent into a double screw extruder for extrusion and granulation, and the material is cooled in a water cooling tank and then granulated on a granulator;

[0023] (4) The obtained granules are dried to a water content of less than 3%, and then sent into a crusher to be crushed to 200-300 mesh to obtain the recycled rubber powder.

[0024] Preferably, in step (3), the internal mixing process is as follows: the recycled rubber particles obtained in step (2) are sent into an internal mixer, and the required weight portions of maleic anhydride grafted polyethylene are added, pre-mixed for 8-12 min, and then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are added and mixed and kneaded for 5 min, and then the internal mixing temperature is adjusted to 85℃, and after keeping for 3 min, the material is turned over once; when the internal mixing temperature rises to 92℃, the material is turned over twice; when the internal mixing temperature rises to 98℃, the material is turned over three times; when the internal mixing temperature rises to 103℃, the material is turned over four times; when the internal mixing temperature rises to 112℃, the material is turned over five times, and then the material is mixed and kneaded for 1 min, discharged, and placed at room temperature for more than 24 h.

[0025] Preferably, the crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP at a mass ratio of 1:2-3.

[0026] Preferably, the foaming agent is composed of foaming agent AC and foaming agent OBSH at a mass ratio of 1:1-1.5.

[0027] Preferably, the bio-based plastic is PLA, PHA, PBS, or PBAT.

[0028] A preparation method of a modified rubber composite nylon elastomer material, comprising the following steps:

[0029] Step 1: mixing the required weight parts of bio-based plastic, bio-based nylon elastomer and EVA in a mixer for 10-15 min to obtain a premix;

[0030] Step 2: adding the premix prepared in step 1 to modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate and hydroxyl silicone oil, mixing and mixing in a mixer at 115-120 DEG C to remove the glue, and placing at room temperature for more than 24 h;

[0031] Step 3: mixing the mixture obtained in step 2 on an open mill, and adding the required weight parts of foaming agent and zinc methacrylate, mixing uniformly, and sheeting to obtain foaming sheet;

[0032] Step 4: cutting the foaming sheet into a shoe sole shape, and foaming and molding in a rubber shoe mold to obtain the modified rubber material.

[0033] Preferably, in step 4, the foaming temperature is 155-165 DEG C.

[0034] Preferably, in step 2, the mixing process specifically includes: adding the premix prepared in step 1 to modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate and hydroxyl silicone oil, mixing and mixing in a mixer for 8 min, then adjusting the mixing temperature to 88 DEG C, keeping for 3 min, and then turning over once; when the mixing temperature rises to 95 DEG C, turning over twice; when the mixing temperature rises to 102 DEG C, turning over three times; when the mixing temperature rises to 110 DEG C, turning over four times; when the mixing temperature rises to 115-118 DEG C, turning over five times, and then mixing for 1 min, removing the glue, and placing at room temperature for more than 24 h.

[0035] From the above description of the present application, compared with the prior art, the beneficial effects of the present application are: by limiting the raw material composition of the modified rubber material, using bio-based plastic, bio-based nylon elastomer and EVA as the main raw material, and adding modified rubber powder and other raw materials, the prepared rubber sole material has good crack resistance and tensile resistance, increases the reusability of waste rubber, solves the recycling problem of waste rubber soles, realizes the recycling and utilization of resources, effectively reduces the raw material cost, and the obtained rubber material can be used for preparing foamed products such as soles, protective equipment, electronic product partitions and noise reduction sheets; wherein, the introduction of hydroxyl silicone oil and SEBS grafting compatibilizer improves the compatibility between the raw materials, stabilizes the interface structure of the prepared rubber sole material, and improves the mechanical properties of the material; the introduction of zinc methacrylate, together with the crosslinking agent and the foaming agent, improves the crosslinking and foaming strength, so that a stable three-dimensional network structure is formed in the prepared rubber sole material, thereby improving the mechanical properties of the prepared rubber sole material;

[0036] The modification method of the modified rubber powder is specifically defined, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene and epoxy soybean oil are used as modifiers, so that the prepared modified rubber powder is uniformly distributed and cannot be accumulated into a group, wherein the maleic anhydride grafted polyethylene cooperates with the carbon nine petroleum resin to improve the interfacial bonding force of the prepared modified rubber powder and other raw materials and improve the interfacial bonding strength thereof; the polyvinyl butyral cooperates with the epoxy soybean oil to improve the impact strength and tensile strength of the prepared modified rubber powder, so that it plays a reinforcing role and can be used as a filler to improve the mechanical properties of the prepared rubber sole material. DETAILED DESCRIPTION

[0037] The application is further described below through a specific embodiment.

[0038] A modified rubber composite nylon elastomer material comprises the following raw materials in parts by weight:

[0039] Bio-based plastic 40-50 parts

[0040] Bio-based nylon elastomer 15-25 parts

[0041] EVA 10-20 parts

[0042] Modified rubber powder 15-20 parts

[0043] SEBS grafted compatibilizer 5-10 parts

[0044] Crosslinking agent 4-6 parts

[0045] Zinc oxide 1-2 parts

[0046] Stearic acid 0.3-1 part

[0047] Zinc stearate 0.3-1 part

[0048] Foaming agent 3-10 parts

[0049] Hydroxyl silicone oil 1-2 parts

[0050] Zinc methacrylate 0.5-1 part.

[0051] The modified rubber powder is obtained by modifying recycled rubber by a modifier, and the modifier comprises polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene and epoxy soybean oil, and specifically, the proportions of the recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene and epoxy soybean oil are 100:4-6:5-10:20-30:1-2 by weight ratio; the modification method specifically comprises the following steps:

[0052] (1) The recovered waste rubber soles are washed and sent into a crusher to be broken into 10-20 mesh, and the iron filings impurities are removed by an iron remover to obtain recycled rubber particles;

[0053] (2) The recycled rubber particles obtained are dried to control the water content below 5%;

[0054] (3) The recycled rubber particles obtained in step (2) are sent into an internal mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, and pre-mixed for 8-12 min, then polyvinyl butyral, epoxy soybean oil, carbon nine petroleum resin are added and mixed for 5 min, then the mixing temperature is adjusted to 85℃, and kept for 3 min before the first turning; when the mixing temperature rises to 92℃, the second turning is carried out; when the mixing temperature rises to 98℃, the third turning is carried out; when the mixing temperature rises to 103℃, the fourth turning is carried out; when the mixing temperature rises to 112℃, the fifth turning is carried out, and then mixed for 1 min, and the material is discharged and placed at room temperature for more than 24 h;

[0055] (4) The obtained material particles are dried to a water content of less than 3%, and then sent into a crusher to be crushed to 200-300 mesh to obtain the rubber recycling powder.

[0056] The crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP in a mass ratio of 1:2-3.

[0057] The foaming agent is composed of foaming agent AC and foaming agent OBSH in a mass ratio of 1:1-1.5.

[0058] The bio-based plastic is PLA, PHA, PBS or PBAT.

[0059] A preparation method of a modified rubber composite nylon elastomer material, comprising the following steps:

[0060] Step 1: Mix the required weight parts of bio-based plastic, bio-based nylon elastomer and EVA in an internal mixer for 10-15 min to obtain a premix;

[0061] Step 2: Add the modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate and hydroxyl silicone oil to the premix prepared in step 1, and mix for 8 min, then adjust the mixing temperature to 88℃, and keep for 3 min before the first turning; when the mixing temperature rises to 95℃, the second turning is carried out; when the sealing temperature rises to 102℃, the third turning is carried out; when the mixing temperature rises to 110℃, the fourth turning is carried out; when the mixing temperature rises to 115-118℃, the fifth turning is carried out, and then mixed for 1 min, and the glue is discharged and placed at room temperature for more than 24 h;

[0062] Step 3: Mix the mixture obtained in step 2 on an open mill, and add the required weight parts of foaming agent and zinc methacrylate, and mix uniformly to obtain a foaming sheet.

[0063] Step 4, cut the foaming sheet into the shape of a shoe sole, put it into a rubber shoe mold for foaming molding, control the foaming temperature to be 155-165℃, and obtain the modified rubber material.

[0064] Example 1

[0065] A modified rubber composite nylon elastomer material comprises the following raw materials by weight:

[0066] PLA 40 parts

[0067] Bio-based nylon elastomer PA11 25 parts

[0068] EVA 10 parts

[0069] Modified rubber powder 20 parts

[0070] SEBS grafted compatibilizer 5 parts

[0071] Crosslinking agent 6 parts

[0072] Zinc oxide 2 parts

[0073] Stearic acid 1 part

[0074] Zinc stearate 0.3 parts

[0075] Foaming agent 3 parts

[0076] Hydroxyl silicone oil 2 parts

[0077] Zinc methacrylate 0.5 parts.

[0078] The modified rubber powder is obtained by modifying the recycled rubber with a modifier, and the modifier comprises polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil. Specifically, the ratio of recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil is 100:4:10:20:2 by weight. The modification method specifically includes the following steps:

[0079] (1) The recycled waste rubber sole is washed and sent to a crusher to be broken to 10 mesh, and the iron filings impurities are removed by an iron remover to obtain recycled rubber particles;

[0080] (2) The obtained recycled rubber particles are dried to control the water content to be less than 5%;

[0081] (3) The recycled rubber particles obtained in step (2) are fed into an internal mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, and pre-mixed for 8 min, then polyvinyl butyral, epoxy soybean oil, carbon nine petroleum resin are added and mixed for 5 min, then the mixing temperature is adjusted to 85°C, and maintained for 3 min before the first turning; when the mixing temperature rises to 92°C, the second turning is performed; when the mixing temperature rises to 98°C, the third turning is performed; when the mixing temperature rises to 103°C, the fourth turning is performed; when the mixing temperature rises to 112°C, the fifth turning is performed, and then mixed for 1 min, and the material is discharged, and placed at room temperature for more than 24 h;

[0082] (4) The obtained granules are dried to a water content of less than 3%, and then fed into a pulverizer to be pulverized to 200 mesh to obtain the rubber recycling powder.

[0083] The crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP in a mass ratio of 1:2.

[0084] The foaming agent is composed of foaming agent AC and foaming agent OBSH in a mass ratio of 1:1.

[0085] A preparation method of a modified rubber composite nylon elastomer material, comprising the following steps:

[0086] Step 1: The required weight parts of bio-based plastic, bio-based nylon elastomer, and EVA are mixed in an internal mixer for 10 min to obtain a premix;

[0087] Step 2: The premix prepared in step 1 is added with modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, and hydroxyl silicone oil, and mixed for 8 min, then the mixing temperature is adjusted to 88°C, and maintained for 3 min before the first turning; when the mixing temperature rises to 95°C, the second turning is performed; when the sealing temperature rises to 102°C, the third turning is performed; when the mixing temperature rises to 110°C, the fourth turning is performed; when the mixing temperature rises to 115°C, the fifth turning is performed, and then mixed for 1 min, and the rubber is discharged, and placed at room temperature for more than 24 h;

[0088] Step 3: The mixture obtained in step 2 is mixed on an open mill, and the required weight parts of foaming agent and zinc methacrylate are added, and the mixture is uniformly sheeted to obtain a foaming sheet;

[0089] Step 4: The foaming sheet is cut into a shoe sole shape, and foamed and formed in a rubber shoe mold, with the foaming temperature controlled at 155°C, to obtain a modified rubber material.

[0090] Example 2

[0091] A modified rubber composite nylon elastomer material, comprising the following weight parts of raw materials:

[0092] PLA 50 parts

[0093] Bio-based nylon elastomer PA1215 parts

[0094] EVA 20 parts

[0095] Modified rubber powder 15 parts

[0096] SEBS grafting compatibilizer 10 parts

[0097] Crosslinking agent 4 parts

[0098] Zinc oxide 1 part

[0099] Stearic acid 0.3 parts

[0100] Zinc stearate 1 part

[0101] Foaming agent 10 parts

[0102] Hydroxyl silicone oil 1 part

[0103] Zinc methacrylate 1 part.

[0104] The modified rubber powder is obtained by modifying the recycled rubber with a modifier, the modifier including polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil, and specifically, the proportions of the recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil are 100:6:5:30:1 by weight; and the modification method specifically includes the following steps:

[0105] (1) The recycled waste rubber soles are washed and sent to a crusher to be broken into 20 mesh, and the iron filings impurities are removed by an iron remover to obtain recycled rubber particles;

[0106] (2) The obtained recycled rubber particles are dried to control the water content to be less than 5%;

[0107] (3) The recycled rubber particles obtained in step (2) are sent to a banbury mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, and pre-mixed for 12 min, then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are mixed and mixed for 5 min, then the mixing temperature is adjusted to 85℃, and one-time material is turned after 3 min; the mixing temperature is raised to 92℃, and the second-time material is turned; the mixing temperature is raised to 98℃, and the third-time material is turned; the mixing temperature is raised to 103℃, and the fourth-time material is turned; the mixing temperature is raised to 112℃, and the fifth-time material is turned, and then mixed for 1 min, and the material is discharged and placed at room temperature for more than 24 h;

[0108] (4) The obtained material particles are dried to a water content of less than 3%, and then sent to a crusher to be crushed to 200-300 mesh to obtain the rubber recycling powder.

[0109] The crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP in a mass ratio of 1:3.

[0110] The foaming agent is composed of foaming agent AC and foaming agent OBSH in a mass ratio of 1:1.5.

[0111] A preparation method of a modified rubber composite nylon elastomer material, comprising the following steps:

[0112] Step 1: Mix the required weight parts of bio-based plastic, bio-based nylon elastomer, and EVA in a mixer for 15 minutes to obtain a premix;

[0113] Step 2: Add the premix prepared in step 1, modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, and hydroxyl silicone oil to the mixer and mix for 8 minutes, then adjust the mixing temperature to 88°C, keep for 3 minutes, and then turn over once; when the mixing temperature rises to 95°C, turn over twice; when the mixing temperature rises to 102°C, turn over three times; when the mixing temperature rises to 110°C, turn over four times; when the mixing temperature rises to 118°C, turn over five times, and then mix for another 1 minute, discharge the glue, and place it at room temperature for more than 24 hours;

[0114] Step 3: Mix the mixture obtained in step 2 on an open mill, and add the required weight parts of foaming agent and zinc methacrylate, mix uniformly, and then sheet the mixture to obtain foaming sheets;

[0115] Step 4: Cut the foaming sheets into the shape of a shoe sole, put them into a rubber shoe mold, and foam to form a modified rubber material, with the foaming temperature controlled at 165°C.

[0116] Example 3

[0117] A modified rubber composite nylon elastomer material, comprising the following weight parts of raw materials:

[0118] PLA 45 parts

[0119] Bio-based nylon elastomer PA56 20 parts

[0120] EVA 15 parts

[0121] Modified rubber powder 18 parts

[0122] SEBS grafting compatibilizer 7 parts

[0123] Crosslinking agent 5 parts

[0124] Zinc oxide 1.5 parts

[0125] Stearic acid 0.5 parts

[0126] Zinc stearate 0.6 parts

[0127] Foaming agent 7 parts

[0128] Hydroxyl silicone oil 1.5 parts

[0129] Zinc methacrylate 0.8 parts.

[0130] The modified rubber powder is obtained by modifying the recycled rubber with a modifier, the modifier including polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil, and specifically, the proportions of the recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil are 100:5:8:25:1.5 by weight ratio; the modification method specifically includes the following steps:

[0131] (1) The recycled waste rubber soles are washed and sent to a crusher to be broken to 15 mesh, and the iron filings impurities are removed by an iron removal machine to obtain recycled rubber particles;

[0132] (2) The obtained recycled rubber particles are dried to control the water content to be less than 5%;

[0133] (3) The recycled rubber particles obtained in step (2) are sent to a banbury mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, and pre-mixed for 10 min, then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are mixed and mixed for 5 min, then the mixing temperature is adjusted to 85℃, and one-time material is turned after 3 min; when the mixing temperature rises to 92℃, the second-time material is turned; when the mixing temperature rises to 98℃, the third-time material is turned; when the mixing temperature rises to 103℃, the fourth-time material is turned; when the mixing temperature rises to 112℃, the fifth-time material is turned, and then mixed for 1 min, and the material is discharged and placed at room temperature for more than 24 h;

[0134] (4) The obtained material particles are dried to a water content of less than 3%, and then sent to a crusher to be crushed to 250 mesh to obtain the rubber recycled powder.

[0135] The crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP in a mass ratio of 1:2.5.

[0136] The foaming agent is composed of foaming agent AC and foaming agent OBSH in a mass ratio of 1:1.2.

[0137] A preparation method of a modified rubber composite nylon elastomer material, including the following steps:

[0138] Step 1, mix the required weight parts of bio-based plastic, bio-based nylon elastomer, and EVA in a banbury mixer for 12 min to obtain a premix;

[0139] Step 2, the premix prepared in step 1 is added to the modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, hydroxyl silicone oil, and mixed in an internal mixer for 8 min, then the mixing temperature is adjusted to 88°C, and maintained for 3 min before the first turning; when the mixing temperature rises to 95°C, the second turning is performed; when the mixing temperature rises to 102°C, the third turning is performed; when the mixing temperature rises to 110°C, the fourth turning is performed; when the mixing temperature rises to 116°C, the fifth turning is performed, and then mixed for another 1 min, discharged, and placed at room temperature for 24 h or more;

[0140] Step 3, the mixture obtained in step 2 is mixed on an open mill, and the required weight of foaming agent and zinc methacrylate is added, and the mixture is uniformly sheeted to obtain foaming sheets;

[0141] Step 4, the foaming sheets are cut into the shape of a sole and placed in a rubber shoe mold for foaming molding, with the foaming temperature controlled at 160°C, to obtain the modified rubber material.

[0142] Comparative Example 1

[0143] The raw material composition is basically the same as that of Example 3, except that the modified rubber powder in the raw material composition is replaced by natural rubber.

[0144] Comparative Example 2

[0145] The raw material composition is basically the same as that of Example 3, except that the modified rubber powder in the raw material composition is replaced by recycled rubber powder directly crushed from waste rubber soles.

[0146] Comparative Example 3

[0147] The raw material composition is basically the same as that of Example 3, except that the modified rubber powder is obtained by modifying recycled rubber with a modifier, and the modifier includes maleic anhydride grafted polyethylene; specifically, the ratio of recycled rubber to maleic anhydride grafted polyethylene is 100:25 by weight.

[0148] Comparative Example 4

[0149] The raw material composition is basically the same as that of Example 3, except that the raw material composition does not include zinc methacrylate.

[0150] The modified rubber materials prepared in Examples 1-3 and Comparative Examples 1-4 are subjected to corresponding mechanical property tests, and the test results are shown in Table 1, where the tensile strength is tested according to GB / T528-2009, the tear strength is tested according to GB / T 529-2008; the abrasion is tested according to SKECHERS SGT-07; and the bending resistance is tested according to SATRA TM92-16.

[0151] Table 1 Performance Test Table of Each Example

[0152]

[0153] It can be seen from the comparison of Example 3 and Comparative Example 1, Comparative Example 2 that the modified rubber powder modified in the application can be used to replace natural rubber; it can be seen from the comparison of Example 3 and Comparative Example 3 that, by using polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene and epoxy soybean oil as the modifier, the prepared modified rubber powder is uniformly distributed and does not accumulate into a group, wherein the maleic anhydride grafted polyethylene cooperates with the carbon nine petroleum resin to improve the interfacial bonding force of the prepared modified rubber powder and other raw materials and improve the interfacial bonding strength thereof; the polyvinyl butyral cooperates with the epoxy soybean oil to improve the impact strength and tensile strength of the prepared modified rubber powder, so that it plays a reinforcing role and can be used as a filler to improve the mechanical properties of the prepared rubber sole material; it can be seen from the comparison of Example 3 and Comparative Example 4 that, by introducing zinc methacrylate and cooperating with a crosslinking agent and a foaming agent, the strength of crosslinking and foaming is improved, so that a stable three-dimensional network structure is formed in the prepared rubber sole material, thereby improving the mechanical properties of the prepared rubber sole material.

[0154] By limiting the composition of the raw materials of the modified rubber material, the application uses bio-based plastic, bio-based nylon elastomer and EVA as the main raw materials, adds modified rubber powder and other raw materials, so that the prepared rubber sole material has good crack resistance and tensile resistance, increases the reusability of waste rubber, solves the recycling problem of waste rubber soles, realizes the recycling and utilization of resources, effectively reduces the raw material cost, and the obtained rubber material can be used to prepare foamed products such as soles, protective equipment, electronic product partition pieces and noise reduction pieces.

[0155] The above description is only a preferred embodiment of the application, and therefore cannot limit the scope of the application, that is, equivalent changes and modifications made according to the patent application scope and content of the description should still be within the scope of the application.

Claims

1. A modified rubber composite nylon elastomeric material characterized by: The raw materials include the following weight parts: Bio-based plastic 40-50 parts Bio-based nylon elastomer 15-25 parts EVA 10-20 parts Modified rubber powder 15-20 parts SEBS grafting compatibilizer 5-10 parts Crosslinking agent 4-6 parts Zinc oxide 1-2 parts Stearic acid 0.3-1 part Zinc stearate 0.3-1 part Foaming agent 3-10 parts Hydroxyl silicone oil 1-2 parts Zinc methacrylate 0.5-1 part; The bio-based plastic is PLA, PHA, PBS or PBAT; The modified rubber powder is obtained by modifying recycled rubber with a modifier, and the modifier includes polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil, wherein the proportions of recycled rubber, polyvinyl butyral, carbon nine petroleum resin, maleic anhydride grafted polyethylene, and epoxy soybean oil are 100:4-6:5-10:20-30:1-2 by weight ratio; The crosslinking agent is composed of crosslinking agent BIBP and crosslinking agent DCP in a mass ratio of 1:2-3.

2. The modified rubber composite nylon elastomer material of claim 1, wherein: The modification method of the modified rubber powder specifically includes the following steps: (1) The recycled waste rubber soles are washed and sent to a crusher to be broken to 10-20 mesh, and the iron filings impurities are removed by an iron remover to obtain recycled rubber particles; (2) The obtained recycled rubber particles are dried to control the water content to be less than 5%; (3) The recycled rubber particles obtained in step (2) are sent to an internal mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, pre-mixed for 8-12 min, and then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are added and mixed and kneaded, and the material is discharged at 112℃, and then sent to a twin-screw extruder for extrusion and granulation, cooled in a water cooling tank, and then granulated on a pelletizer; (4) The obtained granules are dried to a water content of less than 3%, and then sent to a crusher to be crushed to 200-300 mesh to obtain the modified rubber powder.

3. The modified rubber composite nylon elastomer material of claim 2, wherein: In step (3), the mixing process is as follows: the recycled rubber particles obtained in step (2) are sent to an internal mixer, and the required weight parts of maleic anhydride grafted polyethylene are added, pre-mixed for 8-12 min, and then polyvinyl butyral, epoxy soybean oil, and carbon nine petroleum resin are added and mixed and kneaded for 5 min, and then the mixing temperature is adjusted to 85℃, and one-time turning is performed after 3 min; when the mixing temperature rises to 92℃, twice turning is performed; When the mixing temperature rises to 98℃, three times of turning is performed; When the mixing temperature rises to 103℃, four times of turning is performed; When the mixing temperature rises to 112℃, five times of turning is performed, and the material is mixed and kneaded for 1 min, discharged, and placed at room temperature for more than 24 h.

4. The modified rubber composite nylon elastomer material of claim 1, wherein: The foaming agent is composed of foaming agent AC and foaming agent OBSH in a mass ratio of 1:1-1.

5.

5. The method for preparing a modified rubber composite nylon elastomer material according to claim 1, characterized in that: The method includes the following steps: Step 1: Mix the required weight parts of bio-based plastic, bio-based nylon elastomer, and EVA in an internal mixer for 10-15 min to obtain a premix; Step 2: Add the modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, and hydroxyl silicone oil to the premix prepared in step 1, mix and knead at 115-120℃ to discharge the glue, and place at room temperature for more than 24 h; Step 3, the mixture obtained in step 2 is mixed on an open mill, and the required weight parts of foaming agent and zinc methacrylate are added, and the mixture is uniformly sheeted to obtain foamed sheets; Step 4, the foamed sheets are cut into the shape of a shoe sole, and are foamed and molded in a rubber shoe mold to obtain the modified rubber composite nylon elastomer material.

6. The method for preparing a modified rubber composite nylon elastomer material according to claim 5, characterized in that: In step 4, the foaming temperature is 155-165℃.

7. The method for preparing a modified rubber composite nylon elastomer material according to claim 5, characterized in that: In step 2, the internal mixing process specifically includes: the premix prepared in step 1 is added to modified rubber powder, SEBS grafting compatibilizer, crosslinking agent, zinc oxide, stearic acid, zinc stearate, and hydroxyl silicone oil, and is mixed and internally mixed for 8 min, then the internal mixing temperature is adjusted to 88℃, and is kept for 3 min before first turning; when the internal mixing temperature rises to 95℃, second turning is performed; when the internal mixing temperature rises to 102℃, third turning is performed; when the internal mixing temperature rises to 110℃, fourth turning is performed; when the internal mixing temperature rises to 115-118℃, fifth turning is performed, and then internal mixing is performed for 1 min, the rubber is discharged, and is placed at room temperature for 24 h or more.

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