WO2023005233A1

WO2023005233A1 - Bio-based rubber sole and preparation method therefor, and mould

Info

Publication number: WO2023005233A1
Application number: PCT/CN2022/082016
Authority: WO
Inventors: 卢鑫; 林志杰; 许春树; 丁思博; 罗显发; 廖毅彬; 董明生; 王燕; 邱瑞
Original assignee: 茂泰(福建)鞋材有限公司; 盛泰(福建)鞋材有限公司
Priority date: 2021-07-28
Filing date: 2022-03-21
Publication date: 2023-02-02
Also published as: CN113444302B; CN113444302A

Abstract

Disclosed in the present invention are a bio-based rubber sole comprising the following components in parts by weight: 40 parts of bio-based solution polymerised styrene-butadiene rubber, 16-24 parts of bio-based ethylene propylene diene monomer rubber, 38-46 parts of natural rubber, 35-40 parts of white carbon black, 2.1-2.8 parts of silane coupling agent, 0.7-1.1 parts of stearic acid, 0.6-0.9 part of anti-ageing agent, 1.9-2.5 parts of active agent, 3.2-3.8 parts of zinc oxide, 0.7-1.5 parts of polyethylene wax, 1.0-1.8 parts of anti-frosting agent, 0.9-1.4 parts of tackifying resin, 1.2-1.8 parts of vulcanisation accelerator, and 1.9-2.3 parts of insoluble sulphur; in the present application, when the bio-based solution polymerised styrene-butadiene rubber is prepared for polymerisation, carboxylated solution polymerised styrene-butadiene rubber, zinc oxide, stearic acid, and epoxidised soybean oil are mixed in an internal mixer to construct an ester-based cross-linked network structure, having the advantage of no oil separation. In addition, during vulcanisation moulding, ion pairs formed by the zinc ions and carboxyl in the rubber material can be used as strengthening points to increase the degree of crosslinking, enhancing the mechanical performance of the bio-based rubber outsole.

Description

A kind of bio-based rubber sole and its preparation method, mold

technical field

The invention relates to the technical field of shoe sole preparation, in particular to a bio-based rubber shoe sole, a preparation method thereof, and a mold.

Background technique

At present, in response to the national call, reduce carbon emissions and achieve carbon peaking as soon as possible. In the field of shoemaking, it can be done from three aspects, reducing the consumption of resources, using waste as resources, and turning harmful into harmless. This application starts from the aspect of reducing resource consumption, reducing the consumption of non-renewable petroleum resources, The rubber and plastics currently used are all obtained from monomers such as ethylene, propylene, and butadiene extracted from petroleum and polymerized, consuming a large amount of petroleum resources.

In the prior art, soybean oil and epoxidized soybean oil are directly added to the rubber material, and then the rubber product is obtained through physical blending, which has problems such as small amount of addition, poor compatibility, and easy precipitation. In the field of shoe soles, soybean oil is precipitated, resulting in poor bonding strength between the rubber outsole and the foam midsole, easy to open the glue, and high quality risks.

Contents of the invention

The embodiment of the present application provides a bio-based rubber sole and its preparation method and mold, which solves the technical problems of excessive carbon emissions and easy precipitation of soybean oil in the sole in the prior art, and realizes the reduction of the use of non-renewable resources , to obtain a bio-based rubber sole with high adhesive strength, and at the same time achieve the technical effect of rapid edge tearing, which significantly improves production efficiency.

The embodiment of the application provides. A bio-based rubber sole, comprising the following components by weight:

Further, the active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerin, and triethanolamine;

The anti-aging agent is selected from any one or more of anti-aging agent RD, anti-aging agent BHT, anti-aging agent 1010, anti-aging agent MB, anti-aging agent 4010, and anti-aging agent 264;

The tackifying resin is selected from any one or more of carbon five resins, carbon nine resins, modified carbon nine resins, phenolic resins, and coumarone-indene resins;

The vulcanization accelerator is selected from any one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D, vulcanization accelerator DM ;

The silane coupling agent is selected from any one or more of KH-550 and KH-560.

Further, the preparation method of the bio-based solution-polymerized styrene-butadiene rubber is as follows: put 100-300 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer, and then put in 3-6 parts of zinc oxide, 1-3 parts of stearic acid 20-43 parts of epoxy soybean oil is added to the internal mixer to generate heat due to friction in the system, and 20-43 parts of epoxy soybean oil is added, and the mixer is continued, discharged, and cooled to obtain bio-based solution-polymerized styrene-butadiene rubber;

The bio-based solution-polymerized styrene-butadiene rubber has a Mooney viscosity ML(1+4) of 55-65 at 100°C; the bio-based solution-polymerized styrene-butadiene rubber includes 25%-40% of bound styrene.

Further, the bio-based EPDM rubber includes 45%-60% of bio-based ethylene and 5.5%-9% of the third monomer ENB;

The bio-based EPDM rubber has a Mooney viscosity ML(1+4) of 55-80 at 125°C.

A preparation method for bio-based rubber soles, comprising the following steps:

Step (1): mixing bio-based solution-polymerized styrene-butadiene rubber, bio-based EPDM rubber, and natural rubber;

Put in some white carbon black and silane coupling agent for mixing, and then put in the remaining white carbon black, stearic acid, anti-aging agent, active agent, zinc oxide, polyethylene wax, anti-vomiting cream, tackifying resin; clean Once, continue mixing, discharging and cooling;

Step (2): The mixture obtained in step (1) is softened, and then vulcanization accelerator and insoluble sulfur are added; slices are produced as required, and punched according to the production requirements of shoe soles;

Step (3): Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160±5°C for 120-170 seconds, and tear off the burrs by hand.

A rubber film mold comprising

an upper template, the upper template including a first groove area;

A lower formwork connected to the upper formwork, the lower formwork has a lower rubber base area, a lower burr area, and a second groove area;

The edge of the lower rubber base area is connected with the second groove area, and the side of the second groove area away from the lower rubber base area is connected to the lower burr area;

When the upper template is sealingly connected with the lower template, the first groove area is located above the second groove area.

Further, the groove angle at the bottom of the second groove area is 30-60 degrees.

Further, when the upper formwork is sealed and connected to the lower formwork, the position of the sharp corner at the bottom of the second groove area corresponds to the edge position of the first groove area;

When the upper formwork is sealed and connected to the lower formwork, taking the horizontal position as the reference line, the sharp corner position of the bottom of the second groove area is 0-0.3mm away from the edge of the first groove area.

Further, the lower rubber base area includes a first lower rubber base area and a second lower rubber base area, the first lower rubber base area corresponds to the position of the forefoot, and the second lower rubber base area corresponds to the rear heel position, The first lower rubber chassis area and the second lower rubber chassis area are not connected to each other, and the first lower rubber chassis area and the second lower rubber chassis area are respectively connected to the second groove area.

Further, the lower rubber bottom sheet area includes a third lower rubber bottom sheet area, the third lower rubber bottom sheet area corresponds to the position of the center of the foot, and the third lower rubber bottom sheet area is not in contact with the first lower rubber bottom sheet area, the The second lower rubber chassis area is connected, and the third lower rubber chassis area is connected to the second grooved area.

One or more technical solutions provided in the embodiments of this application have at least the following technical effects or advantages:

When this application prepares bio-based solution-polymerized styrene-butadiene rubber for polymerization, carboxylated solution-polymerized styrene-butadiene rubber, zinc oxide, stearic acid, and epoxy soybean oil are banburyed in an internal mixer to construct an ester-based cross-linked network structure, which has The advantage of not separating out oil. In addition, during vulcanization molding, the ion pairs formed by zinc ions and carboxyl groups in the rubber compound can be used as strengthening points, which increases the degree of crosslinking and improves the mechanical properties of the bio-based rubber outsole.

The upper mold in the present application has a first groove area, and the lower mold has a second groove area, and when viewed from the vertical direction, the first groove area is located above the second groove area; from the horizontal direction Viewed from above, the position of the sharp corner at the bottom of the second groove area (the angle of the sharp angle is 30-60 degrees) coincides with or is separated by a certain distance from the edge position of the first groove area. With this design, when removing After flashing, there are almost no burrs on the surface of the rubber backing.

In this application, the upper raw area and the lower raw area are overlapped and connected to each other, so when removing the burrs, you only need to select any position of the burr area of the rubber base and tear it, and the entire burr area can be removed, realizing quick hand tearing The effect of rough edges reduces the trimming and finishing process and significantly improves production efficiency.

The bio-based rubber sole of the present application can be used to prepare both the outsole and the sole sheet. When preparing the sole sheet, since the sole sheet requires four sides, the burrs of the sole sheet need to be connected together. The existing rubber sole formulation has poor fluidity when preparing the sole, as shown in the numerical value of Comparative Example 1 in Table 1. However, the bio-based rubber sole of the present application has good fluidity and is more suitable for preparing shoe sole sheets.

Description of drawings

Fig. 1 is the upper formwork structure schematic diagram of present embodiment 1;

Fig. 2 is the structural representation of the lower formwork of the present embodiment 1;

Fig. 3 is the partial structure schematic diagram of the lower formwork of present embodiment 1;

FIG. 4 is a schematic diagram of the position and structure of the first grooved area and the second grooved area in Embodiment 1;

Fig. 5 is the physical figure (front side) of the rubber back sheet that the mold of present embodiment 1 prepares;

Fig. 6 is the physical figure (remove burrs) of the rubber back sheet that the mold of present embodiment 1 prepares;

Reference signs:

11, the lower rubber base area, 111, the first lower rubber base area, 112, the second lower rubber base area, 12, the lower burr area, 13, the second groove area, 21, the upper rubber base area, 22, the upper burr zone, 23, the first groove zone.

Detailed ways

In order to better understand the above-mentioned technical solution, the above-mentioned technical solution will be described in detail below in conjunction with the specification and specific implementation manners.

Example 1

A rubber film mold is composed of an upper template and a lower template. Referring to FIG. 1 , the upper template has an upper rubber base area 21 , an upper burr area 22 , and a first groove area 23 , and the upper rubber base area 21 is connected to the upper burr area 22 through the first groove area 23 . Referring to Fig. 2 and Fig. 3, the lower template has a lower rubber base area 11, a lower burr area 12, and a second groove area 13. The angle of the groove at the bottom of the second groove area 13 is 60 degrees, and the edges of the lower rubber base area 11 are connected There is a second groove area 13 , and the side of the second groove area 13 facing away from the lower rubber bottom sheet area 11 is connected to the lower burr area 12 .

When the upper formwork is sealed and connected with the lower formwork, the upper rubber base area 21 coincides with the lower rubber base area 11, and the upper burr area 22 coincides with the lower burr area 12. Referring to Fig. 4, from the vertical direction (y direction), the first Groove area 23 is positioned at the top of the second groove area 13; Viewed from the horizontal direction (x direction), the sharp angle position of the bottom of the second groove area 13 (the angle of this angle is 30-60 degree) and the first concave The edge positions of the groove area 23 are coincident or the sharp angle position of the bottom of the second groove area 13 is 0-0.3 mm away from the edge of the first groove area 23 .

The first lower rubber base area 111, the second lower rubber base area 112, and the third lower rubber base area included in the lower rubber base area 11; the first lower rubber base area 111 corresponds to the position of the forefoot, and the second lower rubber base area 112 corresponds to The position of the rear heel, the third lower rubber bottom area corresponds to the position of the center of the foot. The first lower rubber base area 111, the second lower rubber base area 112, and the third lower rubber base area are not connected to each other, but are all connected to the second groove.

In the process of actually using the sole, since the force and friction of different positions of the sole are different, correspondingly, the thickness and shape of different areas in the rubber bottom sheet are also different. Simultaneously, in order to remove the burr faster, the thickness of the second groove area 13 should be smaller than the thickness of the lower rubber base sheet area 11 and the lower burr area 12 .

In the production of the rubber base, in order to improve efficiency, the rubber base area corresponding to the forefoot, heel and sole of the foot will be placed in a mold for production. However, in specific applications, the rubber base area is not attached to the outsole as a whole, but According to the different positions of the soles of the feet, the appropriate rubber bottom sheet is selected for lamination. Therefore, after the preparation is completed, the burrs need to be removed before use.

With reference to Fig. 5, because the upper and lower burr regions 12 of the rubber backsheet are connected to each other, when removing the burr, only need to choose any burr region position of the rubber backsheet to tear, and the whole burr region can be removed. Referring to Fig. 6, it can be seen that the edge of the rubber back sheet after removing the burr area and the groove area is very smooth.

Example 2:

A preparation method for bio-based rubber soles, comprising the steps of:

Step (1): The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, put 100 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer at a speed of 40-50 rpm, and banbury for two minutes; then put in zinc oxide 3 1 part, 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the temperature in the internal mixer rises to 85 ℃, add 27 parts of epoxy soybean oil, and continue banburying for 12 minutes; The resulting mixture is discharged from the internal mixer, transferred to a double-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber; among them, the carboxylated solution-polymerized styrene-butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd. Co., Ltd.; epoxy soybean oil is a commercially available product; bio-based solution polystyrene butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100°C, and the mass ratio of bound styrene to the total amount of styrene and butadiene 34%, the mass ratio of vinyl to the total amount of butadiene is 34%.

Step (2): First put 40 parts of bio-based solution-polymerized styrene-butadiene rubber, 22 parts of Keltan ^@ Eco 6950 (bio-based EPDM 6950) of Arlanxeo Company, and 38 parts of natural rubber 3L into the internal mixer for mixing Refining, temperature 85°C, time 60 seconds; then put 26.67 parts of white carbon black, 2.6 parts of silane coupling agent Si-69 for mixing, temperature 95°C, time 120 seconds; then put 13.33 parts of white carbon black, stearic acid 1801 1 part, 0.8 parts of anti-aging agent RD, 1.5 parts of polyethylene glycol PEG4000, 0.7 parts of diethylene glycol, 3.5 parts of zinc oxide, 1.2 parts of polyethylene wax, 1.5 parts of anti-emetic cream OH3, and 1 part of modified carbon nine resin Internal mixer, temperature 125°C, time 90 seconds; clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to open mixer with temperature lower than 70°C, thickness 4-5mm Unload the film twice, then thin the film with a thickness of 1-2mm for two times, adjust it back to a thickness of 4-5mm and unload the film once, and release the film as needed; leave it at room temperature for 24 hours;

Step (3): The temperature of the wheel table is controlled below 60°C. First, the large material is smelted on the drum to soften, and then 0.3 parts of vulcanization accelerator NS, 1 part of anti-yellowing vulcanization accelerator 6-GR, and vulcanization accelerator TBZTD- 75 0.2 parts, 2 parts of insoluble sulfur; first make 3 to 5 triangle bags, thickness 3-4mm, then make thin 1-2 times, thin pass thickness 1-2mm, then make about three triangle bags, and produce slices as needed ;Finally, it is punched out according to the production demand of the sole.

Step (4): Put the punched rubber sheet into the preheated mold of Example 1, vulcanize and mold at a vulcanization temperature of 160±5°C for 120-170 seconds, and tear off the burrs by hand.

Bio-based EPDM 6950 includes: bio-based ethylene 48%, third monomer ENB 9%, which has a Mooney viscosity ML(1+4) of 65 at 125°C.

Example 3:

A preparation method for bio-based rubber soles, comprising the steps of:

Step (1) The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, 100 parts of carboxylated solution-polymerized styrene-butadiene rubber are put into a banbury mixer at a speed of 40-50 rpm, and banburying for two minutes; then 3 parts of zinc oxide are put into , 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the internal temperature of the internal mixer rises to 85 ℃, add 20 parts of epoxy soybean oil, and continue banburying for 12 minutes; The obtained mixture is discharged from the internal mixer, transferred to a two-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber. Among them, carboxylated solution-polymerized styrene-butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd.; epoxy soybean oil is a commercial product; bio-based solution-polymerized styrene-butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100 ° C, The mass ratio of ethylene to the total amount of styrene and butadiene is 25%, and the mass ratio of vinyl to the total amount of butadiene is 48%.

Step (2): First put 40 parts of bio-based solution polystyrene butadiene rubber, 16 parts of Keltan ^@ Eco 8850 (bio-based EPDM rubber 8850) of Arlanxeo Company, and 44 parts of natural rubber 3L into the internal mixer for mixing Refining, the temperature is 85°C, the time is 60 seconds; then 23.33 parts of white carbon black, 2.1 parts of silane coupling agent Si-69 are put into mixing, the temperature is 95°C, the time is 120 seconds; then 11.67 parts of white carbon black, stearic acid 1801 Put 1.1 parts, 0.9 parts of anti-aging agent, 2.5 parts of active agent, 3.8 parts of zinc oxide, 1.5 parts of polyethylene wax, 1.8 parts of anti-vomiting cream OH3, and 1.4 parts of tackifying resin into the internal mixer at a temperature of 125 ° C for 90 seconds; Clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to the open mill with temperature lower than 70°C, thickness 4-5mm unload 2 times, and then thin thickness 1-2mm Thin pass 2 times, return to 4-5mm thickness and unload once, and release the film as needed; place at room temperature for 24 hours;

Step (3): The temperature of the wheel table is controlled below 60°C. First, the aniseed material is smelted on the drum to soften, and then 1.8 parts of vulcanization accelerator and 2.3 parts of insoluble sulfur are added; first, 3 to 5 triangle bags are made, with a thickness of 3-4mm. , Thinning 1-2 times again, the thickness of the thinning is 1-2mm, and then making about three triangle bags, and the pieces are produced according to the needs; finally, punching according to the production needs of the soles.

Step (4): Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160±5°C for 120-170 seconds, and tear off the burrs by hand.

The active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerin, and triethanolamine;

The vulcanization accelerator is selected from any one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D, vulcanization accelerator DM .

Put the specific products of the above-mentioned active agent, anti-aging agent, tackifying resin, and vulcanization accelerator into Example 3, and then conduct experimental tests on the obtained bio-based rubber outsole. The experimental data are shown in the values of Example 3 in Table 1. Since the obtained values have little difference, the average value is taken for calculation, as shown in Table 1.

Example 4

In this embodiment, the preparation method of a bio-based rubber outsole is basically the same as the preparation method in Example 3, the difference is:

Bio-based EPDM rubber 9950 16 parts, natural rubber SCRWF 40 parts.

Example 5

A preparation method for bio-based rubber soles, comprising the steps of:

Step (1) The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, put 100 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer at a speed of 30-40 rpm, and banbury for two minutes; then put 3 parts of zinc oxide , 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the internal temperature of the internal mixer rises to 85 ℃, add 43 parts of epoxy soybean oil, and continue banburying for 15 minutes; The obtained mixture is discharged from the internal mixer, transferred to a two-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber. Among them, carboxylated solution polystyrene butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd.; epoxy soybean oil is a commercially available product; bio-based solution polystyrene butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100°C, Ethylene accounts for 40% by mass of the total amount of styrene and butadiene, and vinyl accounts for 30% by mass of the total amount of butadiene.

Step (2): First put 40 parts of bio-based solution-polymerized styrene-butadiene rubber, 16 parts of Keltan ^@ Eco 6950 (bio-based EPDM 6950) of Arlanxeo Company, and 38 parts of natural rubber 3L into the internal mixer for mixing Refining, temperature 85°C, time 60 seconds; then put in 25.33 parts of white carbon black, 2.8 parts of silane coupling agent Si-69 and mix, temperature 95°C, time 120 seconds; then put in 12.67 parts of white carbon black, stearic acid 1801 0.7 parts, 0.6 parts of anti-aging agent BHT, 1.4 parts of polyethylene glycol PEG4000, 0.5 parts of diethylene glycol, 3.2 parts of zinc oxide, 0.7 parts of polyethylene wax, 1.0 parts of anti-emetic cream agent OH, 0.9 parts of modified carbon nine resin Internal mixer, temperature 125°C, time 90 seconds; clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to open mixer with temperature lower than 70°C, thickness 4-5mm Unload the film twice, then thin the film with a thickness of 1-2mm for two times, adjust it back to a thickness of 4-5mm and unload the film once, and release the film as needed; leave it at room temperature for 24 hours;

Step (3): The temperature of the wheel bed is controlled below 60°C. First, the aniseed material is smelted on the drum to soften, and then 0.25 parts of vulcanization accelerator NS, 0.75 parts of anti-yellowing vulcanization accelerator 6-GR, and vulcanization accelerator TBZTD- 75 0.2 parts, 1.9 parts of insoluble sulfur; first make 3 to 5 triangle bags, the thickness is 3-4mm, and then make thin 1-2 times, the thickness of the thin pass is 1-2mm, and then make about three triangle bags, and the film is produced as needed ;Finally, it is punched out according to the production demand of the sole.

Comparative example 1

In the present embodiment, the preparation method of the rubber outsole is basically the same as the preparation method in Example 3, the difference is:

Use 7 parts of epoxy soybean oil and 33 parts of solution polystyrene butadiene rubber T2003 to replace 40 parts of bio-based solution polystyrene butadiene rubber.

The rubber sole that embodiment 2-5, comparative example 1 obtains is carried out experimental test, and experimental data is as shown in table 1 below:

Table 1

The test conditions of the ozone testing machine are temperature 50°C, humidity 85%, ozone concentration 300pphm, time 3 hours;

Bonding strength in embodiment 2,3,4,5 tests the bonding strength of big end and shoe sole sheet according to GB/T 532-2008; By the EVA foaming big end of same material and the sole of embodiment preparation by standard process The pieces are assembled and molded, the curing agent is 5%, and placed for 24 hours after molding;

The conditions of the hydrolysis resistance test are a temperature of 70°C, a humidity of 95%, and a time of 168 hours.

The above records are only examples of using the technical content of this creation. Any modifications and changes made by those who are familiar with this technology using this creation belong to the scope of patents claimed by this creation, and are not limited to those disclosed in the examples.

Industrial Applicability

The invention discloses a bio-based rubber sole, which comprises the following components in parts by weight: 40 parts of bio-based solution polystyrene butadiene rubber, 16-24 parts of bio-based EPDM rubber, 38-46 parts of natural rubber, white carbon black 35-40 parts, 2.1-2.8 parts of silane coupling agent, 0.7-1.1 parts of stearic acid, 0.6-0.9 parts of anti-aging agent, 1.9-2.5 parts of active agent, 3.2-3.8 parts of zinc oxide, 0.7-1.5 parts of polyethylene wax , 1.0-1.8 parts of anti-emetic cream agent, 0.9-1.4 parts of tackifying resin, 1.2-1.8 parts of vulcanization accelerator, 1.9-2.3 parts of insoluble sulfur; when preparing bio-based solution-polymerized styrene-butadiene rubber in this application, carboxylated solvent Polystyrene butadiene rubber, zinc oxide, stearic acid, and epoxidized soybean oil are mixed in an internal mixer to build an ester-based cross-linked network structure, which has the advantage of not separating out oil. In addition, during vulcanization molding, the ion pairs formed by zinc ions and carboxyl groups in the rubber compound can be used as strengthening points, which increases the degree of crosslinking and improves the mechanical properties of the bio-based rubber outsole, which has industrial applicability.

Claims

A kind of bio-based rubber sole, is characterized in that, comprises following components by weight:
A kind of bio-based rubber sole according to claim 1, characterized in that,

The active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerin, and triethanolamine;

The anti-aging agent is selected from any one or more of anti-aging agent RD, anti-aging agent BHT, anti-aging agent 1010, anti-aging agent MB, anti-aging agent 4010, and anti-aging agent 264;

The tackifying resin is selected from any one or more of carbon five resins, carbon nine resins, modified carbon nine resins, phenolic resins, and coumarone-indene resins;

The vulcanization accelerator is selected from any one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D, vulcanization accelerator DM ;

The silane coupling agent is selected from any one or more of KH-550 and KH-560.
A kind of bio-based rubber sole according to claim 1, characterized in that,

The preparation method of the bio-based solution-polymerized styrene-butadiene rubber is as follows: 100-300 parts of carboxylated solution-polymerized styrene-butadiene rubber are put into a banbury mixer for internal mixing, and then 3-6 parts of zinc oxide and 1-3 parts of stearic acid are put into the mixture. The friction of the system generates heat, and the temperature in the internal mixer gradually rises; add 20-43 parts of epoxy soybean oil, continue to banbury, discharge, and cool to obtain bio-based solution-polymerized styrene-butadiene rubber;

The bio-based solution-polymerized styrene-butadiene rubber has a Mooney viscosity ML(1+4) of 55-65 at 100°C; the bio-based solution-polymerized styrene-butadiene rubber includes 25%-40% of bound styrene.
The bio-based rubber sole according to claim 1, wherein the bio-based EPDM rubber includes 45%-60% of bio-based ethylene, and 5.5%-9% of the third monomer ENB;

The bio-based EPDM rubber has a Mooney viscosity ML(1+4) of 55-80 at 125°C.
The preparation method of a kind of bio-based rubber sole according to any one of claims 1-4, is characterized in that, comprises the following steps:

Step (1): mixing bio-based solution-polymerized styrene-butadiene rubber, bio-based EPDM rubber, and natural rubber;

Put in some white carbon black and silane coupling agent for mixing, and then put in the remaining white carbon black, stearic acid, anti-aging agent, active agent, zinc oxide, polyethylene wax, anti-vomiting cream, tackifying resin; clean Once, continue mixing, discharging and cooling;

Step (2): The mixture obtained in step (1) is softened, and then vulcanization accelerator and insoluble sulfur are added; slices are produced as required, and punched according to the production requirements of shoe soles;

Step (3): Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160±5°C for 120-170 seconds, and tear off the burrs by hand.
A rubber bottom sheet mold for preparing the bio-based rubber sole of any one of claims 1-4, characterized in that it comprises

an upper template, the upper template including a first groove area;

A lower formwork connected to the upper formwork, the lower formwork has a lower rubber base area, a lower burr area, and a second groove area;

The edge of the lower rubber base area is connected with the second groove area, and the side of the second groove area away from the lower rubber base area is connected to the lower burr area;

When the upper template is sealingly connected with the lower template, the first groove area is located above the second groove area.
The mold for rubber film according to claim 6, characterized in that, the groove angle at the bottom of the second groove area is 30-60 degrees.
A kind of rubber film mold according to claim 7, is characterized in that,

When the upper template is sealed and connected to the lower template, the position of the sharp corner at the bottom of the second groove area corresponds to the edge position of the first groove area;

When the upper template is sealed and connected with the lower template, with the horizontal position as the reference line, the sharp corner position at the bottom of the second groove area is 0-0.3 mm away from the edge of the first groove area.
A kind of rubber film mold according to claim 6, is characterized in that,

The lower rubber base area includes a first lower rubber base area and a second lower rubber base area, the first lower rubber base area corresponds to the position of the forefoot, the second lower rubber base area corresponds to the rear heel position, and the second lower rubber base area corresponds to the position of the rear heel. The lower rubber base area and the second lower rubber base area are not connected to each other, and the first lower rubber base area and the second lower rubber base area are respectively connected to the second groove area.
A kind of rubber film mold according to claim 9, is characterized in that,

The lower rubber base area includes a third lower rubber base area, the third lower rubber base area corresponds to the position of the center of the foot, and the third lower rubber base area is not in contact with the first lower rubber base area, the second lower rubber base area The rubber chassis area is connected, and the third lower rubber chassis area is connected to the second groove area.