CN113444303B - Anti-slippery bio-based rubber sole and preparation method and mold thereof - Google Patents
Anti-slippery bio-based rubber sole and preparation method and mold thereof Download PDFInfo
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- CN113444303B CN113444303B CN202110856838.0A CN202110856838A CN113444303B CN 113444303 B CN113444303 B CN 113444303B CN 202110856838 A CN202110856838 A CN 202110856838A CN 113444303 B CN113444303 B CN 113444303B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/128—Moulds or apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an anti-slippery bio-based rubber sole and a preparation method and a mold thereof, wherein the anti-slippery bio-based rubber sole comprises the following components, by weight, 50 parts of bio-based solution-polymerized styrene-butadiene rubber, 26-34 parts of carboxylated nitrile rubber, 16-24 parts of epoxidized natural rubber, 35-50 parts of white carbon black, 2.1-2.8 parts of a silane coupling agent, 1.2-1.5 parts of stearic acid, 1.0-1.3 parts of an anti-aging agent, 1.9-2.5 parts of an active agent, 4-6 parts of zinc oxide, 1.2-1.5 parts of polyethylene wax, 1.4-1.8 parts of an anti-emetic agent, 1.3-1.7 parts of tackifying resin, 1.0-1.2 parts of a vulcanization accelerator and 1.1-1.5 parts of insoluble sulfur; when the bio-based solution-polymerized styrene-butadiene rubber is prepared for polymerization, the carboxylated solution-polymerized styrene-butadiene rubber, the zinc oxide, the stearic acid and the epoxidized soybean oil are banburied in an internal mixer to construct an ester-based cross-linked network structure, and the bio-based solution-polymerized styrene-butadiene rubber has the advantage of no oil precipitation. In addition, during vulcanization molding, an ion pair formed by zinc ions and carboxyl in the rubber material can be used as a reinforcing point, so that the crosslinking degree is improved, and the mechanical property of the bio-based rubber outsole is improved.
Description
Technical Field
The invention relates to the technical field of sole preparation, in particular to a wet-skid resistant bio-based rubber sole and a preparation method and a mold thereof.
Background
At present, the method responds to the national call, reduces carbon emission and realizes carbon peak reaching as early as possible. The shoe making field can do from 3 aspects, reduces the resource consumption, utilizes waste as resource, and changes harmful into harmless. At present, the used rubber and plastics are all prepared by extracting monomers such as ethylene, propylene, butadiene and the like from petroleum and polymerizing the monomers, thereby consuming a large amount of petroleum resources. In order to reduce the utilization of petroleum resources, soybean oil and epoxidized soybean oil can be directly added into a rubber material and physically blended to prepare a rubber product, but the method has the problems of small addition amount, poor compatibility, easy precipitation and the like, and particularly in the field of soles, the soybean oil is precipitated to cause poor bonding strength between a rubber outsole and a foamed insole, easy rubber cracking and high quality risk.
In addition, the existing waste rubber is usually ground into powder to be used as a filler or used for thermal power generation, so that the utilization value is very low; or the waste rubber is subjected to desulfurization technology to destroy the chemical network structure of vulcanized rubber to prepare regenerated rubber, but the regenerated rubber contains a large amount of harmful polycyclic aromatic hydrocarbon and cannot be used in the field of shoe making.
Disclosure of Invention
The embodiment of the application provides the anti-slippery bio-based rubber sole and the preparation method and the die thereof, so that the technical problems that in the prior art, the carbon emission is too much, soybean oil in the sole is easy to separate out, the high-value recycling of the waste rubber sole is realized, the use of non-renewable resources is reduced, the high-value recycling of waste rubber resources is realized, the anti-slippery bio-based rubber sole with excellent anti-slippery performance is obtained, the technical effect of rapid edge tearing is realized, and the production efficiency is remarkably improved.
The embodiment of the application provides an anti-slippery bio-based rubber sole, which comprises the following components in parts by weight:
further, the active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerol and triethanolamine;
the anti-aging agent is selected from 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 resin, carbon nine resin, modified carbon nine resin, phenolic resin and coumarone-indene resin;
the vulcanization accelerator is selected from one or more of a vulcanization accelerator NS, a vulcanization accelerator TS, a vulcanization accelerator TBZTD, a vulcanization accelerator 6-GR, a vulcanization accelerator M, a vulcanization accelerator D and a 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 comprises the following steps: adding 100-300 parts of carboxylated solution-polymerized styrene-butadiene rubber into an internal mixer for banburying, then adding 3-6 parts of zinc oxide and 1-3 parts of stearic acid, generating heat by system friction, and gradually increasing the temperature in the internal mixer; adding 20-43 parts of epoxidized soybean oil, continuously banburying, discharging and cooling 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 45-70 at 100 ℃; the bio-based solution polymerized styrene-butadiene rubber comprises 25-40% of bound styrene.
Furthermore, the mass fraction of carboxyl of the carboxylated nitrile rubber is 3% -10%, and the mass fraction of bound acrylonitrile is 23% -42%.
A preparation method of an anti-slippery bio-based rubber sole comprises the following steps:
step (1): mixing bio-based solution polymerized styrene-butadiene rubber, carboxylated nitrile rubber and epoxidized natural rubber; adding some white carbon black and silane coupling agent for mixing, and then adding the rest white carbon black, stearic acid, anti-aging agent, active agent, zinc oxide, polyethylene wax, anti-emetic agent and tackifying resin; cleaning once, continuously mixing, discharging and cooling;
step (2): softening the mixture obtained in the step (1), and adding a vulcanization accelerator and insoluble sulfur; the sheets are taken out as required, and the sheets are punched according to the production requirement of the sole;
and (3): and (3) putting the punched rubber sheet into a preheated die, vulcanizing and forming at the vulcanization temperature of 160 +/-5 ℃ for 140-220 seconds, and manually tearing rough edges.
A rubber substrate die comprises
An upper die plate including a first recessed area;
the lower template is connected with the upper template and is provided with a lower rubber bottom sheet area, a lower burr area and a second groove area;
the edge of the lower rubber bottom sheet area is connected with the second groove area, and one side, away from the lower rubber bottom sheet area, of the second groove area is connected with the lower burr area;
when the upper template is in sealing connection with the lower template, the first groove area is located above the second groove area.
Further, the bottom groove angle of the second groove area is 30-60 degrees.
Further, when the upper template is in sealing connection with the lower template, the position of a 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 in sealing connection with the lower template, the sharp angle position at the bottom of the second groove area is 0-0.3mm away from the edge of the first groove area by taking the horizontal position as a datum line.
Further, the lower rubber substrate area comprises a first lower rubber substrate area and a second lower rubber substrate area, the first lower rubber substrate area corresponds to a front sole position, the second lower rubber substrate area corresponds to a rear heel position, the first lower rubber substrate area and the second lower rubber substrate area are not connected with each other, and the first lower rubber substrate area and the second lower rubber substrate area are respectively connected with the second groove area.
Further, the lower rubber substrate area comprises a third lower rubber substrate area, the third lower rubber substrate area corresponds to the position of the foot center, the third lower rubber substrate area is not connected with the first lower rubber substrate area and the second lower rubber substrate area, and the third lower rubber substrate area is connected with the second groove area.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
when the bio-based solution-polymerized styrene-butadiene rubber is prepared for polymerization, the carboxylated solution-polymerized styrene-butadiene rubber, the zinc oxide, the stearic acid and the epoxidized soybean oil are banburied in an internal mixer to construct an ester-based cross-linked network structure, and the bio-based solution-polymerized styrene-butadiene rubber has the advantage of no oil precipitation. In addition, during vulcanization molding, an ion pair formed by zinc ions and carboxyl in the rubber material can be used as a reinforcing point, so that the crosslinking degree is improved, and the mechanical property of the bio-based rubber outsole is improved.
This application is with the biobased solution-polymerized butadiene styrene rubber of ester group crosslinked as the host rubber, collocation carboxylation nitrile rubber and epoxidized natural rubber, adopt insoluble sulfur crosslinking and ester group crosslinking to combine together, the use amount of insoluble sulfur and vulcanization accelerator has been reduced, the difficult cracked sulphur-sulphur bond's in the crosslinked rubber network structure content has been reduced, and simultaneously, use zinc oxide as the catalyst, through the epoxy group in epoxidation natural rubber and the biobased solution-polymerized butadiene styrene rubber structure, carboxylic acid group in with carboxylation nitrile rubber and the biobased solution-polymerized butadiene styrene rubber structure takes place the reaction, thereby introduce hydrolysable ester group in the network structure of crosslinked rubber. Under the catalysis of strong acid or strong base, ester groups in the cross-linked rubber can be selectively hydrolyzed, so that cross-linked bonds in a cross-linked network are broken, the cross-linked density is reduced, and the cross-linked rubber can be used as a sole raw material and used for manufacturing soles again, and the high-value recycling of the cross-linked rubber is realized.
According to the shoe sole, polar rubber containing epoxy groups and carboxylic acid groups is adopted, more hydrophilic ester-based chain segments are arranged in a cross-linked rubber molecular structure, and a small amount of exposed hydrophilic groups such as hydroxyl groups and carboxyl groups are arranged, so that when the sole is contacted with water, the hydrophilic ester-based chain segments, the hydrophilic groups such as the hydroxyl groups and the carboxyl groups reduce the liquid surface tension, a liquid film can be prevented from being formed between the sole and an interface, the grip force on slippery ground is improved, the wet dynamic slip limiting coefficient is obviously improved, and the anti-slippery performance is excellent.
The upper die and the lower die are provided with first groove areas and second groove areas, and the first groove areas are located above the second groove areas when viewed in the vertical direction; when viewed from the horizontal direction, the sharp angle position at the bottom of the second groove area (the angle of the sharp angle is 30-60 degrees) is superposed with or separated from the edge position of the first groove area by a certain distance, and by adopting the design, after the burrs are removed, the surface of the rubber bottom sheet has almost no burrs.
Last burr district in this application is mutual coincidence and is connected with lower burr district, consequently when getting rid of deckle edge, only need select the arbitrary burr position of rubber film to tear, just can get rid of whole burr district, realizes quick hand and tears unedged effect, has reduced the deburring arrangement process, is showing improvement production efficiency.
The anti-slippery bio-based rubber sole of the present application can be used for both the outsole and the sole sheet. When the sole plate is prepared, four sides of the sole plate are needed, so the raw edges of the sole plate need to be connected together, and when the conventional rubber sole formula is used for preparing the sole, the flowability is poor, and the numerical values of comparative example 1 in table 1 are shown. The anti-slippery bio-based rubber sole has good fluidity and is more suitable for preparing the sole piece.
Drawings
FIG. 1 is a schematic diagram of an upper plate structure of this embodiment 1;
fig. 2 is a schematic structural view of the lower template in this embodiment 1;
fig. 3 is a schematic partial structure view of the lower template of this embodiment 1;
FIG. 4 is a schematic view of a location structure of a first recessed area and a second recessed area in this embodiment 1;
FIG. 5 is a real image (front side) of a rubber base sheet prepared by the mold of example 1;
FIG. 6 is a schematic view of a rubber base sheet (flash removed) produced by the mold of this example 1;
reference numerals
11. Lower rubber substrate district, 111, first rubber substrate district, 112, second lower rubber substrate district, 12, lower deckle edge district, 13, second recess district, 21, go up rubber substrate district, 22, go up deckle edge district, 23, first recess district.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1
A rubber bottom sheet die is composed of an upper die plate and a lower die plate. Referring to fig. 1, the upper plate has an upper rubber substrate area 21, an upper burr area 22, and a first groove area 23, and the upper rubber substrate area 21 is connected to the upper burr area 22 through the first groove area 23. Referring to fig. 2 and 3, the lower template has a lower rubber bottom plate 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, the edge of the lower rubber bottom plate area 11 is connected with the second groove area 13, and one side of the second groove area 13 departing from the lower rubber bottom plate area 11 is connected with the lower burr area 12.
When the upper template and the lower template are in sealing connection, the upper rubber substrate area 21 coincides with the lower rubber substrate area 11, the upper burr area 22 coincides with the lower burr area 12, and referring to fig. 4, the first groove area 23 is located above the second groove area 13 when viewed in the vertical direction (y direction); viewed in the horizontal direction (x direction), the position of the sharp corner at the bottom of the second recessed area 13 (the angle of the sharp corner is 30 to 60 degrees) coincides with the position of the edge of the first recessed area 23 or the position of the sharp corner at the bottom of the second recessed area 13 is 0 to 0.3mm from the edge of the first recessed area 23.
The lower rubber substrate area 11 comprises a first lower rubber substrate area 111, a second lower rubber substrate area 112 and a third lower rubber substrate area; the first lower rubber sole area 111 corresponds to the front sole position, the second lower rubber sole area 112 corresponds to the rear heel position, and the third lower rubber sole area corresponds to the arch position. The first lower rubber substrate area 111, the second lower rubber substrate area 112 and the third lower rubber substrate area are not connected with each other, but are connected with the second groove.
In the process of actually using the sole, because the stress and friction conditions of different positions of the sole are different, correspondingly, the thicknesses and the shapes of different areas in the rubber sole are different. Also, for faster burr removal, the thickness of the second recessed area 13 should be less than the thickness of the lower rubber backsheet area 11 and the lower burr area 12.
When producing the rubber film, in order to raise the efficiency, can place preceding sole, heel, the corresponding rubber film district of arch of foot in a mould production, however when specifically using, the rubber film district is not whole to paste on the big end, but according to the difference of sole position, selects suitable rubber film laminating, consequently, still need get rid of the deckle edge after the preparation and just can use.
Referring to fig. 5, since the upper and lower burr regions 12 of the rubber bottom sheet are connected to each other, when the burrs are removed, the whole burr region can be removed by simply selecting any burr region position of the rubber bottom sheet to tear. Referring to FIG. 6, it can be seen that the edges of the rubber backsheet after the burr and groove areas have been removed are very smooth.
Example 2:
a preparation method of an anti-slippery bio-based rubber sole comprises the following steps:
step (1): the preparation method of the bio-based solution polymerized styrene butadiene rubber comprises the following steps: firstly, 100 parts of carboxylated solution-polymerized styrene-butadiene rubber is put into an internal mixer, the rotating speed is 40-50 r/min, and the internal mixing is carried out for two minutes; then adding 3 parts of zinc oxide and 1 part of stearic acid, generating heat by system friction, and gradually increasing the temperature in the internal mixer; when the temperature in the internal mixer rises to 85 ℃, 27 parts of epoxidized soybean oil is added, and the internal mixing is continued for 12 minutes; finally, discharging the obtained mixture from an internal mixer, transferring the mixture to a double-roll open mill, rolling out sheets, and cooling to room temperature to obtain the bio-based solution polymerized styrene butadiene rubber; wherein the carboxylated solution polymerized styrene-butadiene rubber is obtained from Zhenjiang beautification chemical company, inc.; epoxidized soybean oil is a commercially available product; the bio-based solution polymerized styrene-butadiene rubber has a Mooney viscosity ML (1 + 4) at 100 ℃, the mass ratio of the combined styrene to the total amount of the styrene and the butadiene is 34%, and the mass ratio of the vinyl to the total amount of the butadiene is 34%.
Step (2): firstly, 50 parts of bio-based solution-polymerized styrene-butadiene rubber, 1072 parts of carboxylated nitrile-butadiene rubber of Nandi chemical company and 20 parts of epoxidized natural rubber ENR are put into an internal mixer for mixing at the temperature of 80 ℃ for 90 seconds; then 25 parts of white carbon black and 2.5 parts of silane coupling agent Si-69 are added for mixing, the temperature is 90 ℃, and the time is 120 seconds; then 13 parts of white carbon black, 1801.4 parts of stearic acid, 0.8 part of antioxidant RD, 0.4 part of antioxidant MB, 1.4 parts of polyethylene glycol PEG4000, 0.7 part of diethylene glycol, 5.5 parts of zinc oxide, 1.3 parts of polyethylene wax, 1.5 parts of anti-emetic agent OH and 1.5 parts of modified carbon nine resin are put into an internal mixer, the temperature is 115 ℃ and the time is 110 seconds; cleaning once, continuously mixing for 90 seconds at the temperature of 120 ℃; discharging at 123 deg.C, immediately transferring to an open mill at a temperature below 70 deg.C, unloading slices with thickness of 4-5mm for 2 times, thinning to thickness of 1-2mm for 2 times, adjusting to thickness of 4-5mm, unloading slices once, and discharging slices as required; standing at room temperature for 24 hours;
and (3): controlling the temperature of a roller table to be below 60 ℃, softening a large material on a roller, and then adding 0.2 part of vulcanization accelerator NS, 0.8 part of yellowing-resistant vulcanization accelerator 6-GR, 0.2 part of vulcanization accelerator TBZTD-75, and 1.3 parts of insoluble sulfur; firstly, 3-5 triangular bags are made, the thickness of the triangular bags is 3-4mm, then the triangular bags are thinned for 1-2 times, the thickness of the thin bags is 1-2mm, then the triangular bags are made to be about three, and sheets are taken out as required; and finally, blanking according to the production requirement of the sole.
And (4): the rubber sheet after blanking was put into the preheated mold of this example 1, vulcanized and molded at a vulcanization temperature of 162 ℃ for 160 seconds, and then the raw edge was torn by hand.
Example 3:
a preparation method of the anti-slippery bio-based rubber sole comprises the following steps:
the preparation method of the bio-based solution polymerized styrene butadiene rubber in the step (1) comprises the following steps: firstly, 100 parts of carboxylated solution-polymerized styrene-butadiene rubber is put into an internal mixer, and the internal mixing is carried out for two minutes at the rotating speed of 40-50 r/min; then adding 3 parts of zinc oxide and 1 part of stearic acid, generating heat by system friction, and gradually increasing the temperature in the internal mixer; when the temperature in the internal mixer rises to 85 ℃, adding 20 parts of epoxidized soybean oil, and continuously carrying out internal mixing for 12 minutes; and finally discharging the obtained mixture from an internal mixer, transferring the mixture to a double-roll open mill, rolling out sheets, and cooling to room temperature to obtain the bio-based solution polymerized styrene butadiene rubber. Wherein the carboxylated solution polymerized styrene-butadiene rubber is from Zhenjiangqi beautifying chemical company Limited; epoxidized soybean oil is a commercially available product; the bio-based solution polymerized styrene-butadiene rubber has a Mooney viscosity ML (1 + 4) of 60 at 100 ℃, the combined styrene accounts for 25 percent of the mass ratio of the total amount of the styrene and the butadiene, and the vinyl accounts for 48 percent of the mass ratio of the total amount of the butadiene.
Step (2): firstly, 50 parts of bio-based solution-polymerized styrene-butadiene rubber, 1072 parts of carboxylated nitrile rubber of a Nandi chemical company and 18 parts of epoxidized natural rubber ENR are put into an internal mixer for mixing at the temperature of 80 ℃ for 90 seconds; then adding 23 parts of white carbon black and 2.1 parts of silane coupling agent Si-69 for mixing at the temperature of 90 ℃ for 120 seconds; then adding 12 parts of white carbon black, 1801.2 parts of stearic acid, 1.0 part of anti-aging agent, 1.9 parts of active agent, 4 parts of zinc oxide, 1.2 parts of polyethylene wax, 1.4 parts of antiemetic agent OH and 1.3 parts of tackifying resin into an internal mixer, and feeding the mixture at the temperature of 115 ℃ for 110 seconds; cleaning once, continuously mixing for 90 seconds at the temperature of 120 ℃; discharging at 123 deg.C, immediately transferring to an open mill at a temperature below 70 deg.C, unloading slices with thickness of 4-5mm for 2 times, thinning to thickness of 1-2mm for 2 times, adjusting to thickness of 4-5mm, unloading slices once, and discharging slices as required; standing at room temperature for 24 hours;
and (3): controlling the temperature of a wheel table below 60 ℃, softening the large material on a roller, and then adding 1.0 part of vulcanization accelerator and 1.1 part of insoluble sulfur; firstly, packaging 3-5 triangular bags with the thickness of 3-4mm, then thinning for 1-2 times with the thickness of 1-2mm, packaging about three triangular bags, and discharging sheets as required; and finally, blanking according to the production requirement of the sole.
And (4): and (3) putting the punched rubber sheet into a preheated die, vulcanizing and forming at the vulcanization temperature of 157 ℃ for 180 seconds, and manually tearing rough edges.
The active agent is selected from one or more of polyethylene glycol, diethylene glycol, glycerol and triethanolamine;
the anti-aging agent is selected from 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 resin, carbon nine resin, modified carbon nine resin, phenolic resin and coumarone-indene resin;
the vulcanization accelerator is selected from one or more of a vulcanization accelerator NS, a vulcanization accelerator TS, a vulcanization accelerator TBZTD, a vulcanization accelerator 6-GR, a vulcanization accelerator M, a vulcanization accelerator D and a vulcanization accelerator DM.
The concrete products of the activator, the antioxidant, the tackifier resin and the vulcanization accelerator were put into example 3, and the obtained bio-based rubber sole was subjected to experimental tests, wherein experimental data are shown in table 1 as the numerical values of example 3, and the average values were calculated as shown in table 1 as the obtained numerical values are not greatly different.
Example 4
In this example, a method of manufacturing a bio-based rubber outsole is substantially the same as the method of manufacturing in example 3, except that:
3245 parts of carboxylated nitrile rubber and ENR25 parts of epoxidized natural rubber.
Example 5
A preparation method of the anti-slippery bio-based rubber sole comprises the following steps:
the preparation method of the bio-based solution polymerized styrene butadiene rubber in the step (1) comprises the following steps: firstly, 100 parts of carboxylated solution-polymerized styrene-butadiene rubber is put into an internal mixer, the rotating speed is 30-40 r/min, and the internal mixing is carried out for two minutes; then adding 3 parts of zinc oxide and 1 part of stearic acid, generating heat by system friction, and gradually increasing the temperature in the internal mixer; when the temperature in the internal mixer rises to 85 ℃, 43 parts of epoxidized soybean oil is added, and internal mixing is continued for 15 minutes; and finally, discharging the obtained mixture from an internal mixer, transferring the mixture to a double-roll open mill, rolling out sheets, and cooling to room temperature to obtain the bio-based solution polymerized styrene-butadiene rubber. Wherein the carboxylated solution polymerized styrene-butadiene rubber is obtained from Zhenjiang beautification chemical company, inc.; epoxidized soybean oil is a commercially available product; the bio-based solution polymerized styrene-butadiene rubber has a Mooney viscosity ML (1 + 4) at 100 ℃, the combined styrene accounts for 40 percent of the mass ratio of the total amount of the styrene and the butadiene, and the vinyl accounts for 30 percent of the mass ratio of the total amount of the butadiene.
Step (2): firstly, 50 parts of bio-based solution polymerized styrene-butadiene rubber, 1072 parts of carboxylated nitrile rubber of the Nandi chemical company and 24 parts of epoxidized natural rubber ENR are put into an internal mixer for mixing at the temperature of 85 ℃ for 70 seconds; then 27 parts of white carbon black and 2.8 parts of silane coupling agent Si-69 are added for mixing, the temperature is 90 ℃, and the time is 120 seconds; then adding 13 parts of white carbon black, 1801.5 parts of stearic acid, 1.3 parts of antioxidant BHT, 4000.8 parts of polyethylene glycol PEG, 0.7 part of diethylene glycol, 6 parts of zinc oxide, 1.5 parts of polyethylene wax, 1.8 parts of antiemetic agent OH and 1.7 parts of coumarone-indene resin into an internal mixer, and feeding the mixture into the internal mixer at the temperature of 120 ℃ for 90 seconds; cleaning once, continuously mixing at 125 ℃ for 90 seconds; discharging at 125 deg.C, immediately transferring to an open mill with a thickness of 4-5mm, discharging for 2 times, thinning for 2 times, and returning to 4-5mm for discharging once; standing at room temperature for 24 hours;
and (3): controlling the temperature of a roller table to be below 60 ℃, softening a large material on a roller, and then adding 0.3 part of vulcanization accelerator NS, 0.75 part of yellowing-resistant vulcanization accelerator 6-GR, 0.25 part of vulcanization accelerator TBZTD-75 and 1.5 parts of insoluble sulfur; firstly, packaging 3-5 triangular bags with the thickness of 3-4mm, then thinning for 1-2 times with the thickness of 1-2mm, packaging about three triangular bags, and discharging sheets as required; and finally, blanking according to the production requirement of the sole.
And (4): and (3) putting the punched rubber sheet into a preheated die, vulcanizing and forming at the vulcanization temperature of 165 ℃ for 140 seconds, and tearing burrs by hands.
Comparative example 1
In this example, the preparation method of the rubber outsole is basically the same as that in example 3, except that:
7 parts of epoxidized soybean oil and 33 parts of solution polymerized styrene-butadiene rubber T2003 are used to replace 50 parts of bio-based solution polymerized styrene-butadiene rubber.
The rubber soles obtained in examples 2 to 5 and comparative example 1 were subjected to experimental tests, and the experimental data are shown in the following table 1:
TABLE 1
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (7)
1. The anti-slippery bio-based rubber sole is characterized by comprising the following components in parts by weight:
the active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerol and triethanolamine;
the preparation method of the bio-based solution polymerized styrene-butadiene rubber comprises the following steps: adding 100-300 parts of carboxylated solution-polymerized styrene-butadiene rubber into an internal mixer for banburying, then adding 3-6 parts of zinc oxide and 1-3 parts of stearic acid, generating heat by system friction, and gradually increasing the temperature in the internal mixer; adding 20-43 parts of epoxidized soybean oil, continuously banburying, discharging and cooling 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 45-70 at 100 ℃; the bio-based solution polymerized styrene-butadiene rubber comprises 25-40% of bound styrene.
2. The anti-slip bio-based rubber shoe sole according to claim 1,
the anti-aging agent is selected from 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 resin, carbon nine resin, modified carbon nine resin, phenolic resin and coumarone-indene resin;
the vulcanization accelerator is selected from one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D and vulcanization accelerator DM;
the silane coupling agent is selected from any one or more of KH-550 and KH-560.
3. The anti-slippery bio-based rubber shoe sole according to claim 1, wherein the carboxylated nitrile rubber has a carboxyl mass fraction of 3% to 10% and bound acrylonitrile 23% to 42%.
4. The method for preparing a wet skid resistant bio-based rubber shoe sole according to any one of claims 1-3, comprising the steps of:
step (1): mixing bio-based solution polymerized styrene-butadiene rubber, carboxylated nitrile rubber and epoxidized natural rubber; adding some white carbon black and silane coupling agent for mixing, and then adding the rest white carbon black, stearic acid, anti-aging agent, active agent, zinc oxide, polyethylene wax, anti-emetic agent and tackifying resin; cleaning once, continuously mixing, discharging and cooling;
step (2): softening the mixture obtained in the step (1), and adding a vulcanization accelerator and insoluble sulfur; the sheets are taken out as required, and the sheets are punched according to the production requirement of the sole;
and (3): and (3) putting the punched rubber sheet into a preheated die, vulcanizing and forming at the vulcanization temperature of 160 +/-5 ℃ for 140-220 seconds, and manually tearing rough edges.
5. A rubber sole mold for preparing the anti-slippery bio-based rubber sole of any one of claims 1-3, comprising
An upper die plate including a first recessed area;
the lower template is connected with the upper template and is provided with a lower rubber bottom sheet area, a lower burr area and a second groove area;
the edge of the lower rubber bottom sheet area is connected with the second groove area, and one side, away from the lower rubber bottom sheet area, of the second groove area is connected with the lower burr area;
when the upper template is in sealing connection with the lower template, the first groove area is positioned above the second groove area;
when the upper template is in sealing connection with the lower template, the sharp corner position at the bottom of the second groove area corresponds to the edge position of the first groove area;
when the upper template is in sealing connection with the lower template, taking the horizontal position as a reference line, and enabling the position of the sharp corner at the bottom of the second groove region to be 0-0.3mm away from the edge of the first groove region;
the angle of the groove at the bottom of the second groove area is 30-60 degrees.
6. Rubber negative mould according to claim 5,
the lower rubber substrate area comprises a first lower rubber substrate area and a second lower rubber substrate area, the first lower rubber substrate area corresponds to the front sole position, the second lower rubber substrate area corresponds to the rear heel position, the first lower rubber substrate area and the second lower rubber substrate area are not connected with each other, and the first lower rubber substrate area and the second lower rubber substrate area are respectively connected with the second groove area.
7. The rubber negative mold of claim 6,
the lower rubber substrate area comprises a third lower rubber substrate area, the third lower rubber substrate area corresponds to the position of the foot center, the third lower rubber substrate area is not connected with the first lower rubber substrate area and the second lower rubber substrate area, and the third lower rubber substrate area is connected with the second groove area.
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| CN202110856838.0A CN113444303B (en) | 2021-07-28 | 2021-07-28 | Anti-slippery bio-based rubber sole and preparation method and mold thereof |
| PCT/CN2022/081062 WO2023005221A1 (en) | 2021-07-28 | 2022-03-16 | Anti-slippery bio-based rubber sole and preparation method therefor, and mold |
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| CN202110856838.0A CN113444303B (en) | 2021-07-28 | 2021-07-28 | Anti-slippery bio-based rubber sole and preparation method and mold thereof |
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| CN113444302B (en) * | 2021-07-28 | 2023-02-07 | 茂泰(福建)鞋材有限公司 | Bio-based rubber sole and preparation method and mold thereof |
| CN117683279B (en) * | 2024-02-02 | 2024-04-05 | 比音勒芬服饰股份有限公司 | Double-arch bridge type supporting shock-absorbing anti-skid sole and preparation method thereof |
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| KR101311264B1 (en) * | 2011-10-11 | 2013-09-25 | 주식회사 나노텍세라믹스 | Manufacturing method for climbing shoes outsole having good adhesive and non-slip properties |
| JP2014218554A (en) * | 2013-05-02 | 2014-11-20 | ブリヂストンスポーツ株式会社 | Rubber composition and shoe sole and shoe using the same |
| CN105801948B (en) * | 2016-04-26 | 2017-11-24 | 茂泰(福建)鞋材有限公司 | A kind of ice face anti-slip rubber composition and its production method |
| CN110577680A (en) * | 2019-09-20 | 2019-12-17 | 泉州师范学院 | light anti-skid rubber sole material and manufacturing method thereof |
| CN113444303B (en) * | 2021-07-28 | 2023-02-07 | 茂泰(福建)鞋材有限公司 | Anti-slippery bio-based rubber sole and preparation method and mold thereof |
| CN215943578U (en) * | 2021-07-28 | 2022-03-04 | 茂泰(福建)鞋材有限公司 | Rubber substrate mould |
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Address after: No. 588, Jinxin Road, Jiangtou Village, Chendai Town, Jinjiang City, Quanzhou City, Fujian Province, 362000 Patentee after: Maotai (Fujian) New Material Technology Co.,Ltd. Patentee after: Shengtai (Fujian) shoe material Co.,Ltd. Address before: 362000 Chen Dai Zhen Jiang tou Cun, Jinjiang City, Quanzhou City, Fujian Province Patentee before: Maotai(Fujian) Soles Co.,Ltd. Patentee before: Shengtai (Fujian) shoe material Co.,Ltd. |
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