CN111995837B - Anti-aging rubber material for soles and preparation method thereof - Google Patents
Anti-aging rubber material for soles and preparation method thereof Download PDFInfo
- Publication number
- CN111995837B CN111995837B CN202010718808.9A CN202010718808A CN111995837B CN 111995837 B CN111995837 B CN 111995837B CN 202010718808 A CN202010718808 A CN 202010718808A CN 111995837 B CN111995837 B CN 111995837B
- Authority
- CN
- China
- Prior art keywords
- mixed material
- parts
- titanium dioxide
- maleic anhydride
- eva
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to an anti-aging rubber material for soles, which belongs to the technical field of sole processing, and comprises, by weight, 37-54 parts of SBS, 21-28 parts of PS, 15.5-23 parts of maleic anhydride graft modified EVA, 5.5-8 parts of modified silicon-aluminum-carrying titanium dioxide, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 2-4 parts of stearic acid. The anti-aging rubber material for the shoe sole has good anti-aging property and wear resistance, and shows good comprehensive performance.
Description
Technical Field
The application relates to the technical field of sole processing, in particular to an anti-aging rubber material for soles and a preparation method thereof.
Background
Styrene-butadiene-styrene triblock copolymer (SBS) is an important thermoplastic elastomer, which has advantages of light weight, wet skid resistance, no odor, recyclability, and is widely used for soles of sneakers and sports shoes. Pure SBS is used as the material of the sole, and although the sole has high flexibility, the anti-aging property is poor.
Disclosure of Invention
The present application aims to provide an anti-aging rubber material for shoe soles, which has good aging resistance and wear resistance and shows good combination of properties.
The second purpose of the present application is to provide a preparation method of an anti-aging rubber material for shoe soles, which has the advantages of simple preparation and convenient control.
The above object of the present application is achieved by the following technical solutions:
an anti-aging rubber material for soles comprises, by weight, 37-54 parts of SBS, 21-28 parts of PS, 15.5-23 parts of maleic anhydride graft modified EVA, 5.5-8 parts of modified silicon-aluminum-carrying titanium dioxide, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 2-4 parts of stearic acid.
By adopting the technical scheme, the maleic anhydride graft modified EVA and the modified silicon-aluminum-loaded titanium dioxide are added into the raw materials of the anti-aging rubber material, and the anti-aging property and the wear resistance of the anti-aging rubber material are improved through the synergistic effect of the raw materials, so that the anti-aging rubber material has good comprehensive performance.
More preferably, the raw materials of the modified silicon-aluminum-carrying titanium dioxide comprise, by weight, 90-100 parts of a hydrochloric acid solution, 10-20 parts of absolute ethyl alcohol, 5-10 parts of tetrabutyl titanate, 0.3-0.5 part of aluminum chloride, 0.5-1.5 parts of a sodium silicate solution, 160 parts of water 140-containing solvent and 0.3-0.5 part of a coupling agent.
More preferably, the coupling agent is isopropyl triisostearoyl titanate.
More preferably, the concentration of the hydrochloric acid solution is 3-4mol/L, and the concentration of the sodium silicate solution is 4-6 mol/L.
By adopting the technical scheme, silicon-aluminum is loaded on the surface of titanium dioxide, the silicon-aluminum is coated on the surface of the titanium dioxide to form an inorganic protective layer, the silicon-aluminum-loaded titanium dioxide is formed, the conditions of inactivation and yellowing of the titanium dioxide under ultraviolet irradiation are reduced, the use stability and the service life of the titanium dioxide are improved, the silicon-aluminum-loaded titanium dioxide is further modified, the surface of the silicon-aluminum-loaded titanium dioxide is coated with a coupling agent to form an organic protective layer, the compatibility of the modified silicon-aluminum-loaded titanium dioxide and an anti-aging rubber material is improved, the dispersibility of the modified silicon-aluminum-loaded titanium dioxide is also improved, and the anti-aging property and the wear resistance of the anti-aging rubber material are improved.
More preferably, the modified silicon-aluminum-carrying titanium dioxide is prepared by the following method:
adding aluminum chloride into a hydrochloric acid solution, and uniformly mixing to obtain a mixed material A;
adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B;
heating the mixed material A to 40-60 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 20-30min, wherein the intermediate interval between two adjacent dropwise adding of the mixed material B is 5-10min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding of the mixed material B, and carrying out heat preservation treatment for 4-6h after the dropwise adding of the mixed material B is finished to obtain a mixed material C;
adding a sodium silicate solution into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the sodium silicate solution within 10-20min, carrying out ultrasonic treatment within the interval between two adjacent dropwise adding of the sodium silicate solution for 5-10min, carrying out heat preservation treatment for 30-40min after finishing dropwise adding of the sodium silicate solution, adjusting the pH value to be neutral, and filtering to obtain a precipitate D;
roasting the precipitate D at the temperature of 200-250 ℃, wherein the roasting time is 1-2h, the temperature is increased to 550-600 ℃, the roasting time is continued for 3-4h, and the temperature is reduced to obtain a semi-finished product E;
heating water to 60-70 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product E for multiple times, finishing the addition of the semi-finished product E within 40-50min, wherein the intermediate interval between the addition of the two adjacent semi-finished products E is 10-20min, carrying out ultrasonic treatment in the intermediate interval between the addition of the two adjacent semi-finished products E, carrying out heat preservation treatment for 50-60min after the addition of the semi-finished product E is finished, filtering, and drying to obtain the modified silicon-aluminum-carrying titanium dioxide.
By adopting the technical scheme, tetrabutyl titanate is dissolved in absolute ethyl alcohol to obtain a mixed material B, the uniformity of the mixed material B is improved, the mixed material B is added into the mixed material A in a dropwise manner for multiple times, tetrabutyl titanate generates crystals under an acidic condition, aluminum chloride enters the interior of titanium dioxide at the moment and forms an inorganic protective layer, then a sodium silicate solution is added, the sodium silicate solution generates precipitates under the acidic condition and coats the precipitates on the surface of the titanium dioxide to form the inorganic protective layer, then roasting treatment is adopted to form silicon-aluminum-loaded titanium dioxide, namely a semi-finished product E, a coupling agent is coated on the surface of the semi-finished product E to form an organic protective layer, and meanwhile, the modes of ultrasonic treatment and multiple dropwise addition are adopted, so that the dispersity of the modified silicon-aluminum-loaded titanium dioxide is improved, and the stability and the using effect of the modified silicon-aluminum-loaded titanium dioxide are improved.
More preferably, the raw materials of the maleic anhydride graft modified EVA comprise, by weight, 90-100 parts of EVA, 5-10 parts of absolute ethyl alcohol, 1-3 parts of an initiator and 1-4 parts of maleic anhydride.
More preferably, the initiator is dicumyl peroxide.
By adopting the technical scheme, maleic anhydride is grafted to EVA, and the maleic anhydride graft modified EVA plays a good medium role in SBS and PS, so that the compatibility and the bonding strength of the raw materials of the anti-aging rubber material are increased, and the tensile strength of the anti-aging rubber material is improved.
More preferably, the maleic anhydride graft modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material E;
heating EVA to 40-50 ℃ under the condition of continuous stirring, then adding the mixed material E into the EVA in a spraying mode, completing spraying of the mixed material E within 20-30min, standing for 1-2h after completing spraying of the mixed material E, continuing stirring, heating to 170-180 ℃, performing heat preservation for 10-20min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
By adopting the technical scheme, maleic anhydride is dissolved in absolute ethyl alcohol to obtain the mixed material E, then the mixed material E is added into EVA in a spraying mode, the mixed material E is coated on the surface of the EVA and enters the interior of the EVA, the contact area of the maleic anhydride and the EVA is increased, the grafting rate of the maleic anhydride grafted to the EVA is increased, and the using effect of the maleic anhydride grafted modified EVA is improved.
The second application object of the present application is achieved by the following technical scheme:
a preparation method of an anti-aging rubber material for soles specifically adopts the following steps:
under the conditions of continuous stirring and the temperature of 125-135 ℃, SBS, PS, maleic anhydride graft modified EVA and modified silicon-aluminum-loaded titanium dioxide are uniformly mixed, heat preservation treatment is carried out for 10-20min, then polypropylene fiber, petroleum resin and stearic acid are added, uniform mixing is carried out, the temperature is raised to 170-180 ℃, heat preservation treatment is carried out for 3-10min, and the temperature is reduced, so that the anti-aging rubber material is obtained.
By adopting the technical scheme, the preparation method has the advantages of simple preparation and convenience in control.
In summary, the present application has the following beneficial effects:
according to the anti-aging rubber material for the sole, the maleic anhydride grafted modified EVA and the modified silicon-aluminum-loaded titanium dioxide are added into the raw materials of the anti-aging rubber material, so that the anti-aging property and the wear resistance of the anti-aging rubber material are improved through the synergistic effect of the raw materials, and the anti-aging rubber material has good comprehensive performance.
And secondly, optimizing the raw material proportion and the preparation method of the modified silicon-aluminum-loaded titanium dioxide, coating an inorganic protective layer and an organic protective layer on the surface of the titanium dioxide, prolonging the service life of the modified silicon-aluminum-loaded titanium dioxide, increasing the compatibility and the dispersibility of the modified silicon-aluminum-loaded titanium dioxide and the anti-aging rubber material, and improving the anti-aging property and the wear resistance of the anti-aging rubber material. The method adopts the modes of dropping and ultrasonic treatment for multiple times, and increases the dispersibility, the preparation stability and the use effect of the modified silicon-aluminum-loaded titanium dioxide.
And thirdly, the raw material proportion and the preparation method of the maleic anhydride grafted modified EVA are optimized, and the maleic anhydride is grafted to the EVA, so that the compatibility and the bonding strength of the raw materials of the anti-aging rubber material are increased, and the tensile strength of the anti-aging rubber material is improved. The mixed material A is added into the EVA in a spraying mode, so that the grafting rate of maleic anhydride grafted to the EVA is increased, and the using effect of maleic anhydride grafted modified EVA is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
SBS is styrene-butadiene-styrene triblock thermoplastic elastomer F475B selected from Dongguan Yuetai plastics materials Co., Ltd; PS is polypropylene ethylene PG-33, and polypropylene ethylene PG-33 is selected from Beijing Yanshan Xin Tianze chemical Co., Ltd; the polypropylene fiber is selected from Shanghai polypropylene fiber company; the petroleum resin is selected from Shanghai Australian industry Co., Ltd; the coupling agent is isopropyl triisostearoyl titanate; the EVA is EVA3340, and the EVA3340 is selected from Dow; the initiator is dicumyl peroxide.
TABLE 1 examples the contents (unit: Kg) of the respective raw materials of the anti-aging rubber materials
| Raw materials | Example 1 | Example 2 | Example 3 |
| SBS | 37 | 45 | 54 |
| PS | 28 | 24 | 21 |
| Maleic anhydride graft modified EVA | 23 | 20.2 | 15.5 |
| Modified silica-alumina-loaded titanium dioxide | 5.5 | 6.8 | 8 |
| Polypropylene fiber | 1.5 | 1 | 0.5 |
| Petroleum resins | 6 | 5 | 4 |
| Stearic acid | 4 | 3 | 2 |
TABLE 2 examples the content (unit: Kg) of each raw material of the modified silicon-aluminum-supporting titanium dioxide
| Raw materials | Example 1 | Example 4 | Example 5 |
| Hydrochloric acid solution | 90 | 95 | 100 |
| Anhydrous ethanol | 10 | 15 | 20 |
| Tetrabutyl titanate | 5 | 8 | 10 |
| Aluminium chloride | 0.5 | 0.4 | 0.3 |
| Sodium silicate solution | 0.5 | 1 | 1.5 |
| Water (I) | 140 | 150 | 160 |
| Coupling agent | 0.3 | 0.4 | 0.5 |
TABLE 3 example the raw material contents (unit: Kg) of maleic anhydride graft-modified EVA
| Raw materials | Example 1 | Example 6 | Example 7 |
| EVA | 90 | 95 | 100 |
| Anhydrous ethanol | 5 | 8 | 10 |
| Initiator | 1 | 1.9 | 3 |
| Maleic anhydride | 1 | 3.1 | 4 |
Preparation example 1 of modified silica-alumina-supporting titanium dioxide
The modified silicon-aluminum-loaded titanium dioxide is prepared by the following method:
adding aluminum chloride into hydrochloric acid solution with the concentration of 3mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, heating the mixed material A to 60 ℃, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 20min, wherein the intermediate interval between two adjacent dropwise adding of the mixed material B is 5min, carrying out ultrasonic treatment in the intermediate interval between two adjacent dropwise adding of the mixed material B, and carrying out heat preservation treatment for 6h after finishing dropwise adding of the mixed material B to obtain the mixed material C.
And adding a sodium silicate solution with the concentration of 4mol/L into the mixed material C for multiple times in a dropwise adding mode, finishing dropwise adding the sodium silicate solution within 10min, keeping the middle interval between two adjacent dropwise adding of the sodium silicate solution for 5min, performing ultrasonic treatment within the middle interval between two adjacent dropwise adding of the sodium silicate solution, after finishing dropwise adding of the sodium silicate solution, performing heat preservation treatment for 40min, adjusting the pH value to be neutral, and filtering to obtain a precipitate D.
And roasting the precipitate D at the temperature of 200 ℃ for 2h, heating to 550 ℃, continuing roasting for 4h, and cooling to obtain a semi-finished product E.
Heating water to 70 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product E for multiple times, finishing the addition of the semi-finished product E within 40min, carrying out ultrasonic treatment within the intermediate interval between the addition of two adjacent semi-finished products E, carrying out heat preservation treatment for 60min after the addition of the semi-finished product E is finished, and filtering and drying to obtain the modified silicon-aluminum-loaded titanium dioxide.
Preparation example 2 of modified silica-alumina-supporting titanium dioxide
The modified silicon-aluminum-loaded titanium dioxide is prepared by the following method:
adding aluminum chloride and sodium silicate solution into hydrochloric acid solution with the concentration of 3.5mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, heating the mixed material A to 50 ℃, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 30min, wherein the intermediate interval between two adjacent dropwise adding of the mixed material B is 5min, carrying out ultrasonic treatment in the intermediate interval between two adjacent dropwise adding of the mixed material B, and carrying out heat preservation treatment for 5h after finishing dropwise adding of the mixed material B to obtain the mixed material C.
And adding a sodium silicate solution with the concentration of 5mol/L into the mixed material C for multiple times in a dropwise adding mode, finishing dropwise adding the sodium silicate solution within 20min, keeping the temperature for 35min after the dropwise adding of the sodium silicate solution is finished, adjusting the pH value to be neutral, and filtering to obtain a precipitate D, wherein the intermediate interval between two adjacent dropwise adding of the sodium silicate solution is 5 min.
And roasting the precipitate D at 230 ℃ for 1.5h, heating to 580 ℃, continuing roasting for 3.5h, and cooling to obtain a semi-finished product E.
Heating water to 65 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product E for multiple times, finishing the addition of the semi-finished product E within 50min, carrying out ultrasonic treatment within the intermediate interval between the addition of two adjacent semi-finished products E, after finishing the addition of the semi-finished product E, carrying out heat preservation treatment for 55min, filtering and drying to obtain the modified silicon-aluminum-loaded titanium dioxide.
Preparation example 3 of modified silica-alumina-supporting titanium dioxide
The modified silicon-aluminum-loaded titanium dioxide is prepared by the following method:
adding aluminum chloride and sodium silicate solution into hydrochloric acid solution with the concentration of 4mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, heating the mixed material A to 40 ℃, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 30min, wherein the intermediate interval between two adjacent dropwise adding of the mixed material B is 10min, carrying out ultrasonic treatment in the intermediate interval between two adjacent dropwise adding of the mixed material B, and carrying out heat preservation treatment for 4h after finishing dropwise adding of the mixed material B to obtain the mixed material C.
And adding a sodium silicate solution with the concentration of 6mol/L into the mixed material C for multiple times in a dropwise adding mode, finishing dropwise adding the sodium silicate solution within 20min, wherein the interval between two adjacent dropwise adding of the sodium silicate solution is 10min, carrying out ultrasonic treatment within the interval between two adjacent dropwise adding of the sodium silicate solution, after finishing dropwise adding of the sodium silicate solution, carrying out heat preservation treatment for 30min, adjusting the pH value to be neutral, and filtering to obtain a precipitate D.
And roasting the precipitate D at the temperature of 250 ℃ for 1h, heating to 600 ℃, continuing roasting for 3h, and cooling to obtain a semi-finished product E.
Heating water to 60 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product E for multiple times, finishing the addition of the semi-finished product E within 50min, carrying out ultrasonic treatment within the intermediate interval between the addition of two adjacent semi-finished products E, carrying out heat preservation treatment for 50min after the addition of the semi-finished product E is finished, and filtering and drying to obtain the modified silicon-aluminum-loaded titanium dioxide.
Preparation example 1 of maleic anhydride graft-modified EVA
The maleic anhydride grafted and modified EVA is prepared by the following method:
and adding an initiator and maleic anhydride into the absolute ethyl alcohol, and uniformly mixing to obtain a mixed material E.
Heating EVA to 40 ℃ under the condition of continuous stirring, then adding the mixed material E into the EVA in a spraying mode, spraying the mixed material E within 30min, standing for 2h after spraying the mixed material E, continuously stirring, heating to 170 ℃, carrying out heat preservation treatment for 20min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Preparation example 2 of maleic anhydride graft-modified EVA
The maleic anhydride grafted modified EVA is prepared by the following method:
and adding an initiator and maleic anhydride into the absolute ethyl alcohol, and uniformly mixing to obtain a mixed material E.
Heating EVA to 45 ℃ under the condition of continuous stirring, then adding the mixed material E into the EVA in a spraying mode, spraying the mixed material E within 25min, standing for 1.5h after spraying the mixed material E, continuously stirring, heating to 175 ℃, carrying out heat preservation treatment for 15min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Preparation example 3 of maleic anhydride graft-modified EVA
The maleic anhydride grafted modified EVA is prepared by the following method:
and adding an initiator and maleic anhydride into the absolute ethyl alcohol, and uniformly mixing to obtain a mixed material E.
Heating EVA to 50 ℃ under the condition of continuous stirring, then adding the mixed material E into the EVA in a spraying mode, spraying the mixed material E within 20min, standing for 1h after spraying the mixed material E, continuously stirring, heating to 180 ℃, carrying out heat preservation treatment for 10min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Example 1
An anti-aging rubber material for soles, which comprises the raw materials in the proportion shown in table 1;
wherein, the modified silicon-aluminum-loaded titanium dioxide adopts preparation example 1 of the modified silicon-aluminum-loaded titanium dioxide, and the raw material ratio of the modified silicon-aluminum-loaded titanium dioxide is shown in table 2;
maleic anhydride graft-modified EVA preparation example 1 was prepared using maleic anhydride graft-modified EVA, and the raw material ratios of the maleic anhydride graft-modified EVA are shown in Table 3.
A preparation method of an anti-aging rubber material for soles specifically adopts the following steps:
under the conditions of continuously stirring and 125 ℃, SBS, PS, maleic anhydride graft modified EVA and modified silicon-aluminum-loaded titanium dioxide are uniformly mixed, heat preservation treatment is carried out for 20min, then polypropylene fiber, petroleum resin and stearic acid are added, uniform mixing is carried out, the temperature is raised to 170 ℃, heat preservation treatment is carried out for 10min, and the temperature is reduced, so that the anti-aging rubber material is obtained.
Example 2
An anti-aging rubber material for soles, which comprises the raw materials in the proportion shown in table 1;
wherein, the modified silicon-aluminum-loaded titanium dioxide adopts preparation example 2 of the modified silicon-aluminum-loaded titanium dioxide, and the raw material ratio of the modified silicon-aluminum-loaded titanium dioxide is shown in Table 2;
maleic anhydride graft-modified EVA preparation example 2 was used, and the raw material ratio of maleic anhydride graft-modified EVA is shown in Table 3.
A preparation method of an anti-aging rubber material for soles specifically adopts the following steps:
under the conditions of continuously stirring and 125 ℃, SBS, PS, maleic anhydride graft modified EVA and modified silicon-aluminum-loaded titanium dioxide are uniformly mixed, heat preservation treatment is carried out for 20min, then polypropylene fiber, petroleum resin and stearic acid are added, uniform mixing is carried out, the temperature is raised to 170 ℃, heat preservation treatment is carried out for 10min, and the temperature is reduced, so that the anti-aging rubber material is obtained.
Example 3
An anti-aging rubber material for soles, which comprises the raw materials in the proportion shown in table 1;
wherein, the modified silicon-aluminum-loaded titanium dioxide adopts preparation example 3 of the modified silicon-aluminum-loaded titanium dioxide, and the raw material ratio of the modified silicon-aluminum-loaded titanium dioxide is shown in table 2;
maleic anhydride graft-modified EVA preparation 3 was prepared using maleic anhydride graft-modified EVA, and the raw material ratios of the maleic anhydride graft-modified EVA are shown in Table 3.
A preparation method of an anti-aging rubber material for soles specifically adopts the following steps:
under the conditions of continuously stirring and 125 ℃, SBS, PS, maleic anhydride graft modified EVA and modified silicon-aluminum-loaded titanium dioxide are uniformly mixed, heat preservation treatment is carried out for 20min, then polypropylene fiber, petroleum resin and stearic acid are added, uniform mixing is carried out, the temperature is raised to 170 ℃, heat preservation treatment is carried out for 10min, and the temperature is reduced, so that the anti-aging rubber material is obtained.
Example 4
The present example differs from example 2 in the raw material ratio of the modified silicon-loaded aluminum titanium dioxide, which is shown in table 2.
Example 5
The present example differs from example 2 in the raw material ratio of the modified silicon-loaded aluminum titanium dioxide, which is shown in table 2.
Example 6
The present example differs from example 4 in the raw material composition of maleic anhydride graft-modified EVA, which is shown in Table 3.
Example 7
The present example differs from example 4 in the raw material composition of maleic anhydride graft-modified EVA, which is shown in Table 3.
Comparative example 1
An anti-aging rubber material for shoe soles, which is different from example 6 in that no modified silicon-aluminum-carrying titanium dioxide is added to the raw material of the anti-aging rubber material.
Comparative example 2
An anti-aging rubber material for shoe soles, which is different from example 6 in that the modified silica-alumina-bearing titanium dioxide is replaced with the same amount of titanium dioxide in the raw material of the anti-aging rubber material.
The titanium dioxide is prepared by the following method:
and (3) taking a hydrochloric acid solution with the concentration of 3.5mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, the mixed material A is heated to 50 ℃, then the mixed material B is added into the mixed material A in a dropwise adding mode for multiple times, the dropwise adding of the mixed material B is completed within 30min, the intermediate interval between two adjacent dropwise adding of the mixed material B is 5min, ultrasonic treatment is carried out in the intermediate interval between two adjacent dropwise adding of the mixed material B, after the dropwise adding of the mixed material B is completed, heat preservation is carried out for 5h, the PH value is adjusted to be neutral, and the precipitate C is obtained through filtration.
And roasting the precipitate C at 230 ℃ for 1.5h, heating to 580 ℃, continuing to roast for 3.5h, and cooling to obtain the titanium dioxide.
Wherein the weight ratio of the hydrochloric acid solution to the absolute ethyl alcohol to the tetrabutyl titanate is 95:15: 8.
Comparative example 3
An anti-aging rubber material for shoe soles, which is different from example 6 in that in the raw material of the anti-aging rubber material, an equivalent amount of silica-alumina-bearing titanium dioxide is substituted for the modified silica-alumina-bearing titanium dioxide.
The silicon-aluminum-loaded titanium dioxide is prepared by the following method:
adding aluminum chloride into hydrochloric acid solution with the concentration of 3.5mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, heating the mixed material A to 50 ℃, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 30min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 5min, carrying out ultrasonic treatment in the intermediate interval between two adjacent dropwise adding processes of the mixed material B, and obtaining the mixed material C after the dropwise adding processes of the mixed material B are finished.
And adding a sodium silicate solution with the concentration of 5mol/L into the mixed material C for multiple times in a dropwise adding mode, finishing dropwise adding the sodium silicate solution within 20min, keeping the temperature for 35min after the dropwise adding of the sodium silicate solution is finished, adjusting the pH value to be neutral, and filtering to obtain a precipitate D, wherein the intermediate interval between two adjacent dropwise adding of the sodium silicate solution is 5 min.
And roasting the precipitate D at 230 ℃ for 1.5h, heating to 580 ℃, continuing roasting for 3.5h, and cooling to obtain the silicon-aluminum-loaded titanium dioxide.
Wherein the weight ratio of the hydrochloric acid solution to the absolute ethyl alcohol to the tetrabutyl titanate to the aluminum chloride to the sodium silicate solution is 95:15:8:0.4: 1.
Comparative example 4
An anti-aging rubber material for shoe soles, which is different from example 6 in that modified silica-alumina-carrying titania is replaced with an equal amount of modified titania in the raw material of the anti-aging rubber material.
The modified titanium dioxide is prepared by the following method:
and (3) taking a hydrochloric acid solution with the concentration of 3.5mol/L, and uniformly mixing to obtain a mixed material A.
And adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B.
Under the condition of continuous stirring, the mixed material A is heated to 50 ℃, then the mixed material B is added into the mixed material A in a dropwise adding mode for multiple times, the dropwise adding of the mixed material B is completed within 30min, the intermediate interval between two adjacent dropwise adding of the mixed material B is 5min, ultrasonic treatment is carried out in the intermediate interval between two adjacent dropwise adding of the mixed material B, after the dropwise adding of the mixed material B is completed, heat preservation is carried out for 5h, the PH value is adjusted to be neutral, and the precipitate C is obtained through filtration.
And roasting the precipitate C at 230 ℃ for 1.5h, heating to 580 ℃, continuing roasting for 3.5h, and cooling to obtain a semi-finished product D.
Heating water to 65 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product D for multiple times, finishing the addition of the semi-finished product D within 50min, carrying out ultrasonic treatment within the intermediate interval between the addition of two adjacent semi-finished products D, carrying out heat preservation treatment for 55min after the addition of the semi-finished product D is finished, filtering and drying to obtain the modified titanium dioxide.
Wherein the weight ratio of the hydrochloric acid solution to the absolute ethyl alcohol to the tetrabutyl titanate to the water to the coupling agent is 95:15:8:150: 0.4.
Comparative example 5
An anti-aging rubber material for shoe soles, which is different from example 6 in that maleic anhydride graft-modified EVA was not added to the raw material of the anti-aging rubber material.
Comparative example 6
An anti-aging rubber material for shoe soles, which is different from example 6 in that in the raw material of the anti-aging rubber material, maleic anhydride graft-modified EVA was replaced with an equal amount of EVA.
Comparative example 7
An anti-aging rubber material for soles is characterized in that modified silicon-aluminum-loaded titanium dioxide and maleic anhydride graft modified EVA are not added in raw materials of the anti-aging rubber material.
Test pieces were prepared for the anti-aging rubber materials for shoe soles of examples 1 to 7 and comparative examples 1 to 7, and the following property tests were carried out, and the test results are shown in Table 4.
Wherein, the tensile strength is detected according to GB/T528-2009 determination of vulcanized rubber or thermoplastic rubber-tensile stress strain performance;
GB/T689-2014 & lt abrasion resistance measurement of vulcanized rubber (using an Akron abrasion tester) carries out the detection of abrasion volume;
GB/T16585-1996 test method for the Artificial weathering (fluorescent ultraviolet lamp) of vulcanized rubber, the ageing resistance of which is determined and expressed as the rate of change of tensile strength.
TABLE 4 test results
| Detecting items | Tensile Strength/(MPa) | Tensile Strength Change Rate/(%) | Abrasion volume/(cm)3/1.61km) |
| Example 1 | 18.8 | 79.5 | 0.357 |
| Example 2 | 19.3 | 80.6 | 0.346 |
| Example 3 | 18.5 | 80.4 | 0.361 |
| Example 4 | 19.9 | 82.6 | 0.315 |
| Example 5 | 19.6 | 81.5 | 0.324 |
| Example 6 | 21.3 | 82.5 | 0.316 |
| Example 7 | 20.6 | 82.5 | 0.317 |
| Comparative example 1 | 20.1 | 72.3 | 0.564 |
| Comparative example 2 | 17.6 | 76.5 | 0.452 |
| Comparative example 3 | 17.8 | 78.9 | 0.431 |
| Comparative example 4 | 20.6 | 75.9 | 0.442 |
| Comparative example 5 | 18.5 | 82.5 | 0.319 |
| Comparative example 6 | 18.3 | 82.4 | 0.318 |
| Comparative example 7 | 18.1 | 72.3 | 0.546 |
As can be seen from Table 4, the anti-aging rubber material has good tensile strength and tensile strength change rate, the maximum tensile strength reaches 21.3MPa, the maximum tensile strength change rate reaches 82.6%, and the anti-aging rubber material also has low abrasion volume, and the minimum abrasion volume is 0.315cm3/1.61km,。
Comparing example 6 with comparative examples 1 to 4, it can be seen that the addition of the modified silica-alumina-loaded titanium dioxide to the raw material of the anti-aging rubber material can significantly reduce the wear-resistant volume of the anti-aging rubber material and significantly improve the tensile strength change rate of the anti-aging rubber material, mainly because the modified silica-alumina-loaded titanium dioxide coats the surface of the titanium dioxide with the inorganic protective layer and the organic protective layer, increasing the service life of the modified silica-alumina-loaded titanium dioxide, and also increasing the compatibility and dispersibility of the modified silica-alumina-loaded titanium dioxide and the anti-aging rubber material, and increasing the wear resistance and anti-aging property of the anti-aging rubber material.
Comparing the example 6 with the comparative examples 5 to 6, it can be seen that the addition of maleic anhydride graft modified EVA to the raw material of the anti-aging rubber material can significantly improve the tensile strength and shore hardness of the anti-aging rubber material, which is probably because the molecular weight of PS is much larger than that of the PS block in SBS, making it difficult for PS to enter SBS and form three phases, and destroying the structure of SBS, and the addition of maleic anhydride graft modified EVA to SBS and PS plays a good role as a medium in SBS and PS, increasing the compatibility and bonding strength of SBS and PS, and improving the tensile strength of the anti-aging rubber material.
Comparing the example 6 with the comparative examples 1 and 7, it can be seen that the addition of the maleic anhydride graft modified EVA and the modified silicon-aluminum-loaded titanium dioxide to the raw materials of the anti-aging rubber material can significantly improve the tensile strength and the change rate of the tensile strength of the anti-aging rubber material and significantly reduce the wear-resistant volume of the anti-aging rubber material, which is mainly due to the influence of the synergistic effect between the maleic anhydride graft modified EVA and the modified silicon-aluminum-loaded titanium dioxide.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (3)
1. An anti-aging rubber material for soles is characterized in that: the raw materials of the anti-aging rubber material comprise, by weight, 37-54 parts of SBS, 21-28 parts of PS, 15.5-23 parts of maleic anhydride graft modified EVA, 5.5-8 parts of modified silicon-aluminum-carrying titanium dioxide, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 2-4 parts of stearic acid;
the raw materials of the modified silicon-aluminum-carrying titanium dioxide comprise, by weight, 90-100 parts of hydrochloric acid solution, 10-20 parts of absolute ethyl alcohol, 5-10 parts of tetrabutyl titanate, 0.3-0.5 part of aluminum chloride, 0.5-1.5 parts of sodium silicate solution, 160 parts of water 140-doped materials and 0.3-0.5 part of coupling agent; the coupling agent is isopropyl triisostearoyl titanate; the concentration of the hydrochloric acid solution is 3-4mol/L, and the concentration of the sodium silicate solution is 4-6 mol/L;
the modified silicon-aluminum-loaded titanium dioxide is prepared by the following method:
adding aluminum chloride into a hydrochloric acid solution, and uniformly mixing to obtain a mixed material A; adding tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material B; heating the mixed material A to 40-60 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material A in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 20-30min, wherein the intermediate interval between two adjacent dropwise adding of the mixed material B is 5-10min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding of the mixed material B, and carrying out heat preservation treatment for 4-6h after the dropwise adding of the mixed material B is finished to obtain a mixed material C; adding a sodium silicate solution into the mixed material C for multiple times in a dripping mode, finishing dripping the sodium silicate solution within 10-20min, carrying out ultrasonic treatment within the interval between two adjacent times of dripping the sodium silicate solution for 5-10min, carrying out heat preservation treatment for 30-40min after finishing dripping the sodium silicate solution, adjusting p H value to be neutral, and filtering to obtain a precipitate D; roasting the precipitate D at the temperature of 200-250 ℃, wherein the roasting time is 1-2h, the temperature is increased to 550-600 ℃, the roasting time is continued for 3-4h, and the temperature is reduced to obtain a semi-finished product E; heating water to 60-70 ℃, adding a coupling agent into the water, uniformly mixing, then adding the semi-finished product E for multiple times, finishing the addition of the semi-finished product E within 40-50min, wherein the intermediate interval between the addition of the two adjacent semi-finished products E is 10-20min, carrying out ultrasonic treatment in the intermediate interval between the addition of the two adjacent semi-finished products E, carrying out heat preservation treatment for 50-60min after the addition of the semi-finished product E is finished, filtering and drying to obtain the modified silicon-aluminum-carrying titanium dioxide;
the raw materials of the maleic anhydride graft modification EVA comprise, by weight, 90-100 parts of EVA, 5-10 parts of absolute ethyl alcohol, 1-3 parts of an initiator and 1-4 parts of maleic anhydride;
the maleic anhydride graft modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material E; heating EVA to 40-50 ℃ under the condition of continuous stirring, then adding the mixed material E into the EVA in a spraying mode, completing spraying of the mixed material E within 20-30min, standing for 1-2h after completing spraying of the mixed material E, continuing stirring, heating to 170-180 ℃, performing heat preservation for 10-20min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
2. The anti-aging rubber material for the shoe sole as claimed in claim 1, wherein: the initiator is dicumyl peroxide.
3. A method for preparing an anti-aging rubber material for shoe soles according to any one of claims 1 to 2, characterized in that: the method specifically comprises the following steps:
under the conditions of continuous stirring and the temperature of 125-135 ℃, SBS, PS, maleic anhydride graft modified EVA and modified silicon-aluminum-loaded titanium dioxide are uniformly mixed, heat preservation treatment is carried out for 10-20min, then polypropylene fiber, petroleum resin and stearic acid are added, uniform mixing is carried out, the temperature is raised to 170-180 ℃, heat preservation treatment is carried out for 3-10min, and the temperature is reduced, so that the anti-aging rubber material is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010718808.9A CN111995837B (en) | 2020-07-23 | 2020-07-23 | Anti-aging rubber material for soles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010718808.9A CN111995837B (en) | 2020-07-23 | 2020-07-23 | Anti-aging rubber material for soles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111995837A CN111995837A (en) | 2020-11-27 |
| CN111995837B true CN111995837B (en) | 2022-06-17 |
Family
ID=73466523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010718808.9A Active CN111995837B (en) | 2020-07-23 | 2020-07-23 | Anti-aging rubber material for soles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111995837B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292455B (en) * | 2021-12-31 | 2023-04-28 | 浙江恒诚鞋业有限公司 | Rubber sheet for anti-skid shoes and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454928A (en) * | 2003-05-14 | 2003-11-12 | 阳范文 | Ultrahigh wear-resistant thermoplastic elastomer material for shoe-sole |
| CN104448671A (en) * | 2014-12-19 | 2015-03-25 | 东莞市国立科技有限公司 | Low-cost and high-wear-resistance TPR modified material and preparation method thereof |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
| CN107629387A (en) * | 2017-04-14 | 2018-01-26 | 莆田市三迪鞋服有限公司 | A kind of improved TPR ultra-light sole materials |
| CN109134899A (en) * | 2018-09-20 | 2019-01-04 | 何治伟 | A kind of preparation method of acid-alkali-corrosive-resisting wear-resisting type aluminum-plastic composite membrane |
| CN110643133A (en) * | 2019-10-25 | 2020-01-03 | 温州市胜帆鞋材有限公司 | TPR sole and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2045287A4 (en) * | 2006-07-26 | 2010-03-03 | Ube Industries | Rubber composition for shoe sole and rubber foam composition |
-
2020
- 2020-07-23 CN CN202010718808.9A patent/CN111995837B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454928A (en) * | 2003-05-14 | 2003-11-12 | 阳范文 | Ultrahigh wear-resistant thermoplastic elastomer material for shoe-sole |
| CN104448671A (en) * | 2014-12-19 | 2015-03-25 | 东莞市国立科技有限公司 | Low-cost and high-wear-resistance TPR modified material and preparation method thereof |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
| CN107629387A (en) * | 2017-04-14 | 2018-01-26 | 莆田市三迪鞋服有限公司 | A kind of improved TPR ultra-light sole materials |
| CN109134899A (en) * | 2018-09-20 | 2019-01-04 | 何治伟 | A kind of preparation method of acid-alkali-corrosive-resisting wear-resisting type aluminum-plastic composite membrane |
| CN110643133A (en) * | 2019-10-25 | 2020-01-03 | 温州市胜帆鞋材有限公司 | TPR sole and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111995837A (en) | 2020-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995837B (en) | Anti-aging rubber material for soles and preparation method thereof | |
| CN112029222B (en) | Wear-resistant rubber material for soles and preparation method and application thereof | |
| CN104927215A (en) | Wear-resistant and flame-retardant plastic track | |
| CN105155293A (en) | Anti-microbial synthetic leather and preparation method thereof | |
| TW201716523A (en) | Topcoat composition, method of coating substrates with the same, and substrate | |
| JP2012514101A (en) | High transparency blended ionomer composition and articles containing the same | |
| CN113696573B (en) | Toughened home decoration base film and preparation method thereof | |
| CN108219632A (en) | The grit powder coating and its processing method prepared by modified polyester resin | |
| CN109208349A (en) | A kind of manufacture craft of nylon uvioresistant fabric | |
| CN112920517A (en) | Electrolyte-resistant ethylene propylene diene monomer rubber and preparation method thereof | |
| CN106272804B (en) | Plastic film enhancing flexible decoration veneer and preparation method thereof that a kind of no aldehyde is water-fast | |
| CN102276906B (en) | Modified ethane-vinyl alcohol copolymer composite material and preparation technology thereof | |
| CN112175287A (en) | Reinforced and toughened polypropylene composite material for automobile steering wheel | |
| CN111691206A (en) | Cloth dye with good antibacterial effect | |
| CN105482747B (en) | A kind of high-strength impact-resistant acrylate adhesive and preparation method thereof | |
| CN110330240A (en) | A kind of composite fireproof glass colorless transparent gel material and preparation method thereof | |
| CN115838576B (en) | Aldehyde-free adhesive and application thereof in preparation of P2-P12-grade particle board | |
| CN109206999A (en) | A kind of timber Diamond Search coating | |
| CN114213723B (en) | Wear-resistant high-strength shoe material and preparation method thereof | |
| CN112175251B (en) | Novel nanocomposite vamp and preparation method thereof | |
| CN109825246B (en) | Natural fermentation adhesive and preparation method thereof | |
| CN113338078A (en) | Food fresh-keeping card film-coating method | |
| CN112265098A (en) | Preparation method of chemical color-changing composite floor | |
| CN106397815A (en) | Method for improving adhesive power of ink in plastic prints | |
| CN107177141B (en) | Method for modifying surface of polyvinyl chloride resin by propylene-vinyl chloride copolymer emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |