CN112225952A - Sandal sole and production method thereof - Google Patents
Sandal sole and production method thereof Download PDFInfo
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- CN112225952A CN112225952A CN202011016303.4A CN202011016303A CN112225952A CN 112225952 A CN112225952 A CN 112225952A CN 202011016303 A CN202011016303 A CN 202011016303A CN 112225952 A CN112225952 A CN 112225952A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000007799 cork Substances 0.000 claims abstract description 82
- 239000000843 powder Substances 0.000 claims abstract description 76
- 238000002156 mixing Methods 0.000 claims abstract description 55
- 229920001971 elastomer Polymers 0.000 claims abstract description 46
- 239000005060 rubber Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 27
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 27
- 229920001194 natural rubber Polymers 0.000 claims abstract description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 17
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 238000009998 heat setting Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 240000001548 Camellia japonica Species 0.000 claims description 34
- 235000018597 common camellia Nutrition 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000004636 vulcanized rubber Substances 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 7
- 235000013312 flour Nutrition 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 235000006467 Camellia japonica Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229930013930 alkaloid Natural products 0.000 description 2
- -1 bromobutyl Chemical group 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
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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
- C08L7/00—Compositions of natural rubber
-
- 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
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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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- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- 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)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The application relates to the field of soles, and particularly discloses a sandal sole and a production method thereof. The sole is prepared from the following raw materials in parts by weight: 70-80 parts of natural rubber; 20-30 parts of brominated butyl rubber; 6-8 parts of a compatilizer; 1.5-3 parts of sulfur; 1-2 parts of an accelerator; 2-3 parts of stearic acid; 4-5 parts of zinc oxide; 20-30 parts of a filler; 0.2-0.5 part of anti-aging agent; 50-80 parts of cork powder. The production method of the sole comprises the following steps: s1 blending; s2 mixing: uniformly mixing the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder, heating to 70-80 ℃, and mixing for 20-30min to obtain a rubber material; s3, vulcanization molding; and S4 heat setting. The sole of this application has light, the good, advantage that tear strength is high of resilience.
Description
Technical Field
The application relates to the field of soles, in particular to a sandal sole and a production method thereof.
Background
Sandals are open type footwear, i.e. the sole is fixed to the foot by straps, studs. Because most of the foot area of the sandal can be exposed when the sandal is worn, the sandal is convenient to ventilate and dissipate heat, and is very suitable for being worn in summer. Sandals are classified into flat shoes, wedge shoes and high-heeled shoes according to the type of sole structure, wherein the flat shoes are most comfortable to wear.
Common sandal sole materials are straw rope, cork, EVA, PVC, PU, rubber, etc., wherein the rubber sole has excellent resilience, wear resistance and skid resistance but is heavy, while the cork sole has the advantages of lightness, softness and comfort. In order to combine the advantages of cork and rubber, the cork and rubber can be compounded to form the sole, namely the cork and rubber sole. The cork rubber is made up by using rubber, cork granules and additive according to a certain proportion through the processes of plastication, mixing and vulcanization moulding. The microstructure of cork is composed of cells filled with air, and is equivalent to the incorporation of a plurality of natural micro-bubbles in rubber, thereby being beneficial to improving the resilience of the sole.
However, the compatibility of the cork particles with natural rubber is not good, and if the cork particles are too high in filling amount and too small in particle size, the tear resistance of the sole is liable to be greatly reduced.
Disclosure of Invention
In order to improve compatibility of cork powder and natural rubber, the present application provides a sandal sole.
In a first aspect, the application provides a sandal sole, which adopts the following technical scheme:
a sandal sole is prepared from the following raw materials in parts by weight:
70-80 parts of natural rubber;
20-30 parts of brominated butyl rubber;
6-8 parts of a compatilizer;
1.5-3 parts of sulfur;
1-2 parts of an accelerator;
2-3 parts of stearic acid;
4-5 parts of zinc oxide;
20-30 parts of a filler;
0.2-0.5 part of anti-aging agent;
50-80 parts of cork powder.
By adopting the technical scheme, the rubber base material adopts nonpolar natural rubber and polar brominated butyl rubber to be blended with the help of the compatilizer. The brominated butyl rubber has a main chain basically saturated by the butyl rubber and has strong polar bromine atoms, so that the brominated butyl rubber has excellent ageing resistance and weather resistance, but poor resilience. On one hand, the interaction force between the chains is improved, the viscosity and the wear resistance of the sole material are ensured, on the other hand, the internal resistance of the molecular chains is increased, the amplitude attenuation is fast, and the ground-grasping force of the sole is strong.
More importantly, the compatibility between the rubber base material and the cork powder is improved after blending, so that the filling amount of the cork powder can be increased to more than 50wt%, and the particle size can be larger than 100 meshes. Although the resilience performance of the rubber base material is reduced after blending, the resilience performance of the sole is improved to make up for the loss of the resilience performance caused by blending because a large number of natural micro-bubbles are formed in the rubber due to the increase of the filling amount of the cork powder. The increased filling amount of the light cork powder is also beneficial to reducing the overall density of the sole and ensuring light weight, so that the wearing comfort is improved, and the excellent tear resistance can be ensured.
Further, the preparation process of the compatilizer is as follows: heating 20-30 parts of chlorinated polyethylene to 170-180 ℃ until the chlorinated polyethylene is completely melted, adding 4-6 parts of maleic anhydride and 0.2-0.4 part of dibenzoyl peroxide, reacting for 15-20min, cooling and discharging to obtain the compatilizer.
By adopting the technical scheme, on one hand, the maleic anhydride grafted chlorinated polyethylene is beneficial to promoting the compatibility of the natural rubber and the brominated butyl rubber, and on the other hand, more active groups are introduced to form chemical bonding with the cork, so that the rebound resilience and the tear resistance of the rubber are improved.
Further, the cork powder is modified by the following modification process:
step one, uniformly mixing 10-15 parts of 2, 2-dimethylolpropionic acid and 40-50 parts of PPG-2000, heating to 140 ℃, continuously stirring until the 2, 2-dimethylolpropionic acid is dissolved, cooling to 60-70 ℃, then adding 15-20 parts of diphenylmethane diisocyanate, and continuously stirring for 2-3 hours to obtain a prepolymer;
step two, uniformly mixing 2-4 parts of triethylamine, 6-10 parts of aminopropyltriethoxysilane, 30-40 parts of the prepolymer and 50-60 parts of water, and shearing and emulsifying for 20-30min to obtain a modified emulsion;
and thirdly, immersing the cork powder into the modified emulsion, heating to 50-60 ℃, taking out after 3-5h, and drying to obtain the modified cork powder.
By adopting the technical scheme, the cork powder is subjected to soaking modification by the modified emulsion, so that on one hand, the waterproof performance of the cork powder is enhanced, and on the other hand, the bonding performance of the cork powder and natural rubber/brominated butyl rubber is improved.
Further, the addition amount of the cork powder is 70-80 parts.
By adopting the technical scheme, if the modified cork powder is adopted, the addition amount can exceed 70wt% due to better compatibility with natural rubber/brominated butyl rubber, and the effect is fully exerted.
Further, the particle size of the cork powder is 500 meshes.
By adopting the technical scheme, if the modified cork powder is adopted, the particle size can reach 500 meshes due to better compatibility with natural rubber/brominated butyl rubber, the modified cork powder is uniformly dispersed, and the anti-tearing performance of the sole is not easily affected.
Further, the sole also comprises 3-5 parts of camellia extract, and the preparation process of the camellia extract is as follows:
firstly, picking camellia leaves, cutting up the camellia leaves, drying and grinding the camellia leaves to obtain leaf powder;
and secondly, soaking the leaf powder into ethanol, heating to 60-70 ℃, keeping for 2-3h, and finally filtering and evaporating to remove the ethanol to obtain the camellia extract.
By adopting the technical scheme, alkaloid, polysaccharide and the like in the camellia extract have specific properties and high activity, and can be combined with modified cork powder and natural rubber to promote the compatibility of the modified cork powder and the natural rubber.
Further, the filler is a mixture of white carbon black and light calcium carbonate.
By adopting the technical scheme, the white carbon black mainly plays a role in reinforcement, and the mechanical properties such as wear resistance, tear strength, tensile strength and the like of the rubber are improved; the light calcium carbonate mainly plays a role in filling, improves the volume of rubber, reduces the cost of rubber products, improves the processing performance, and does not obviously influence the performance of the rubber products.
In a second aspect, the application provides a method for producing sandal soles, which adopts the following technical scheme:
a production method of sandal soles comprises the following steps:
s1 blending: weighing and mixing natural rubber, brominated butyl rubber and a compatilizer according to the required weight parts of the formula, heating to 50-60 ℃, and mixing for 5-10min to obtain rubber compound;
s2 mixing: uniformly mixing the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder, heating to 70-80 ℃, and mixing for 20-30min to obtain a rubber material;
s3 vulcanization molding: putting the rubber material into a vulcanization forming mold, heating to 160-180 ℃, and vulcanizing for 15-30min to obtain vulcanized rubber;
s4 heat setting: and (3) putting the vulcanized rubber into a heat setting mold, heating to 140-160 ℃, and keeping for 15-20min to obtain the sandal sole.
Further, 3-5 parts of camellia extract is added in the step of S2 mixing.
In summary, the present application has the following beneficial effects:
1. according to the shoe sole, the rubber base material formed by blending natural rubber and brominated butyl rubber is adopted, and the cork powder is subjected to soaking modification by using the aqueous polyurethane emulsion, so that the compatibility of the cork powder and the rubber base material is improved, and the shoe sole can still keep excellent tear resistance under the condition of high filling amount of the cork powder;
2. the camellia extract is preferably adopted in the application, and because alkaloids, polysaccharides and the like in the camellia extract have specific properties and high activity, the camellia extract can be combined with modified cork powder and natural rubber to promote the compatibility of the modified cork powder and the natural rubber.
Drawings
Fig. 1 is a flow chart of a method provided herein.
Detailed Description
The present application will now be described in further detail with reference to the following figures and examples, in which: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples are available from ordinary commercial sources unless otherwise specified.
The embodiment of the application adopts the following raw materials:
brominated butyl rubber was purchased from exxonmobil; the accelerator is a mixture of an accelerator TMTD and an accelerator D in equal mass ratio; the anti-aging agent is anti-aging agent RD; the cork powder is purchased from cork powder factories in east tai city, and pure natural cork of portugal is selected as the material; chlorinated polyethylene, designation 361, purchased from Dandongde chemical Co., Liaoning, Ltd; the Camellia japonica Linne leaf is leaf of Camellia japonica Linne (with scientific name: Camellia japonica L.).
Example 1:
a sandal sole is prepared from the following raw materials in parts by weight:
70 parts of natural rubber;
30 parts of brominated butyl rubber;
6 parts of a compatilizer;
1.5 parts of sulfur;
1 part of an accelerator;
2 parts of stearic acid;
4 parts of zinc oxide;
20 parts of filler, wherein the filler is a mixture of white carbon black and light calcium carbonate in a mass ratio of 2: 1;
0.2 part of anti-aging agent;
50 parts of cork powder with the particle size of 100 meshes.
The preparation process of the compatilizer is as follows: heating 20 parts of chlorinated polyethylene to 170 ℃ until the chlorinated polyethylene is completely melted, adding 4 parts of maleic anhydride and 0.2 part of dibenzoyl peroxide, reacting for 15min, cooling and discharging to obtain the compatilizer.
A production method of sandal soles comprises the following steps:
s1 blending: weighing and mixing the natural rubber, the brominated butyl rubber and the compatilizer according to the parts by weight required by the formula, heating to 50 ℃, and mixing for 5min to obtain mixed rubber;
s2 mixing: putting the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder into a rubber mixing mill, uniformly mixing, heating to 70 ℃, and mixing for 20min to obtain a rubber material;
s3 vulcanization molding: putting the rubber material into a vulcanization forming die, heating to 160 ℃, and vulcanizing for 15min to obtain vulcanized rubber;
s4 heat setting: and (3) putting the vulcanized rubber into a heat setting mold, heating to 140 ℃, and keeping for 15min to obtain the sandal sole.
Example 2:
a sandal sole is prepared from the following raw materials in parts by weight:
80 parts of natural rubber;
20 parts of brominated butyl rubber;
8 parts of a compatilizer;
3 parts of sulfur;
2 parts of an accelerator;
3 parts of stearic acid;
5 parts of zinc oxide;
30 parts of filler, wherein the filler is a mixture of white carbon black and light calcium carbonate in a mass ratio of 2: 1;
0.5 part of anti-aging agent;
60 parts of cork powder with the particle size of 100 meshes.
The preparation process of the compatilizer is as follows: heating 30 parts of chlorinated polyethylene to 180 ℃ until the chlorinated polyethylene is completely melted, adding 6 parts of maleic anhydride and 0.4 part of dibenzoyl peroxide, reacting for 20min, cooling and discharging to obtain the compatilizer.
A production method of sandal soles comprises the following steps:
s1 blending: weighing and mixing the natural rubber, the brominated butyl rubber and the compatilizer according to the weight parts required by the formula, heating to 60 ℃, and mixing for 10min to obtain mixed rubber;
s2 mixing: putting the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder into a rubber mixing mill, uniformly mixing, heating to 80 ℃, and mixing for 30min to obtain a rubber material;
s3 vulcanization molding: putting the rubber material into a vulcanization forming die, heating to 180 ℃, and vulcanizing for 30min to obtain vulcanized rubber;
s4 heat setting: and (3) putting the vulcanized rubber into a heat setting mold, heating to 160 ℃, and keeping for 20min to obtain the sandal sole.
Example 3:
a sandal sole is prepared from the following raw materials in parts by weight:
75 parts of natural rubber;
25 parts of brominated butyl rubber;
7 parts of a compatilizer;
2 parts of sulfur;
1.5 parts of an accelerator;
2.5 parts of stearic acid;
4.5 parts of zinc oxide;
25 parts of filler, wherein the filler is a mixture of white carbon black and light calcium carbonate in a mass ratio of 2: 1;
0.4 part of anti-aging agent;
65 parts of cork powder with the particle size of 100 meshes.
The preparation process of the compatilizer is as follows: heating 25 parts of chlorinated polyethylene to 175 ℃ until the chlorinated polyethylene is completely melted, adding 5 parts of maleic anhydride and 0.3 part of dibenzoyl peroxide, reacting for 18min, cooling and discharging to obtain the compatilizer.
A production method of sandal soles comprises the following steps:
s1 blending: weighing and mixing the natural rubber, the brominated butyl rubber and the compatilizer according to the weight parts required by the formula, heating to 55 ℃, and mixing for 8min to obtain mixed rubber;
s2 mixing: putting the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder into a rubber mixing mill, uniformly mixing, heating to 75 ℃, and mixing for 25min to obtain a rubber material;
s3 vulcanization molding: putting the rubber material into a vulcanization forming die, heating to 170 ℃, and vulcanizing for 20min to obtain vulcanized rubber;
s4 heat setting: and (3) putting the vulcanized rubber into a heat setting mold, heating to 150 ℃ for 18min to obtain the sandal sole.
Example 4:
the difference from the example 3 is that modified cork powder and the like are used for replacing cork powder, and the preparation process of the modified cork powder is as follows:
step one, uniformly mixing 10 parts of 2, 2-dimethylolpropionic acid and 40 parts of PPG-2000, heating to 120 ℃, continuously stirring until the 2, 2-dimethylolpropionic acid is dissolved, cooling to 60 ℃, then adding 15 parts of diphenylmethane diisocyanate, and continuously stirring for 2 hours to obtain a prepolymer;
step two, uniformly mixing 2 parts of triethylamine, 6 parts of aminopropyltriethoxysilane, 30 parts of the prepolymer and 50 parts of water, and shearing and emulsifying for 20min to obtain a modified emulsion;
and thirdly, immersing the cork powder with the particle size of 100 meshes into the modified emulsion, heating to 50 ℃, taking out after 3 hours, and drying to obtain the modified cork powder.
Example 5:
the difference from the example 3 is that modified cork powder and the like are used for replacing cork powder, and the preparation process of the modified cork powder is as follows:
step one, uniformly mixing 15 parts of 2, 2-dimethylolpropionic acid and 50 parts of PPG-2000, heating to 140 ℃, continuously stirring until the 2, 2-dimethylolpropionic acid is dissolved, cooling to 70 ℃, then adding 20 parts of diphenylmethane diisocyanate, and continuously stirring for 3 hours to obtain a prepolymer;
step two, uniformly mixing 4 parts of triethylamine, 10 parts of aminopropyltriethoxysilane, 40 parts of the prepolymer and 60 parts of water, and shearing and emulsifying for 30min to obtain a modified emulsion;
and thirdly, immersing the cork powder with the particle size of 100 meshes into the modified emulsion, heating to 60 ℃, taking out after 5 hours, and drying to obtain the modified cork powder.
Example 6:
the difference from the example 3 is that modified cork powder and the like are used for replacing cork powder, and the preparation process of the modified cork powder is as follows:
step one, uniformly mixing 12 parts of 2, 2-dimethylolpropionic acid and 45 parts of PPG-2000, heating to 130 ℃, continuously stirring until the 2, 2-dimethylolpropionic acid is dissolved, cooling to 65 ℃, then adding 18 parts of diphenylmethane diisocyanate, and continuously stirring for 2.5 hours to obtain a prepolymer;
step two, uniformly mixing 3 parts of triethylamine, 8 parts of aminopropyltriethoxysilane, 35 parts of the prepolymer and 55 parts of water, and shearing and emulsifying for 25min to obtain a modified emulsion;
and thirdly, immersing the cork powder with the particle size of 100 meshes into the modified emulsion, heating to 55 ℃, taking out after lasting for 4 hours, and drying to obtain the modified cork powder.
Example 7:
the difference from example 6 is that the modified cork flour was 70 parts.
Example 8:
the difference from example 6 is that 80 parts of modified cork powder.
Example 9:
the difference from example 6 is that the particle size of the modified cork flour is 300 mesh.
Example 10:
the difference from example 6 is that the particle size of the modified cork flour is 500 mesh.
Example 11:
the difference from example 6 is that the sole further comprises 3 parts of camellia extract, which is added during the mixing in S2. The preparation process of the camellia extract comprises the following steps:
firstly, picking and chopping camellia leaves, drying for 15min at 110 ℃, grinding into powder, and sieving with a 50-mesh sieve to obtain leaf powder;
and secondly, soaking the leaf powder into 50wt% ethanol solution, heating to 60 ℃, keeping for 2 hours, and finally filtering and evaporating to remove ethanol to obtain the camellia extract.
Example 12:
the difference from example 6 is that the sole further comprises 5 parts of camellia extract, which is added during the mixing in S2. The preparation process of the camellia extract comprises the following steps:
firstly, picking and chopping camellia leaves, drying for 15min at 110 ℃, grinding into powder, and sieving with a 50-mesh sieve to obtain leaf powder;
and secondly, soaking the leaf powder into 50wt% ethanol solution, heating to 70 ℃, keeping for 3 hours, and finally filtering and evaporating to remove ethanol to obtain the camellia extract.
Example 13:
the difference from example 6 is that the sole further comprises 4 parts of camellia extract, which is added during the mixing in S2. The preparation process of the camellia extract comprises the following steps:
firstly, picking and chopping camellia leaves, drying for 15min at 110 ℃, grinding into powder, and sieving with a 50-mesh sieve to obtain leaf powder;
and secondly, soaking the leaf powder into 50wt% ethanol solution, heating to 65 ℃, keeping for 2.5 hours, and finally filtering and evaporating to remove ethanol to obtain the camellia extract.
Comparative example 1:
the difference from example 3 is that 100 parts of natural rubber, excluding bromobutyl rubber and the compatibilizer.
Comparative example 2:
the difference from example 3 is that 100 parts of natural rubber, 20 parts of cork flour excluding bromobutyl rubber and compatibilizer.
Comparative example 3:
the difference from example 3 is that cork flour is not included.
And (3) performance testing:
the shoe soles of examples 1 to 13 and comparative examples 1 to 3 were subjected to a tear strength test according to the method described in GB/T3903.12-2005 "test method for outsole tear Strength of footwear", and the results are shown in Table 1.
The soles of examples 1 to 13 and comparative examples 1 to 3 were subjected to a rebound resilience test by referring to the method described in GB/T1681-2009 test for rebound resilience of vulcanized rubber, and the results are shown in Table 1.
TABLE 1 sole Performance test results recording sheet
| Tear Strength (N/mm) | Rebound resilience (%) | |
| Example 1 | 34.5 | 72 |
| Example 2 | 34.3 | 73 |
| Example 3 | 34.9 | 76 |
| Example 4 | 36.3 | 76 |
| Example 5 | 36.6 | 77 |
| Example 6 | 36.8 | 77 |
| Example 7 | 36.6 | 81 |
| Example 8 | 36.7 | 85 |
| Example 9 | 37.6 | 76 |
| Example 10 | 38.1 | 77 |
| Example 11 | 40.8 | 76 |
| Example 12 | 40.6 | 77 |
| Example 13 | 40.1 | 76 |
| Comparative example 1 | 22.6 | 59 |
| Comparative example 2 | 33.6 | 52 |
| Comparative example 3 | 34.4 | 44 |
As can be seen from table 1:
1. comparing the test results of examples 1-3 and comparative example 1, the compatibility of the natural rubber and cork powder is improved after blending modification, so that the tear resistance and the resilience of the sole are improved, and example 3 is a preferred example;
2. the comparison of the test results of the examples 3-6 shows that the compatibility of the modified cork powder and the blended rubber material is further improved, thereby being beneficial to improving the tear resistance of the sole;
3. comparison of the test results of examples 6-10 shows that high loading levels and small particle sizes can be used to improve the tear resistance and rebound resilience of the shoe sole due to the further improved compatibility of the modified cork flour with the blended rubber material;
4. the comparison of the test results of the embodiment 3 and the embodiments 11 to 13 can show that the camellia extract can further improve the compatibility of the blended rubber and the modified cork powder, so that the modified cork powder has a certain reinforcing effect and is beneficial to improving the tear resistance of the sole;
5. the test results of comparative examples 1 and 2 are compared, and the shoe sole tearing strength is easily reduced greatly due to the excessively high cork powder filling amount under the condition that the natural rubber is taken as the base material;
6. the comparison of the test results of comparative example 3 and example 3 can reveal that the addition of cork flour helps to improve the resilience of the sole.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The sandal sole is characterized by being prepared from the following raw materials in parts by weight:
70-80 parts of natural rubber;
20-30 parts of brominated butyl rubber;
6-8 parts of a compatilizer;
1.5-3 parts of sulfur;
1-2 parts of an accelerator;
2-3 parts of stearic acid;
4-5 parts of zinc oxide;
20-30 parts of a filler;
0.2-0.5 part of anti-aging agent;
50-80 parts of cork powder.
2. A sandal sole as claimed in claim 1 wherein: the preparation process of the compatilizer is as follows: heating 20-30 parts of chlorinated polyethylene to 170-180 ℃ until the chlorinated polyethylene is completely melted, adding 4-6 parts of maleic anhydride and 0.2-0.4 part of dibenzoyl peroxide, reacting for 15-20min, cooling and discharging to obtain the compatilizer.
3. A sandal sole as claimed in claim 1 wherein: the cork powder is modified, and the modification process is as follows:
step one, uniformly mixing 10-15 parts of 2, 2-dimethylolpropionic acid and 40-50 parts of PPG-2000, heating to 140 ℃, continuously stirring until the 2, 2-dimethylolpropionic acid is dissolved, cooling to 60-70 ℃, then adding 15-20 parts of diphenylmethane diisocyanate, and continuously stirring for 2-3 hours to obtain a prepolymer;
step two, uniformly mixing 2-4 parts of triethylamine, 6-10 parts of aminopropyltriethoxysilane, 30-40 parts of the prepolymer and 50-60 parts of water, and shearing and emulsifying for 20-30min to obtain a modified emulsion;
and thirdly, immersing the cork powder into the modified emulsion, heating to 50-60 ℃, taking out after 3-5h, and drying to obtain the modified cork powder.
4. A sandal sole as claimed in claim 3 wherein: the addition amount of the cork powder is 70-80 parts.
5. A sandal sole as claimed in claim 3 wherein: the particle size of the cork powder is 500 meshes.
6. A sandal sole as claimed in claim 3 wherein: the sole also comprises 3-5 parts of camellia extract, and the preparation process of the camellia extract is as follows:
firstly, picking camellia leaves, cutting up the camellia leaves, drying and grinding the camellia leaves to obtain leaf powder;
and secondly, soaking the leaf powder into ethanol, heating to 60-70 ℃, keeping for 2-3h, and finally filtering and evaporating to remove the ethanol to obtain the camellia extract.
7. A sandal sole as claimed in claim 1 wherein: the filler is a mixture of white carbon black and light calcium carbonate.
8. A method for producing a sandal sole as claimed in any one of claims 1 to 7 comprising the steps of:
s1 blending: weighing and mixing natural rubber, brominated butyl rubber and a compatilizer according to the required weight parts of the formula, heating to 50-60 ℃, and mixing for 5-10min to obtain rubber compound;
s2 mixing: uniformly mixing the rubber compound, sulfur, an accelerator, stearic acid, zinc oxide, a filler, an anti-aging agent and cork powder, heating to 70-80 ℃, and mixing for 20-30min to obtain a rubber material;
s3 vulcanization molding: putting the rubber material into a vulcanization forming mold, heating to 160-180 ℃, and vulcanizing for 15-30min to obtain vulcanized rubber;
s4 heat setting: and (3) putting the vulcanized rubber into a heat setting mold, heating to 140-160 ℃, and keeping for 15-20min to obtain the sandal sole.
9. The method for producing a sandal sole as claimed in claim 8, further comprising the steps of: 3-5 parts of camellia extract is added in the step of mixing S2.
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