WO2023005233A1 - Semelle en caoutchouc d'origine biologique et son procédé de préparation, et moule - Google Patents
Semelle en caoutchouc d'origine biologique et son procédé de préparation, et moule Download PDFInfo
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- WO2023005233A1 WO2023005233A1 PCT/CN2022/082016 CN2022082016W WO2023005233A1 WO 2023005233 A1 WO2023005233 A1 WO 2023005233A1 CN 2022082016 W CN2022082016 W CN 2022082016W WO 2023005233 A1 WO2023005233 A1 WO 2023005233A1
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 120
- 239000005060 rubber Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000004073 vulcanization Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 17
- 239000003549 soybean oil Substances 0.000 claims abstract description 17
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 8
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 8
- 229920001194 natural rubber Polymers 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- 238000009415 formwork Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000001721 carbon Chemical class 0.000 claims description 5
- 210000002683 foot Anatomy 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 210000004744 fore-foot Anatomy 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003457 anti-vomiting effect Effects 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000003921 oil Substances 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000005062 Polybutadiene Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 230000003474 anti-emetic effect Effects 0.000 description 3
- 239000002111 antiemetic agent Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 240000004760 Pimpinella anisum Species 0.000 description 2
- 235000012550 Pimpinella anisum Nutrition 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/128—Moulds or apparatus therefor
-
- 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
-
- 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
Definitions
- the invention relates to the technical field of shoe sole preparation, in particular to a bio-based rubber shoe sole, a preparation method thereof, and a mold.
- soybean oil and epoxidized soybean oil are directly added to the rubber material, and then the rubber product is obtained through physical blending, which has problems such as small amount of addition, poor compatibility, and easy precipitation.
- soybean oil is precipitated, resulting in poor bonding strength between the rubber outsole and the foam midsole, easy to open the glue, and high quality risks.
- the embodiment of the present application provides a bio-based rubber sole and its preparation method and mold, which solves the technical problems of excessive carbon emissions and easy precipitation of soybean oil in the sole in the prior art, and realizes the reduction of the use of non-renewable resources , to obtain a bio-based rubber sole with high adhesive strength, and at the same time achieve the technical effect of rapid edge tearing, which significantly improves production efficiency.
- a bio-based rubber sole comprising the following components by weight:
- the active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerin, and triethanolamine;
- the anti-aging agent is selected from any one or more of anti-aging agent RD, anti-aging agent BHT, anti-aging agent 1010, anti-aging agent MB, anti-aging agent 4010, and anti-aging agent 264;
- the tackifying resin is selected from any one or more of carbon five resins, carbon nine resins, modified carbon nine resins, phenolic resins, and coumarone-indene resins;
- the vulcanization accelerator is selected from any one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D, vulcanization accelerator DM ;
- the silane coupling agent is selected from any one or more of KH-550 and KH-560.
- the preparation method of the bio-based solution-polymerized styrene-butadiene rubber is as follows: put 100-300 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer, and then put in 3-6 parts of zinc oxide, 1-3 parts of stearic acid 20-43 parts of epoxy soybean oil is added to the internal mixer to generate heat due to friction in the system, and 20-43 parts of epoxy soybean oil is added, and the mixer is continued, discharged, and cooled to obtain bio-based solution-polymerized styrene-butadiene rubber;
- the bio-based solution-polymerized styrene-butadiene rubber has a Mooney viscosity ML(1+4) of 55-65 at 100°C; the bio-based solution-polymerized styrene-butadiene rubber includes 25%-40% of bound styrene.
- bio-based EPDM rubber includes 45%-60% of bio-based ethylene and 5.5%-9% of the third monomer ENB;
- the bio-based EPDM rubber has a Mooney viscosity ML(1+4) of 55-80 at 125°C.
- a preparation method for bio-based rubber soles comprising the following steps:
- Step (1) mixing bio-based solution-polymerized styrene-butadiene rubber, bio-based EPDM rubber, and natural rubber;
- Step (2) The mixture obtained in step (1) is softened, and then vulcanization accelerator and insoluble sulfur are added; slices are produced as required, and punched according to the production requirements of shoe soles;
- Step (3) Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160 ⁇ 5°C for 120-170 seconds, and tear off the burrs by hand.
- a rubber film mold comprising
- the upper template including a first groove area
- a lower formwork connected to the upper formwork, the lower formwork has a lower rubber base area, a lower burr area, and a second groove area;
- the edge of the lower rubber base area is connected with the second groove area, and the side of the second groove area away from the lower rubber base area is connected to the lower burr area;
- the first groove area is located above the second groove area.
- the groove angle at the bottom of the second groove area is 30-60 degrees.
- the position of the sharp corner at the bottom of the second groove area corresponds to the edge position of the first groove area
- the sharp corner position of the bottom of the second groove area is 0-0.3mm away from the edge of the first groove area.
- the lower rubber base area includes a first lower rubber base area and a second lower rubber base area, the first lower rubber base area corresponds to the position of the forefoot, and the second lower rubber base area corresponds to the rear heel position,
- the first lower rubber chassis area and the second lower rubber chassis area are not connected to each other, and the first lower rubber chassis area and the second lower rubber chassis area are respectively connected to the second groove area.
- the lower rubber bottom sheet area includes a third lower rubber bottom sheet area, the third lower rubber bottom sheet area corresponds to the position of the center of the foot, and the third lower rubber bottom sheet area is not in contact with the first lower rubber bottom sheet area, the The second lower rubber chassis area is connected, and the third lower rubber chassis area is connected to the second grooved area.
- the upper mold in the present application has a first groove area
- the lower mold has a second groove area
- the first groove area is located above the second groove area; from the horizontal direction Viewed from above, the position of the sharp corner at the bottom of the second groove area (the angle of the sharp angle is 30-60 degrees) coincides with or is separated by a certain distance from the edge position of the first groove area.
- the upper raw area and the lower raw area are overlapped and connected to each other, so when removing the burrs, you only need to select any position of the burr area of the rubber base and tear it, and the entire burr area can be removed, realizing quick hand tearing
- the effect of rough edges reduces the trimming and finishing process and significantly improves production efficiency.
- the bio-based rubber sole of the present application can be used to prepare both the outsole and the sole sheet.
- the sole sheet since the sole sheet requires four sides, the burrs of the sole sheet need to be connected together.
- the existing rubber sole formulation has poor fluidity when preparing the sole, as shown in the numerical value of Comparative Example 1 in Table 1.
- the bio-based rubber sole of the present application has good fluidity and is more suitable for preparing shoe sole sheets.
- Fig. 1 is the upper formwork structure schematic diagram of present embodiment 1;
- Fig. 2 is the structural representation of the lower formwork of the present embodiment 1;
- Fig. 3 is the partial structure schematic diagram of the lower formwork of present embodiment 1;
- FIG. 4 is a schematic diagram of the position and structure of the first grooved area and the second grooved area in Embodiment 1;
- Fig. 5 is the physical figure (front side) of the rubber back sheet that the mold of present embodiment 1 prepares;
- Fig. 6 is the physical figure (remove burrs) of the rubber back sheet that the mold of present embodiment 1 prepares;
- a rubber film mold is composed of an upper template and a lower template.
- the upper template has an upper rubber base area 21 , an upper burr area 22 , and a first groove area 23 , and the upper rubber base area 21 is connected to the upper burr area 22 through the first groove area 23 .
- the lower template has a lower rubber base area 11, a lower burr area 12, and a second groove area 13.
- the angle of the groove at the bottom of the second groove area 13 is 60 degrees, and the edges of the lower rubber base area 11 are connected
- There is a second groove area 13 and the side of the second groove area 13 facing away from the lower rubber bottom sheet area 11 is connected to the lower burr area 12 .
- the upper rubber base area 21 coincides with the lower rubber base area 11
- the upper burr area 22 coincides with the lower burr area 12.
- the first Groove area 23 is positioned at the top of the second groove area 13; Viewed from the horizontal direction (x direction), the sharp angle position of the bottom of the second groove area 13 (the angle of this angle is 30-60 degree) and the first concave
- the edge positions of the groove area 23 are coincident or the sharp angle position of the bottom of the second groove area 13 is 0-0.3 mm away from the edge of the first groove area 23 .
- the first lower rubber base area 111, the second lower rubber base area 112, and the third lower rubber base area are not connected to each other, but are all connected to the second groove.
- the thickness of the second groove area 13 should be smaller than the thickness of the lower rubber base sheet area 11 and the lower burr area 12 .
- the rubber base area corresponding to the forefoot, heel and sole of the foot will be placed in a mold for production.
- the rubber base area is not attached to the outsole as a whole, but According to the different positions of the soles of the feet, the appropriate rubber bottom sheet is selected for lamination. Therefore, after the preparation is completed, the burrs need to be removed before use.
- a preparation method for bio-based rubber soles comprising the steps of:
- Step (1) The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, put 100 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer at a speed of 40-50 rpm, and banbury for two minutes; then put in zinc oxide 3 1 part, 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the temperature in the internal mixer rises to 85 °C, add 27 parts of epoxy soybean oil, and continue banburying for 12 minutes; The resulting mixture is discharged from the internal mixer, transferred to a double-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber; among them, the carboxylated solution-polymerized styrene-butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd.
- bio-based solution polystyrene butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100°C, and the mass ratio of bound styrene to the total amount of styrene and butadiene 34%, the mass ratio of vinyl to the total amount of butadiene is 34%.
- Step (2) First put 40 parts of bio-based solution-polymerized styrene-butadiene rubber, 22 parts of Keltan @ Eco 6950 (bio-based EPDM 6950) of Arlanxeo Company, and 38 parts of natural rubber 3L into the internal mixer for mixing Refining, temperature 85°C, time 60 seconds; then put 26.67 parts of white carbon black, 2.6 parts of silane coupling agent Si-69 for mixing, temperature 95°C, time 120 seconds; then put 13.33 parts of white carbon black, stearic acid 1801 1 part, 0.8 parts of anti-aging agent RD, 1.5 parts of polyethylene glycol PEG4000, 0.7 parts of diethylene glycol, 3.5 parts of zinc oxide, 1.2 parts of polyethylene wax, 1.5 parts of anti-emetic cream OH3, and 1 part of modified carbon nine resin Internal mixer, temperature 125°C, time 90 seconds; clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to open mixer with temperature lower than 70°C
- Step (3) The temperature of the wheel table is controlled below 60°C. First, the large material is smelted on the drum to soften, and then 0.3 parts of vulcanization accelerator NS, 1 part of anti-yellowing vulcanization accelerator 6-GR, and vulcanization accelerator TBZTD- 75 0.2 parts, 2 parts of insoluble sulfur; first make 3 to 5 triangle bags, thickness 3-4mm, then make thin 1-2 times, thin pass thickness 1-2mm, then make about three triangle bags, and produce slices as needed ;Finally, it is punched out according to the production demand of the sole.
- vulcanization accelerator NS 1 part of anti-yellowing vulcanization accelerator 6-GR
- vulcanization accelerator TBZTD- 75 0.2 parts, 2 parts of insoluble sulfur
- Step (4) Put the punched rubber sheet into the preheated mold of Example 1, vulcanize and mold at a vulcanization temperature of 160 ⁇ 5°C for 120-170 seconds, and tear off the burrs by hand.
- Bio-based EPDM 6950 includes: bio-based ethylene 48%, third monomer ENB 9%, which has a Mooney viscosity ML(1+4) of 65 at 125°C.
- a preparation method for bio-based rubber soles comprising the steps of:
- Step (1) The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, 100 parts of carboxylated solution-polymerized styrene-butadiene rubber are put into a banbury mixer at a speed of 40-50 rpm, and banburying for two minutes; then 3 parts of zinc oxide are put into , 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the internal temperature of the internal mixer rises to 85 °C, add 20 parts of epoxy soybean oil, and continue banburying for 12 minutes; The obtained mixture is discharged from the internal mixer, transferred to a two-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber.
- carboxylated solution-polymerized styrene-butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd.; epoxy soybean oil is a commercial product; bio-based solution-polymerized styrene-butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100 ° C, The mass ratio of ethylene to the total amount of styrene and butadiene is 25%, and the mass ratio of vinyl to the total amount of butadiene is 48%.
- Step (2) First put 40 parts of bio-based solution polystyrene butadiene rubber, 16 parts of Keltan @ Eco 8850 (bio-based EPDM rubber 8850) of Arlanxeo Company, and 44 parts of natural rubber 3L into the internal mixer for mixing Refining, the temperature is 85°C, the time is 60 seconds; then 23.33 parts of white carbon black, 2.1 parts of silane coupling agent Si-69 are put into mixing, the temperature is 95°C, the time is 120 seconds; then 11.67 parts of white carbon black, stearic acid 1801 Put 1.1 parts, 0.9 parts of anti-aging agent, 2.5 parts of active agent, 3.8 parts of zinc oxide, 1.5 parts of polyethylene wax, 1.8 parts of anti-vomiting cream OH3, and 1.4 parts of tackifying resin into the internal mixer at a temperature of 125 ° C for 90 seconds; Clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to the open mill with temperature lower than 70°C, thickness 4-5
- Step (3) The temperature of the wheel table is controlled below 60°C. First, the aniseed material is smelted on the drum to soften, and then 1.8 parts of vulcanization accelerator and 2.3 parts of insoluble sulfur are added; first, 3 to 5 triangle bags are made, with a thickness of 3-4mm. , Thinning 1-2 times again, the thickness of the thinning is 1-2mm, and then making about three triangle bags, and the pieces are produced according to the needs; finally, punching according to the production needs of the soles.
- Step (4) Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160 ⁇ 5°C for 120-170 seconds, and tear off the burrs by hand.
- the active agent is selected from any one or more of polyethylene glycol, diethylene glycol, glycerin, and triethanolamine;
- the anti-aging agent is selected from any one or more of anti-aging agent RD, anti-aging agent BHT, anti-aging agent 1010, anti-aging agent MB, anti-aging agent 4010, and anti-aging agent 264;
- the tackifying resin is selected from any one or more of carbon five resins, carbon nine resins, modified carbon nine resins, phenolic resins, and coumarone-indene resins;
- the vulcanization accelerator is selected from any one or more of vulcanization accelerator NS, vulcanization accelerator TS, vulcanization accelerator TBZTD, vulcanization accelerator 6-GR, vulcanization accelerator M, vulcanization accelerator D, vulcanization accelerator DM .
- Example 3 Put the specific products of the above-mentioned active agent, anti-aging agent, tackifying resin, and vulcanization accelerator into Example 3, and then conduct experimental tests on the obtained bio-based rubber outsole.
- the experimental data are shown in the values of Example 3 in Table 1. Since the obtained values have little difference, the average value is taken for calculation, as shown in Table 1.
- the preparation method of a bio-based rubber outsole is basically the same as the preparation method in Example 3, the difference is:
- a preparation method for bio-based rubber soles comprising the steps of:
- Step (1) The preparation method of bio-based solution-polymerized styrene-butadiene rubber: first, put 100 parts of carboxylated solution-polymerized styrene-butadiene rubber into a banbury mixer at a speed of 30-40 rpm, and banbury for two minutes; then put 3 parts of zinc oxide , 1 part of stearic acid, heat is generated by system friction, and the temperature in the internal mixer gradually increases; when the internal temperature of the internal mixer rises to 85 °C, add 43 parts of epoxy soybean oil, and continue banburying for 15 minutes; The obtained mixture is discharged from the internal mixer, transferred to a two-roll mill, calendered, and cooled to room temperature to obtain bio-based solution-polymerized styrene-butadiene rubber.
- carboxylated solution polystyrene butadiene rubber comes from Zhenjiang Chimei Chemical Co., Ltd.; epoxy soybean oil is a commercially available product; bio-based solution polystyrene butadiene rubber has a Mooney viscosity ML(1+4) of 60 at 100°C, Ethylene accounts for 40% by mass of the total amount of styrene and butadiene, and vinyl accounts for 30% by mass of the total amount of butadiene.
- Step (2) First put 40 parts of bio-based solution-polymerized styrene-butadiene rubber, 16 parts of Keltan @ Eco 6950 (bio-based EPDM 6950) of Arlanxeo Company, and 38 parts of natural rubber 3L into the internal mixer for mixing Refining, temperature 85°C, time 60 seconds; then put in 25.33 parts of white carbon black, 2.8 parts of silane coupling agent Si-69 and mix, temperature 95°C, time 120 seconds; then put in 12.67 parts of white carbon black, stearic acid 1801 0.7 parts, 0.6 parts of anti-aging agent BHT, 1.4 parts of polyethylene glycol PEG4000, 0.5 parts of diethylene glycol, 3.2 parts of zinc oxide, 0.7 parts of polyethylene wax, 1.0 parts of anti-emetic cream agent OH, 0.9 parts of modified carbon nine resin Internal mixer, temperature 125°C, time 90 seconds; clean once, continue mixing, temperature 125°C, time 90 seconds; discharge temperature 125°C, immediately transfer to open mixer with
- Step (3) The temperature of the wheel bed is controlled below 60°C.
- the aniseed material is smelted on the drum to soften, and then 0.25 parts of vulcanization accelerator NS, 0.75 parts of anti-yellowing vulcanization accelerator 6-GR, and vulcanization accelerator TBZTD- 75 0.2 parts, 1.9 parts of insoluble sulfur; first make 3 to 5 triangle bags, the thickness is 3-4mm, and then make thin 1-2 times, the thickness of the thin pass is 1-2mm, and then make about three triangle bags, and the film is produced as needed ;Finally, it is punched out according to the production demand of the sole.
- Step (4) Put the blanked rubber sheet into a preheated mold, vulcanize and mold at a vulcanization temperature of 160 ⁇ 5°C for 120-170 seconds, and tear off the burrs by hand.
- the preparation method of the rubber outsole is basically the same as the preparation method in Example 3, the difference is:
- test conditions of the ozone testing machine are temperature 50°C, humidity 85%, ozone concentration 300pphm, time 3 hours;
- Bonding strength in embodiment 2,3,4,5 tests the bonding strength of big end and shoe sole sheet according to GB/T 532-2008;
- the EVA foaming big end of same material and the sole of embodiment preparation by standard process The pieces are assembled and molded, the curing agent is 5%, and placed for 24 hours after molding;
- the conditions of the hydrolysis resistance test are a temperature of 70°C, a humidity of 95%, and a time of 168 hours.
- the invention discloses a bio-based rubber sole, which comprises the following components in parts by weight: 40 parts of bio-based solution polystyrene butadiene rubber, 16-24 parts of bio-based EPDM rubber, 38-46 parts of natural rubber, white carbon black 35-40 parts, 2.1-2.8 parts of silane coupling agent, 0.7-1.1 parts of stearic acid, 0.6-0.9 parts of anti-aging agent, 1.9-2.5 parts of active agent, 3.2-3.8 parts of zinc oxide, 0.7-1.5 parts of polyethylene wax , 1.0-1.8 parts of anti-emetic cream agent, 0.9-1.4 parts of tackifying resin, 1.2-1.8 parts of vulcanization accelerator, 1.9-2.3 parts of insoluble sulfur; when preparing bio-based solution-polymerized styrene-butadiene rubber in this application, carboxylated solvent Polystyrene butadiene rubber, zinc oxide, stearic acid, and epoxidized soybean oil are mixed in an internal mixer to build an ester-based
- the ion pairs formed by zinc ions and carboxyl groups in the rubber compound can be used as strengthening points, which increases the degree of crosslinking and improves the mechanical properties of the bio-based rubber outsole, which has industrial applicability.
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- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
Est divulguée dans la présente invention une semelle en caoutchouc d'origine biologique comprenant les composants suivants en parties en poids : 40 parties de caoutchouc styrène-butadiène polymérisé en solution d'origine biologique, 16 à 24 parties de caoutchouc monomère éthylène-propylène-diène d'origine biologique, 38 à 46 parties de caoutchouc naturel, 35 à 40 parties de noir de carbone blanc, 2,1 à 2,8 parties d'agent de couplage au silane, 0,7 à 1,1 partie d'acide stéarique, 0,6 à 0,9 partie d'agent anti-âge, 1,9 à 2,5 parties d'agent actif, 3,2 à 3,8 parties d'oxyde de zinc, 0,7 à 1,5 partie de cire de polyéthylène, 1,0 à 1,8 partie d'agent anti-givrage, 0,9 à 1,4 partie de résine tackifiante, 1,2 à 1,8 partie d'accélérateur de vulcanisation, et 1,9 à 2,3 parties de soufre insoluble ; dans la présente demande, lorsque le caoutchouc styrène-butadiène polymérisé en solution d'origine biologique est préparé pour la polymérisation, du caoutchouc styrène-butadiène polymérisé en solution carboxylée, de l'oxyde de zinc, de l'acide stéarique et de l'huile de soja époxydée sont mélangés dans un mélangeur interne pour construire une structure de réseau réticulé à base d'ester, ayant l'avantage de ne pas séparer l'huile. De plus, pendant le moulage par vulcanisation, des paires d'ions formées par les ions de zinc et le carboxyle dans le matériau de caoutchouc peuvent être utilisées comme points de renforcement pour augmenter le degré de réticulation, améliorant les performances mécaniques de la semelle d'usure en caoutchouc d'origine biologique.
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CN113444302B (zh) * | 2021-07-28 | 2023-02-07 | 茂泰(福建)鞋材有限公司 | 一种生物基橡胶鞋底及其制备方法、模具 |
CN115612236A (zh) * | 2022-10-10 | 2023-01-17 | 茂泰(福建)鞋材有限公司 | 一种射出成型的生物基橡胶鞋底及其制备方法 |
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US20100146823A1 (en) * | 2008-12-11 | 2010-06-17 | Mizuno Corporation | Sole and method of manufacturing sole |
US20160160037A1 (en) * | 2014-12-05 | 2016-06-09 | Ljo, Inc. | Composition and Process of Manufacture for a Shoe Sole Component for Footwear |
CN106046460A (zh) * | 2016-07-14 | 2016-10-26 | 吴明才 | 一种高弹性耐磨的橡胶鞋底材料及其制备方法 |
CN113444302A (zh) * | 2021-07-28 | 2021-09-28 | 茂泰(福建)鞋材有限公司 | 一种生物基橡胶鞋底及其制备方法、模具 |
CN113444303A (zh) * | 2021-07-28 | 2021-09-28 | 茂泰(福建)鞋材有限公司 | 一种抗湿滑生物基橡胶鞋底及其制备方法、模具 |
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CN215943578U (zh) * | 2021-07-28 | 2022-03-04 | 茂泰(福建)鞋材有限公司 | 一种橡胶底片模具 |
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US20100146823A1 (en) * | 2008-12-11 | 2010-06-17 | Mizuno Corporation | Sole and method of manufacturing sole |
US20160160037A1 (en) * | 2014-12-05 | 2016-06-09 | Ljo, Inc. | Composition and Process of Manufacture for a Shoe Sole Component for Footwear |
CN106046460A (zh) * | 2016-07-14 | 2016-10-26 | 吴明才 | 一种高弹性耐磨的橡胶鞋底材料及其制备方法 |
CN113444302A (zh) * | 2021-07-28 | 2021-09-28 | 茂泰(福建)鞋材有限公司 | 一种生物基橡胶鞋底及其制备方法、模具 |
CN113444303A (zh) * | 2021-07-28 | 2021-09-28 | 茂泰(福建)鞋材有限公司 | 一种抗湿滑生物基橡胶鞋底及其制备方法、模具 |
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