A kind of sole material for women's shoes and preparation method thereof

Abstract

The invention discloses a sole material for women's shoes, comprising the following weight parts: EVA: 100-200 parts, alcohol-base solution: 2-10 parts, catalyst: 0.01-0.5 parts, organic solvent: 50-150 parts, modified PIB: 1-10 parts, cross-linking agent: 1-5 parts, foaming agent: 2-10 parts, auxiliary agent: 1-5 parts; the modified PIB is prepared by reacting PIB with acrylic isocyanate compounds. The object of the invention is to provide a sole material for women's shoes with good mechanical properties and wear resistance.

Description

Technical Field

[0001] The invention relates to polymer materials, and more particularly to a sole material for women's shoes. Background Art

[0002] EVA is widely used as a common sole material for women's shoes. It is generally obtained by adding a foaming agent to EVA for foaming and molding. However, EVA has certain defects, such as poor wear resistance. Therefore, the modification of EVA is a major topic. In the prior art, some scholars have modified EVA by using PIB, i.e. polyisobutylene, to enhance its wear resistance. However, in the actual research and development process, it was found that although the wear resistance has been improved to a certain extent, the mechanical properties of the material, such as tensile strength, have also decreased. Summary of the invention

[0003] In view of the deficiencies in the prior art, the object of the present invention is to provide a sole material for women's shoes with good mechanical properties and wear resistance.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] A sole material for women's shoes,

[0006] Includes the following parts by weight:

[0007] EVA: 100~200 copies

[0008] Alcohol-base solution: 2~10 parts

[0009] Catalyst: 0.01~0.5 parts

[0010] Organic solvent: 50~150 parts

[0011] Modified PIB: 1~10 parts

[0012] Cross-linking agent: 1~5 parts

[0013] Foaming agent: 2~10 parts

[0014] Additives: 1~5 parts;

[0015] The modified PIB is prepared by reacting PIB with an acrylic isocyanate compound.

[0016] As a further improvement of the present invention,

[0017] The cross-linking agent is dicumyl peroxide.

[0018] As a further improvement of the present invention,

[0019] The foaming agent is azodicarbonamide.

[0020] As a further improvement of the present invention,

[0021] The alcohol-alkali solution is a 0.5-2 mol / L sodium hydroxide ethanol solution.

[0022] As a further improvement of the present invention,

[0023] The auxiliary agent is a mixture of zinc oxide, stearic acid and zinc stearate.

[0024] As a further improvement of the present invention,

[0025] The organic solvent is toluene.

[0026] As a further improvement of the present invention,

[0027] The acrylic isocyanate compound is isocyanoethyl methacrylate.

[0028] As another object of the present invention, a method for preparing a sole material for women's shoes is provided:

[0029] Step 1: Add EVA to a reaction vessel, then add an alcohol-base solution and an organic solvent, and stir evenly at a constant temperature of 70-80°C for 1-3 hours to obtain pretreated EVA;

[0030] Step 2: Take the modified PIB, pretreated EVA and catalyst, add them into the rheometer, mix them at 80-100°C for 10-20 minutes, mix them evenly, hot press them at 80-100°C in a flat vulcanizer at a gauge pressure of 10 MPa, and cool them to room temperature to obtain the base material;

[0031] Step 3: Add the base material into a mixer and knead it at 80°C, then add the cross-linking agent, foaming agent and auxiliary agent, and knead for 10-15 minutes to obtain the sole material.

[0032] As a further improvement of the present invention,

[0033] The preparation method of the modified PIB:

[0034] Step 1: Prepare sodium borohydride solution in an ice bath at -5~0℃, then slowly add boron trifluoride etherate and react for 1~3h;

[0035] Step 2: Prepare PIB into a PIB solution, add the PIB solution to the solution in step 1-1, and react for 15 to 20 hours;

[0036] Step 3: adding sodium hydroxide to adjust the pH value to 10-12, slowly adding hydrogen peroxide solution, reacting for 5-8 hours, washing with water, extracting, drying the organic layer, rotary evaporation, and drying to obtain polyisobutylene PIB-OH with a hydroxyl terminal group;

[0037] Step 4: Under nitrogen protection, add PIB-OH to the reaction vessel, then add the solvent, start stirring, then add KH, and react in an oil bath at 45°C for 8-15h;

[0038] Step 5: After the reaction is completed, return the mixture to room temperature, take the supernatant and add it to the reaction container, and add the acrylic isocyanate compound to react for 1 to 3 hours;

[0039] Step 6: Rotate the product to evaporate the solvent at 60-70°C and dry it in an oven to obtain modified PIB.

[0040] The invention has the beneficial effects that the invention mainly modifies EVA by modifying PIB, wherein the modified PIB is prepared by subjecting PIB to a borohydride oxidation reaction with a terminal group of PIB-OH, then reacting by adding an acrylic isocyanate compound, initiating polymerization by oxygen anions, utilizing the PIB-OH with a hydroxyl terminal group to react with potassium hydride to produce a polyisobutylene oxygen anion macromolecular initiator, initiating polymerization of monomer acrylic acid groups, and obtaining a modified PIB with an isocyanate terminal group, and then adding the modified PIB to EVA, wherein the EVA is first saponified, and then catalyzed by a catalyst, so that the isocyanate group can be polymerized on the EVA, thereby playing a role in modifying the EVA, and compared with the traditional process of adding PIB, the modification process is transformed from physical blending to chemical reaction, forming chemical bonds, and while retaining the PIB to improve the wear resistance, the mechanical properties are also improved. DETAILED DESCRIPTION

[0041] Example 1: Preparation of modified PIB:

[0042] Step 1: Under ice bath conditions at -5 to 0°C, dissolve 1 part by weight of sodium borohydride in 5 parts of tetrahydrofuran to prepare a sodium borohydride solution, then slowly dropwise add 4 parts by weight of boron trifluoride etherate, and react for 1 hour;

[0043] Step 2: Take 100 parts of PIB by mass and add it to 100 parts of tetrahydrofuran to prepare a PIB solution, add the PIB solution to the solution in step 1, and react for 15 hours;

[0044] Step 3: adding sodium hydroxide to adjust the pH value to 10, slowly dropping 5 parts by weight of 30% hydrogen peroxide solution, reacting for 6 hours, washing with water, extracting, drying the organic layer, rotary evaporation, and drying to obtain polyisobutylene PIB-OH with a hydroxyl terminal group;

[0045] Step 4: Under nitrogen protection, add the obtained PIB-OH into a reaction vessel, then add 100 parts of tetrahydrofuran, start stirring, then add 2 parts of KH, and react in an oil bath at 45°C for 10 hours;

[0046] Step 5: After the reaction is completed, the temperature is restored to room temperature, the supernatant is added to the reaction vessel, and 15 parts of isocyanoethyl methacrylate are added to react for 1 hour;

[0047] Step 6: Rotate the product to evaporate the solvent at 60°C and dry it in an oven to obtain modified PIB.

[0048] Example 2: Preparation of sole material pair for women's shoes:

[0049] Step 1: 100 parts of EVA are added to a reaction container, followed by 5 parts of an alcohol-base solution (2 mol / L sodium hydroxide ethanol solution) and 70 parts of anhydrous toluene, and stirred evenly at a constant temperature of 80°C for 1 hour to obtain pretreated EVA;

[0050] Step 2: Take 5 parts of the modified PIB obtained in Example 1, the pretreated EVA obtained in Step 1, and 0.2 parts of dibutyltin dilaurate, add them to a rheometer, and knead them at 80° C. for 15 minutes. After kneading evenly, perform hot pressing molding at 80° C. in a flat vulcanizer at a gauge pressure of 10 MPa, and cool to room temperature to obtain a base material;

[0051] Step 3: Add the base material into a mixer and knead it at 80°C, then add 2 parts of dicumyl peroxide, 5 parts of azodicarbonamide, 2.5 parts of zinc oxide, 1 part of stearic acid, and 1.5 parts of zinc stearate, and mix for 10 minutes to obtain the sole material.

[0052] Comparative Example 1:

[0053] Step 1: 100 parts of EVA are added to a reaction container, followed by 5 parts of an alcohol-base solution (2 mol / L sodium hydroxide ethanol solution) and 70 parts of anhydrous toluene, and stirred evenly at a constant temperature of 80°C for 1 hour to obtain pretreated EVA;

[0054] Step 2: The pretreated EVA obtained in step 1 and 0.2 parts of dibutyltin dilaurate are added to a rheometer, and kneaded at 80° C. for 15 minutes. After kneading evenly, hot pressing is performed in a flat plate vulcanizer at 80° C. and a gauge pressure of 10 MPa, and the base material is cooled to room temperature;

[0055] Step 3: Add the base material into a mixer and knead it at 80°C, then add 2 parts of dicumyl peroxide, 5 parts of azodicarbonamide, 2.5 parts of zinc oxide, 1 part of stearic acid, and 1.5 parts of zinc stearate, and mix for 10 minutes to obtain the sole material.

[0056] Comparative Example 2:

[0057] Step 1: 100 parts of EVA are added to a reaction container, followed by 5 parts of an alcohol-base solution (2 mol / L sodium hydroxide ethanol solution) and 70 parts of anhydrous toluene, and stirred evenly at a constant temperature of 80°C for 1 hour to obtain pretreated EVA;

[0058] Step 2: Take 5 parts of PIB, the pretreated EVA obtained in step 1, and 0.2 parts of dibutyltin dilaurate, add them to a rheometer, and knead them at 80°C for 15 minutes. After kneading evenly, perform hot pressing at 80°C in a flat plate vulcanizer at a gauge pressure of 10 MPa, and cool to room temperature to obtain a base material;

[0059] Step 3: Add the base material into a mixer and knead it at 80°C, then add 2 parts of dicumyl peroxide, 5 parts of azodicarbonamide, 2.5 parts of zinc oxide, 1 part of stearic acid, and 1.5 parts of zinc stearate, and mix for 10 minutes to obtain the sole material.

[0060] Ingredients:

[0061] raw material factory Sodium borohydride Shanghai Jinjinle Industrial Co., Ltd. Tetrahydrofuran Shanghai Jinjinle Industrial Co., Ltd. Boron trifluoride etherate Boron trifluoride etherate PIB (Polyisobutylene 1000) Jilin Longye Chemical Co., Ltd. Sodium hydroxide Shanghai Jinjinle Industrial Co., Ltd. 30% hydrogen peroxide solution Nanjing Chemical Reagent Co., Ltd. KH Shanghai Jinjinle Industrial Co., Ltd. Ethanol Shanghai Jinjinle Industrial Co., Ltd. EVA (7350M) Formosa Plastics Corporation Toluene Shanghai Jinjinle Industrial Co., Ltd. Isocyanoethyl methacrylate Hubei Yongkuo Technology Co., Ltd. Dibutyltin dilaurate Shanghai Jinjinle Industrial Co., Ltd. Dicumyl peroxide Akzo Nobel Ltd. Azodicarbonamide Guangzhou Jiangyan Chemical Co., Ltd. Zinc Oxide Hubei Yongkuo Technology Co., Ltd. Stearic acid Wuhan Jingbiao Technology Co., Ltd. Zinc stearate Hubei Jusheng Technology Co., Ltd.

[0062] Detection:

[0063] 1. Friction coefficient test, using ASTMF 1677-05;

[0064] 2. Hardness test, Shore C hardness tester;

[0065] 3. Tensile strength test, GB / T 6344-2008;

[0066] 4. Elongation at break test, GB / T 6344-2008.

[0067] Friction coefficient hardness Tensile strength (MPa) Elongation at break (%) Embodiment 2 0.58 62 4.2 479 Comparative Example 1 0.40 60 3.8 375 Comparative Example 2 0.55 56 2.7 482

[0068] As a specific implementation method of the improvement,

[0069] Example 2 uses modified PIB and saponified EVA for blending reaction modification, Comparative Example 1 is saponified EVA, and Comparative Example 2 is blended modification of saponified EVA and ordinary PIB. It can be seen from the experimental results that the wear resistance in Example 2 is greatly improved compared with Comparative Example 1, and the hardness, tensile strength and elongation at break are also greatly improved. In Comparative Example 2, although the friction coefficient is also improved, the hardness and tensile strength are reduced.

[0070] The invention has the beneficial effects that the invention mainly modifies EVA by modifying PIB, wherein the modified PIB is prepared by subjecting PIB to a borohydride oxidation reaction with a terminal group of PIB-OH, then reacting by adding an acrylic isocyanate compound, initiating polymerization by oxygen anions, utilizing the PIB-OH with a hydroxyl terminal group to react with potassium hydride to produce a polyisobutylene oxygen anion macromolecular initiator, initiating polymerization of monomer acrylic acid groups, and obtaining a modified PIB with an isocyanate terminal group, and then adding the modified PIB to EVA, wherein the EVA is first saponified, and then catalyzed by a catalyst, so that the isocyanate group can be polymerized on the EVA, thereby playing a role in modifying the EVA, and compared with the traditional process of adding PIB, the modification process is transformed from physical blending to chemical reaction, forming chemical bonds, and while retaining the PIB to improve the wear resistance, the mechanical properties are also improved.

[0071] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A sole material for women's shoes, characterized in that: Includes the following parts by weight: EVA: 100~200 copies Alcohol-base solution: 2~10 parts Catalyst: 0.01~0.5 parts Organic solvent: 50~150 parts Modified PIB: 1~10 parts Cross-linking agent: 1~5 parts Foaming agent: 2~10 parts Additives: 1~5 parts; The modified PIB is prepared by reacting PIB with an acrylic isocyanate compound; Its preparation method is: Step 1: Add EVA to a reaction vessel, then add an alcohol-base solution and an organic solvent, and stir evenly at a constant temperature of 70-80°C for 1-3 hours to obtain pretreated EVA; Step 2: Take the modified PIB, pretreated EVA and catalyst, add them into the rheometer, mix them at 80-100°C for 10-20 minutes, mix them evenly, hot press them at 80-100°C in a flat vulcanizer at a gauge pressure of 10 MPa, and cool them to room temperature to obtain the base material; Step 3: Add the base material into a mixer and knead it at 80°C, then add a cross-linking agent, a foaming agent, and an auxiliary agent, and knead for 10-15 minutes to obtain the sole material; The preparation method of the modified PIB: Step 1: Prepare sodium borohydride solution under ice bath conditions at -5~0℃, then slowly add boron trifluoride etherate and react for 1~3h; Step 2: Prepare PIB into a PIB solution, add the PIB solution to the solution in step 1, and react for 15 to 20 hours; Step 3: adding sodium hydroxide to adjust the pH value to 10-12, slowly adding hydrogen peroxide solution, reacting for 5-8 hours, washing with water, extracting, drying the organic layer, rotary evaporation, and drying to obtain polyisobutylene PIB-OH with a hydroxyl terminal group; Step 4: Under nitrogen protection, add PIB-OH to the reaction vessel, then add the solvent, start stirring, then add KH, and react in an oil bath at 45°C for 8-15h; Step 5: After the reaction is completed, return the mixture to room temperature, take the supernatant and add it to the reaction container, and add the acrylic isocyanate compound to react for 1 to 3 hours; Step 6: Rotate the product to evaporate the solvent at 60-70°C and dry it in an oven to obtain modified PIB.

2. The sole material for women's shoes according to claim 1, characterized in that: The cross-linking agent is dicumyl peroxide.

3. The sole material for women's shoes according to claim 1, characterized in that: The foaming agent is azodicarbonamide.

4. The sole material for women's shoes according to claim 1, characterized in that: The alcohol-alkali solution is a 0.5-2 mol / L sodium hydroxide ethanol solution.

5. The sole material for women's shoes according to claim 4, characterized in that: The auxiliary agent is a mixture of zinc oxide, stearic acid and zinc stearate.

6. The sole material for women's shoes according to claim 5, characterized in that: The organic solvent is toluene.

7. The sole material for women's shoes according to claim 1, characterized in that: The acrylic isocyanate compound is isocyanoethyl methacrylate.

8. A method for preparing a sole material for women's shoes according to any one of claims 1 to 7, characterized in that: Step 1: Add EVA to a reaction vessel, then add an alcohol-base solution and an organic solvent, and stir evenly at a constant temperature of 70-80°C for 1-3 hours to obtain pretreated EVA; Step 2: Take the modified PIB, pretreated EVA and catalyst, add them into the rheometer, mix them at 80-100°C for 10-20 minutes, mix them evenly, hot press them at 80-100°C in a flat vulcanizer at a gauge pressure of 10 MPa, and cool them to room temperature to obtain the base material; Step 3: Add the base material into a mixer and knead it at 80°C, then add a cross-linking agent, a foaming agent, and an auxiliary agent, and knead for 10-15 minutes to obtain the sole material; The preparation method of the modified PIB: Step 1: Prepare sodium borohydride solution under ice bath conditions at -5~0℃, then slowly add boron trifluoride etherate and react for 1~3h; Step 2: Prepare PIB into a PIB solution, add the PIB solution to the solution in step 1, and react for 15 to 20 hours; Step 3: adding sodium hydroxide to adjust the pH value to 10-12, slowly adding hydrogen peroxide solution, reacting for 5-8 hours, washing with water, extracting, drying the organic layer, rotary evaporation, and drying to obtain polyisobutylene PIB-OH with a hydroxyl terminal group; Step 4: Under nitrogen protection, add PIB-OH to the reaction vessel, then add the solvent, start stirring, then add KH, and react in an oil bath at 45°C for 8-15h; Step 5: After the reaction is completed, return the mixture to room temperature, take the supernatant and add it to the reaction container, and add the acrylic isocyanate compound to react for 1 to 3 hours; Step 6: Rotate the product to evaporate the solvent at 60-70°C and dry it in an oven to obtain modified PIB.