CN114907607A - Light cold-resistant EVA sole and preparation method thereof - Google Patents
Light cold-resistant EVA sole and preparation method thereof Download PDFInfo
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- CN114907607A CN114907607A CN202210461285.3A CN202210461285A CN114907607A CN 114907607 A CN114907607 A CN 114907607A CN 202210461285 A CN202210461285 A CN 202210461285A CN 114907607 A CN114907607 A CN 114907607A
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/0085—Use of fibrous compounding ingredients
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2205/06—Flexible foams
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
A light cold-resistant EVA sole and a preparation method thereof, wherein the EVA sole comprises the following raw materials: EVA, silicon rubber, hydrogenated nitrile rubber, thermoplastic elastomer, maleic anhydride grafting EVA, foaming agent, cross-linking agent, accelerant, expanded vermiculite powder, asbestos fiber, epoxidized soybean oil, thiourea, calcium chloride, this application limits EVA, silicon rubber, hydrogenated nitrile rubber, thermoplastic elastomer to use each other, and add maleic anhydride grafting EVA and increase compatibility and adhesion between each raw materials, in order to improve the cold resistance of EVA sole that makes, make it can be under the cold environment of north or severe cold district, keep good compliance and elasticity, satisfy the requirement to sole comfort level in north or severe cold district.
Description
Technical Field
The invention belongs to the field of EVA sole preparation, and particularly relates to a light cold-resistant EVA sole and a preparation method thereof.
Background
At present, various soles are mostly made of EVA or rubber materials, the cost is controllable, and the performances such as elasticity, hardness and the like can be adjusted according to the requirements, so that the requirements of people are basically met. However, whether the rubber sole or the EVA sole is used in an extremely cold environment, various physical indexes such as flexibility and the like are seriously reduced, and when the temperature is reduced to a certain degree, the sole may even be broken, and further improvement is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a light cold-resistant EVA sole, and also aims to provide a method for preparing the EVA sole.
The invention adopts the following technical scheme:
a light cold-resistant EVA sole comprises the following raw materials in parts by weight:
furthermore, the accelerator consists of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.68-0.82: 0.5-0.7.
Further, the cross-linking agent is a cross-linking agent BIBP.
Further, the foaming agent is a foaming agent AC.
Further, the EVA comprises 18-25 parts of EVA7470 and 22-35 parts of EVA 33121.
A preparation method of a light cold-resistant EVA sole comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 12-18min to obtain a premix;
step two, putting the premix prepared in the step one and the raw materials except the foaming agent, the cross-linking agent and the accelerator into an internal mixer, mixing and internally mixing, discharging rubber at the temperature of 115 ℃ and 120 ℃, and standing at room temperature for more than 24 hours;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
and step four, cutting the foaming sheet into a sole shape, and placing the sole shape into a shoe mold for foaming and molding to obtain the light cold-resistant EVA sole.
Further, in the second step, the banburying process specifically includes: adding the premix prepared in the step one and other raw materials except the foaming agent, the cross-linking agent and the accelerator into an internal mixer, and mixing and banburying for 5-10 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; when the banburying temperature is raised to 96 ℃, performing secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; and (4) after the banburying temperature is raised to 115-120 ℃, performing five times of material turning, banburying for 1min, discharging the rubber, and standing at room temperature for more than 24 h.
Further, in the fourth step, the foaming temperature is 152-165 ℃.
Further, in the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the sheet is taken out with the thickness of 2-3 mm.
As can be seen from the above description of the present invention, compared with the prior art, the beneficial effects of the present invention are:
firstly, EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer are limited to be mixed mutually, maleic anhydride grafted EVA is added to increase the compatibility and the adhesion among raw materials, the glass transition temperature of a mixed material is reduced, so that the cold resistance of the prepared EVA sole is improved, good flexibility and elasticity can be kept in the cold environment of the north or alpine regions, and the requirement of the north or alpine regions on the comfort level of the sole is met; the low-temperature resistance of the prepared EVA sole is further improved by introducing thiourea and calcium chloride to be matched with the silicon rubber and the hydrogenated nitrile rubber, and the thiourea can be matched with an accelerator to improve the foaming effect of the EVA sole so as to ensure the overall mechanical property of the EVA sole; introducing epoxidized soybean oil to be matched with the main raw material, increasing the gap between high-molecular chain segments, and reducing the glass transition temperature of the blending material so as to ensure the elasticity of the prepared EVA sole in a low-temperature environment; although the used raw materials are conventional additives, the raw materials have interaction through reasonable raw material composition and part adjustment so as to improve the low temperature resistance of the EVA sole;
secondly, asbestos fiber and expanded vermiculite powder are introduced as reinforcing agents, wherein the asbestos fiber is a good light material, and the expanded vermiculite powder is a porous light material, and the asbestos fiber and the expanded vermiculite powder are matched with each other, so that the density of the foamed EVA sole can be greatly reduced while the reinforcing effect is achieved, and the light EVA sole is obtained; meanwhile, the expanded vermiculite powder and the asbestos fibers are both materials with small contractibility and are matched with the silicon rubber and the hydrogenated nitrile rubber, so that the dimensional stability of the foamed EVA sole can be ensured;
thirdly, zinc stearate, urea and triethylenediamine are limited to be used as accelerators to be matched with a foaming agent, so that the vulcanization speed of the EVA sole is approximately synchronous with the foaming speed, a closed cell structure with small and uniform pores is obtained, the formed closed cell structures are in mutually independent states, and bubbles are not communicated, so that the prepared foamed sole has better anti-skid performance and wear resistance; the foamed hydrogenated nitrile rubber has excellent elasticity so as to ensure the overall mechanical property of the prepared foamed sole; meanwhile, the urea serving as the accelerator can be matched with thiourea and calcium chloride and used as an antiperspirant to further improve the low-temperature resistance of the EVA sole and meet the requirement of northern or alpine regions on the comfort level of the sole.
Detailed Description
The invention is further described below by means of specific embodiments.
A light cold-resistant EVA sole comprises the following raw materials in parts by weight:
wherein the accelerator consists of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.68-0.82: 0.5-0.7.
The preparation method comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 12-18min to obtain a premix;
step two, adding the premix prepared in the step one and other raw materials except the foaming agent, the crosslinking agent and the accelerator into an internal mixer, and mixing and banburying for 5-10 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; after the banburying temperature rises to 96 ℃, carrying out secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; when the banburying temperature is increased to 115-120 ℃, the materials are turned for five times, then the banburying is carried out for 1min, the rubber is discharged, and the mixture is placed at room temperature for more than 24 h;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
cutting the foaming sheet into a sole shape, placing the sole shape into a shoe mold, and foaming and molding to obtain the light cold-resistant EVA sole, wherein the foaming temperature is 152-.
In the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the sheet is taken out with the thickness of 2-3 mm.
Example 1
A light cold-resistant EVA sole comprises the following raw materials in parts by weight:
wherein the accelerant is composed of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.68: 0.7.
The preparation method comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 12min to obtain a premix;
step two, adding the premix prepared in the step one and other raw materials except the foaming agent, the crosslinking agent and the accelerator into an internal mixer, and mixing and banburying for 10 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; when the banburying temperature is raised to 96 ℃, performing secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; after the banburying temperature is raised to 115 ℃, the materials are turned for five times, banburying is carried out for 1min, the rubber is discharged, and the mixture is placed at room temperature for more than 24 h;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
and step four, cutting the foaming sheet into a sole shape, putting the sole shape into a shoe mold, and foaming and molding to obtain the light cold-resistant EVA sole, wherein the foaming temperature is 152 ℃.
In the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the EVA foaming sheet is taken out with the thickness of 2 mm.
Example 2
A light cold-resistant EVA sole comprises the following raw materials in parts by weight:
wherein the accelerator consists of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.82: 0.5.
The preparation method comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 18min to obtain a premix;
step two, adding the premix prepared in the step one and other raw materials except the foaming agent, the crosslinking agent and the accelerator into an internal mixer, and mixing and banburying for 5 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; when the banburying temperature is raised to 96 ℃, performing secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; after the banburying temperature is raised to 120 ℃, the materials are turned over for five times, banburying is carried out for 1min, the rubber is discharged, and the mixture is placed at room temperature for more than 24 h;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
and step four, cutting the foaming sheet into a sole shape, putting the sole shape into a shoe mold, and foaming and molding to obtain the light cold-resistant EVA sole, wherein the foaming temperature is 165 ℃.
In the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the EVA foaming sheet is taken out with the thickness of 3 mm.
Example 3
A light cold-resistant EVA sole comprises the following raw materials in parts by weight:
wherein the accelerator consists of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.75: 0.6.
The preparation method comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 15min to obtain a premix;
step two, adding the premix prepared in the step one and other raw materials except the foaming agent, the crosslinking agent and the accelerator into an internal mixer, and mixing and banburying for 7 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; when the banburying temperature is raised to 96 ℃, performing secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; after the banburying temperature rises to 118 ℃, the materials are turned over for five times, banburying is carried out for 1min, the rubber is discharged, and the mixture is placed at room temperature for more than 24 h;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
and step four, cutting the foaming sheet into a sole shape, placing the sole shape into a shoe mold, and foaming and molding to obtain the light cold-resistant EVA sole, wherein the foaming temperature is 158 ℃.
In the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the EVA foaming sheet is taken out with the thickness of 2 mm.
Comparative example 1
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: the raw materials are not added with thiourea and calcium chloride.
Comparative example 2
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: thiourea is not added in the raw material composition.
Comparative example 3
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: calcium chloride is not added in the raw material composition.
Comparative example 4
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: epoxidized soybean oil is not added in the raw material composition.
Comparative example 5
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: in the raw material composition, the asbestos fiber and the expanded vermiculite powder are replaced by talcum powder in equal amount.
Comparative example 6
The raw material composition and the preparation method are basically consistent with those of the example 3, and the differences are as follows: the feed composition of the accelerator does not include urea.
The EVA soles prepared in examples 1-3 and comparative examples 1-6 were tested to obtain the following data:
wherein, the resilience test adopts a GT-7042-RE type impact elasticity testing machine, and the slip resistance performance is as follows TM 144: 2011 test method, STM603 instrument and ice surface instrument from SATRA technology of UK, ice surface temperature-6 to-8 deg.C.
TABLE 1 data table of each example
Can know through above-mentioned table, the EVA sole of this application preparation has the light, elasticity of quality and the good advantage of skid resistance, satisfies the requirement to the sole comfort level in north or severe cold district.
The EVA sole is limited to be mutually mixed with the silicon rubber, the hydrogenated nitrile rubber and the thermoplastic elastomer, and the maleic anhydride is added to graft the EVA so as to increase the compatibility and the adhesion among raw materials, so that the cold resistance of the prepared EVA sole is improved, the prepared EVA sole can keep good flexibility and elasticity in the cold environment of the north or the alpine region, and the requirement of the north or the alpine region on the comfort level of the sole is met; the low-temperature resistance of the prepared EVA sole is further improved by introducing thiourea and calcium chloride to be matched with the silicon rubber and the hydrogenated nitrile rubber, and the thiourea can be matched with an accelerator to improve the foaming effect of the EVA sole so as to ensure the overall mechanical property of the EVA sole; introducing epoxidized soybean oil to be matched with the main raw material so as to ensure the elasticity of the prepared EVA sole in a low-temperature environment; although the raw materials used are conventional additives, the raw materials have interaction through reasonable raw material composition and part adjustment, so that the low temperature resistance of the EVA shoe sole is improved.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents and modifications within the scope of the description.
Claims (9)
1. The utility model provides a cold-resistant EVA sole of light which characterized in that: the feed comprises the following raw materials in parts by weight:
2. the light cold-resistant EVA shoe sole of claim 1, wherein: the accelerator consists of zinc stearate, urea and triethylenediamine according to the mass ratio of 1:0.68-0.82: 0.5-0.7.
3. The light cold-resistant EVA shoe sole of claim 1, wherein: the cross-linking agent is a cross-linking agent BIBP.
4. The light cold-resistant EVA sole of claim 1, wherein: the foaming agent is foaming agent AC.
5. The light cold-resistant EVA shoe sole of claim 1, wherein: the EVA comprises 18-25 parts of EVA7470 and 22-35 parts of EVA 33121.
6. The preparation method of the light cold-resistant EVA sole is characterized by comprising the following steps: the method comprises the following steps:
firstly, placing EVA, silicon rubber, hydrogenated nitrile rubber and thermoplastic elastomer in required parts by weight into an internal mixer for internal mixing for 12-18min to obtain a premix;
step two, putting the premix prepared in the step one and the raw materials except the foaming agent, the cross-linking agent and the accelerator into an internal mixer, mixing and internally mixing, discharging rubber at the temperature of 115 ℃ and 120 ℃, and standing at room temperature for more than 24 hours;
mixing the internally mixed mixture on an open mill, adding accurately weighed foaming agent, crosslinking agent and accelerator, uniformly mixing the materials, and then sheet-shaped discharging to obtain a foamed sheet;
and step four, cutting the foaming sheet into a sole shape, and placing the sole shape into a shoe mold for foaming and molding to obtain the light cold-resistant EVA sole.
7. The preparation method of the light cold-resistant EVA sole according to claim 6, wherein the preparation method comprises the following steps: in the second step, the banburying process specifically comprises the following steps: adding the premix prepared in the step one and other raw materials except the foaming agent, the crosslinking agent and the accelerator into an internal mixer, and mixing and banburying for 5-10 min; then adjusting the banburying temperature to 90 ℃, keeping for 3min and then turning for one time; when the banburying temperature is raised to 96 ℃, performing secondary material turning; when the banburying temperature is raised to 102 ℃, turning materials for three times; stirring for four times when the banburying temperature is raised to 110 ℃; and (4) after the banburying temperature is raised to 115-120 ℃, performing five times of material turning, banburying for 1min, discharging the rubber, and standing at room temperature for more than 24 h.
8. The preparation method of the light cold-resistant EVA sole according to claim 6, wherein the preparation method comprises the following steps: in the fourth step, the foaming temperature is 152-165 ℃.
9. The preparation method of the light cold-resistant EVA sole according to claim 6, wherein the preparation method comprises the following steps: in the third step, the EVA foaming sheet is thinned at least twice in an open mill, and the sheet is taken out with the thickness of 2-3 mm.
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Address after: No. 588, Jinxin Middle Road, Jiangtou village, Chendai Town, Jinjiang City, Quanzhou City, Fujian Province, 362000 Applicant after: Maotai (Fujian) New Material Technology Co.,Ltd. Applicant after: Shengtai (Fujian) shoe material Co.,Ltd. Address before: No. 588, Jinxin Middle Road, Jiangtou village, Chendai Town, Jinjiang City, Quanzhou City, Fujian Province, 362000 Applicant before: Maotai(Fujian) Soles Co.,Ltd. Applicant before: Shengtai (Fujian) shoe material Co.,Ltd. |
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