CN112724648B - Anti-aging sole material and preparation method thereof - Google Patents
Anti-aging sole material and preparation method thereof Download PDFInfo
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- CN112724648B CN112724648B CN202011604693.7A CN202011604693A CN112724648B CN 112724648 B CN112724648 B CN 112724648B CN 202011604693 A CN202011604693 A CN 202011604693A CN 112724648 B CN112724648 B CN 112724648B
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
Abstract
The invention is suitable for the technical field of articles for daily use, and provides an anti-aging sole material which comprises the following raw materials in parts by weight: 30-50 parts of polyvinyl chloride polyurethane, 15-35 parts of hydrogenated styrene-butadiene-styrene copolymer, 1-7 parts of anti-aging modification auxiliary agent, 10-18 parts of foaming agent, 1-5 parts of softener, 1-5 parts of plasticizer and 1-5 parts of antioxidant. The invention also provides a preparation method of the anti-aging sole material, which is characterized in that the hydrogenated styrene-butadiene-styrene copolymer and the polyvinyl chloride polyurethane are mixed for use, the hydrogenated styrene-butadiene-styrene copolymer has an ordered structure and high crystallinity, and can effectively lock gas generated by a foaming agent, so that the material is lighter, and the problems of uneven foaming, hole stringing, surface depression and the like are solved; meanwhile, an anti-aging modification auxiliary agent is added in an auxiliary manner, a main chain saturated structure is increased, the sole structure is distributed more finely and orderly, and the anti-aging performance of the sole is effectively improved.
Description
Technical Field
The invention relates to the technical field of articles for daily use, in particular to an anti-aging sole material and a preparation method thereof.
Background
With the improvement of living standard of people, people begin to pursue high-quality life in all aspects, and focus on pursuing better comfort level in the aspect of selecting shoes. The sole material is a companion of footwear products, and the quality of the sole material is continuously improved along with the development of the footwear products. The traditional sole material mainly adopts natural materials, mainly animal leather, fiber fabric, natural milk rubber and the like, and the modern sole mainly adopts artificial materials, mainly synthetic rubber, plastic, metal and the like.
The problem of aging of polymeric materials has been of concern, particularly for rubber articles. The aging of rubber is mainly the phenomenon that rubber products are affected by external factors such as heat, oxygen, light, mechanical stress, ozone, harmful metal ions, chemical media and the like during storage or use, so that the rubber products are subjected to physical and chemical changes, the performance of the rubber products is deteriorated, and the use value of the rubber products is gradually lost. Aging is a process by which the properties of a material change from good to bad.
The basic principle of rubber aging is that rubber generates chemical reactions such as crosslinking or degradation under the action of aging factors such as heat, oxygen, light, ozone and the like, and macroscopically shows the change of physical-mechanical properties, so that the service performance is finally lost. The factors that cause rubber aging are quite complex in a wide variety of use environments. The aging mechanism is different under different factors. Among them, thermo-oxidative aging is the most basic and important aging phenomenon of polymers such as rubber. Thermal oxidative aging is a free radical chain type autocatalytic oxidation reaction which is mainly carried out according to a free radical reaction process, wherein one method for improving the thermal oxidative aging resistance of rubber is to add a substance which reacts with a free radical to stop the generation of the free radical chain type autocatalytic oxidation reaction.
The anti-aging performance of the sole material on the market at present is obviously reduced after the sole material is used for a period of time, so that the tensile strength of the sole material is directly influenced, cracks and even breakage are easy to occur, and the service life of the sole material is greatly shortened.
Disclosure of Invention
The embodiment of the invention provides an anti-aging sole material, aiming at mixing hydrogenated styrene-butadiene-styrene copolymer with polyvinyl chloride polyurethane for use, wherein the hydrogenated styrene-butadiene-styrene copolymer has an ordered structure and high crystallinity, can effectively lock gas generated by a foaming agent, enables the material to be lighter, and solves the problems of uneven foaming, cross pores, surface depression and the like; meanwhile, an anti-aging modification auxiliary agent is added in an auxiliary manner, a main chain saturated structure is increased, the sole structure is distributed more finely and orderly, and the anti-aging performance of the sole is effectively improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an anti-aging sole material comprises the following raw materials in parts by weight:
30-50 parts of polyvinyl chloride polyurethane, 15-35 parts of hydrogenated styrene-butadiene-styrene copolymer, 1-7 parts of anti-aging modification auxiliary agent, 10-18 parts of foaming agent, 1-5 parts of softener, 1-5 parts of plasticizer and 1-5 parts of antioxidant.
Further, the foaming agent is sodium dodecyl sulfate.
Further, the softening agent is stearic acid.
Further, the plasticizer is propyl acetate.
Further, the antioxidant is isooctyl acrylate.
Further, the preparation method of the anti-aging modification auxiliary agent comprises the following steps:
1) grinding wollastonite into powder, and then putting the powder into an oven to dry;
2) adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1:3, stirring for 20-30 min, and cooling to room temperature.
Further, the grinding precision in the step 1) is 20-30 meshes.
The invention also discloses a preparation method of the anti-aging sole material, which comprises the following steps:
1) weighing polyvinyl chloride polyurethane and hydrogenated styrene-butadiene-styrene copolymer according to the weight parts, mixing and placing in an internal mixer, banburying at 85-105 ℃ for 20-25 min, and cooling to obtain premixed rubber for later use;
2) adding an anti-aging modification auxiliary agent and a foaming agent into the premixed rubber, placing the premixed rubber in a high-speed kneading machine, kneading the premixed rubber for 5-10 min at the temperature of 150-200 ℃, continuously adding a softening agent, a plasticizer and an antioxidant, and continuously kneading the kneaded rubber for 15-20 min to obtain a mixed material;
3) extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming;
4) and (3) carrying out irradiation crosslinking on the molded product obtained in the step 3) by adopting a high-energy electron ray to obtain the anti-aging sole material.
The invention has the following beneficial effects:
according to the invention, the hydrogenated styrene-butadiene-styrene copolymer and the polyvinyl chloride polyurethane are mixed for use, the hydrogenated styrene-butadiene-styrene copolymer has an ordered structure and high crystallinity, and can effectively lock gas generated by a foaming agent, so that the material is lighter, and the problems of uneven foaming, hole stringing, surface depression and the like are solved; meanwhile, an anti-aging modification auxiliary agent is added in an auxiliary manner, a main chain saturated structure is increased, the sole structure is distributed more finely and orderly, and the anti-aging performance of the sole is effectively improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The hydrogenated styrene-butadiene-styrene copolymer is mixed with the polyvinyl chloride polyurethane for use, has an ordered structure and high crystallinity, can effectively lock gas generated by a foaming agent, enables the material to be lighter, and solves the problems of uneven foaming, hole crossing, surface depression and the like;
the anti-aging modification auxiliary agent is added in an auxiliary manner, the main chain saturated structure is increased, the sole structure is distributed more finely and orderly, and the anti-aging performance of the sole is effectively improved.
Specifically, the embodiment of the invention provides an anti-aging sole material which comprises the following raw materials in parts by weight:
30-50 parts of polyvinyl chloride polyurethane, 15-35 parts of hydrogenated styrene-butadiene-styrene copolymer, 1-7 parts of anti-aging modification auxiliary agent, 10-18 parts of foaming agent, 1-5 parts of softener, 1-5 parts of plasticizer and 1-5 parts of antioxidant.
In the embodiment of the invention, the foaming agent is sodium dodecyl sulfate.
In the embodiment of the invention, the softening agent is stearic acid.
In the embodiment of the invention, the plasticizer is propyl acetate.
In the embodiment of the invention, the antioxidant is isooctyl acrylate.
In the embodiment of the invention, the preparation method of the anti-aging modification auxiliary agent comprises the following steps:
1) grinding wollastonite into powder, and then putting the powder into an oven for drying;
2) adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1:3, stirring for 20-30 min, and cooling to room temperature.
In the embodiment of the invention, the grinding precision in the step 1) is 20-30 meshes.
The embodiment of the invention also provides a preparation method of the anti-aging sole material, which comprises the following steps:
1) weighing polyvinyl chloride polyurethane and hydrogenated styrene-butadiene-styrene copolymer according to the weight parts, mixing and placing in an internal mixer, banburying at 85-105 ℃ for 20-25 min, and cooling to obtain premixed rubber for later use;
2) adding an anti-aging modification auxiliary agent and a foaming agent into the premixed rubber, placing the premixed rubber in a high-speed kneading machine, kneading the premixed rubber for 5-10 min at the temperature of 150-200 ℃, continuously adding a softening agent, a plasticizer and an antioxidant, and continuously kneading the kneaded rubber for 15-20 min to obtain a mixed material;
3) extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming;
4) and (3) carrying out irradiation crosslinking on the molded product obtained in the step 3) by adopting a high-energy electron ray to obtain the anti-aging sole material.
The technical solution and the technical effect of the present invention will be further described by specific examples.
Example 1
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 1g of anti-aging modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding the mixed material through a double-screw extruder for granulation, and plasticizing and molding; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 2
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into the wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 20g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, carrying out internal mixing at the temperature of 100 ℃ for 20min, and cooling to obtain pre-mixed rubber; weighing 1g of anti-aging modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 3
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into the wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 25g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 1g of anti-aging modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 4
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into the wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 30g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 1g of anti-aging modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 5
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 35g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 1g of anti-aging modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 6
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 2g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding the mixed material through a double-screw extruder for granulation, and plasticizing and molding; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 7
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 3g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 8
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 4g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 9
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into the wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 5g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 10
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 6g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 11
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 15g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 7g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Example 12
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane and 25g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 4g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding the mixed material through a double-screw extruder for granulation, and plasticizing and molding; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Control group
Taking a common sole material sold in the market.
The sole materials in examples 1 to 12 and the control group were subjected to an aging test at 100 ℃ for 48 hours, and the tensile strength, impact strength and elongation at break of each group of products were measured, and the specific data are shown in table 1:
TABLE 1
| Numbering | Item of implementation | Tensile Strength (MPa) | Impact strength (kJ/square meter) | Elongation at Break (%) |
| 1 | Example 1 | 10.6 | 33 | 18.3 |
| 2 | Example 2 | 10.9 | 36 | 18.1 |
| 3 | Example 3 | 11.2 | 42 | 17.6 |
| 4 | Example 4 | 11.0 | 39 | 17.9 |
| 5 | Example 5 | 10.8 | 35 | 18.2 |
| 6 | Example 6 | 10.7 | 34 | 18.1 |
| 7 | Example 7 | 11.1 | 40 | 17.4 |
| 8 | Example 8 | 11.4 | 45 | 17.1 |
| 9 | Example 9 | 11.2 | 43 | 17.3 |
| 10 | Example 10 | 10.8 | 41 | 17.6 |
| 11 | Example 11 | 10.5 | 37 | 17.9 |
| 12 | Example 12 | 11.7 | 48 | 16.4 |
| 13 | Control group | 8.3 | 26 | 23.3 |
As can be seen from Table 1, the sole material prepared by the invention has more excellent tensile and impact resistance in an aging test compared with the common sole materials sold in the market, wherein the sole material prepared by the embodiment 12 has the highest tensile strength and impact resistance, the lowest elongation at break and the most excellent aging resistance; according to examples 1 to 5, when the amount of the hydrogenated styrene-butadiene-styrene copolymer is 25g, the prepared sole material has the highest tensile strength and impact strength, the lowest elongation at break and the most excellent aging resistance; according to the embodiments 1 and 6 to 12, when the dosage of the anti-aging modification auxiliary agent is 4g, the prepared sole material has the highest tensile strength and impact strength, the lowest elongation at break and the most excellent anti-aging performance.
Further, the invention is based on the preparation steps of example 12, and the single factor deletion comparative experiment is performed on the hydrogenated styrene-butadiene-styrene copolymer and the anti-aging modification auxiliary agent, and the experimental result shows that different factors are deleted, and the finally prepared sole material has a certain difference in anti-aging performance, which is concretely shown in the following comparative examples.
Comparative example 1
Grinding a certain amount of wollastonite into powder of 30 meshes, and then putting the powder into an oven for drying; adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, stirring for 30min, and cooling to room temperature to obtain an aging-resistant modified auxiliary agent for later use, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1: 3; weighing 40g of polyvinyl chloride polyurethane, placing the polyvinyl chloride polyurethane in an internal mixer, carrying out internal mixing for 20min at the temperature of 100 ℃, and cooling to obtain pre-mixed rubber; weighing 4g of ageing-resistant modification auxiliary agent and 14g of foaming agent, adding into the premixed glue, placing into a high-speed kneading machine, kneading for 10min at 150 ℃, continuously adding 3g of softening agent, 3g of plasticizer and 3g of antioxidant, and continuously kneading for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Comparative example 2
Weighing 40g of polyvinyl chloride polyurethane and 25g of hydrogenated styrene-butadiene-styrene copolymer, mixing and placing in an internal mixer, banburying at 100 ℃ for 20min, and cooling to obtain premixed rubber; weighing 14g of foaming agent, adding the foaming agent into the premixed glue, placing the premixed glue in a high-speed kneader, kneading the mixture for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading the mixture for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
Comparative example 3
Weighing 40g of polyvinyl chloride polyurethane, placing the polyvinyl chloride polyurethane in an internal mixer, carrying out internal mixing for 20min at the temperature of 100 ℃, and cooling to obtain pre-mixed rubber; weighing 14g of foaming agent, adding the foaming agent into the premixed glue, placing the premixed glue in a high-speed kneader, kneading the mixture for 10min at 150 ℃, continuously adding 3g of softener, 3g of plasticizer and 3g of antioxidant, and continuously kneading the mixture for 20min to obtain a mixed material; extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming; and then, carrying out irradiation crosslinking on the formed product by adopting high-energy electron rays to obtain the anti-aging sole material.
The sole materials in comparative examples 1-3 are subjected to a 100 ℃ aging test for 48 hours to measure the tensile strength, impact strength and elongation at break of each group of products, and the specific data are shown in Table 2:
TABLE 2
As can be seen from Table 2, the aging resistance of the anti-aging sole material prepared by the invention is greatly improved compared with the single use of the hydrogenated styrene-butadiene-styrene copolymer and the single use of the anti-aging modification auxiliary agent.
In general, the hydrogenated styrene-butadiene-styrene copolymer and the polyvinyl chloride polyurethane are mixed for use, the hydrogenated styrene-butadiene-styrene copolymer has an ordered structure and high crystallinity, and can effectively lock gas generated by a foaming agent, so that the material is lighter, and the problems of uneven foaming, hole stringing, surface depression and the like are solved; meanwhile, an anti-aging modification auxiliary agent is added in an auxiliary manner, a main chain saturated structure is increased, the sole structure is distributed more finely and orderly, and the anti-aging performance of the sole is effectively improved.
It should be understood that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The anti-aging sole material is characterized by comprising the following raw materials in parts by weight:
30-50 parts of polyvinyl chloride polyurethane, 15-35 parts of hydrogenated styrene-butadiene-styrene copolymer, 1-7 parts of anti-aging modification auxiliary agent, 10-18 parts of foaming agent, 1-5 parts of softener, 1-5 parts of plasticizer and 1-5 parts of antioxidant; the preparation method of the anti-aging modification auxiliary agent comprises the following steps:
1) grinding wollastonite into powder, and then putting the powder into an oven to dry;
2) adding nano zinc dioxide and nano ceramic powder into wollastonite powder, uniformly mixing, wherein the mass ratio of wollastonite to nano zinc dioxide to nano ceramic powder is 10:1:3, stirring for 20-30 min, and cooling to room temperature.
2. The aging-resistant sole material according to claim 1, characterized by comprising the following raw materials in parts by weight:
35-45 parts of polyvinyl chloride polyurethane, 20-30 parts of hydrogenated styrene-butadiene-styrene copolymer, 3-5 parts of anti-aging modification auxiliary agent, 12-16 parts of foaming agent, 2-4 parts of softener, 2-4 parts of plasticizer and 2-4 parts of antioxidant.
3. The aging-resistant sole material according to claim 1, characterized by comprising the following raw materials in parts by weight:
40 parts of polyvinyl chloride polyurethane, 25 parts of hydrogenated styrene-butadiene-styrene copolymer, 4 parts of ageing-resistant modification auxiliary agent, 14 parts of foaming agent, 3 parts of softening agent, 3 parts of plasticizer and 3 parts of antioxidant.
4. The aging-resistant sole material of claim 1, wherein the foaming agent is sodium lauryl sulfate.
5. The aging-resistant sole material according to claim 1, wherein the softening agent is stearic acid.
6. The aging-resistant sole material of claim 1, wherein the plasticizer is propyl acetate.
7. The age-resistant sole material of claim 1, wherein the antioxidant is isooctyl acrylate.
8. The aging-resistant sole material according to claim 1, wherein the grinding precision in the step 1) is 20-30 meshes.
9. A preparation method of the anti-aging sole material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
1) weighing polyvinyl chloride polyurethane and hydrogenated styrene-butadiene-styrene copolymer according to the weight parts, mixing and placing in an internal mixer, banburying at 85-105 ℃ for 20-25 min, and cooling to obtain premixed rubber for later use;
2) adding an anti-aging modification auxiliary agent and a foaming agent into the premixed rubber, placing the premixed rubber in a high-speed kneading machine, kneading the premixed rubber for 5-10 min at the temperature of 150-200 ℃, continuously adding a softening agent, a plasticizer and an antioxidant, and continuously kneading the kneaded rubber for 15-20 min to obtain a mixed material;
3) extruding and granulating the mixed material through a double-screw extruder, and plasticizing and forming;
4) and (3) carrying out irradiation crosslinking on the molded product obtained in the step 3) by adopting a high-energy electron ray to obtain the anti-aging sole material.
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| GB1048267A (en) * | 1963-09-12 | 1966-11-16 | Marley Tile Co Ltd | Flooring materials comprising polyurethane foam materials |
| JPH06200106A (en) * | 1993-01-06 | 1994-07-19 | Tosoh Corp | Production of polyvinyl chloride-polyurethane elastomer |
| CN103805044B (en) * | 2014-01-23 | 2016-03-23 | 福建宝利特科技股份有限公司 | A kind of preparation method of ultrasonic-assisted synthesis leather use polyurethane foam slurry |
| CN103937092A (en) * | 2014-03-20 | 2014-07-23 | 安徽春辉仪表线缆集团有限公司 | Thermally conductive and insulating power cable sheath material |
| CN105542323B (en) * | 2016-01-20 | 2018-01-16 | 苏州市景荣科技有限公司 | A kind of heat oxygen aging resistance rubber soles material and preparation method thereof |
| CN107383766A (en) * | 2017-08-31 | 2017-11-24 | 安徽华海特种电缆集团有限公司 | A kind of high-temperature-resistant, tensile controls CABLE MATERIALS |
| CN109354817A (en) * | 2018-11-01 | 2019-02-19 | 晋江市新奇美鞋材发展有限公司 | A kind of fireproof wear-resisting rubber soles material and preparation method thereof |
| CN110903629A (en) * | 2019-12-21 | 2020-03-24 | 惠安伟盛鞋业有限公司 | High-elasticity wear-resistant polyurethane foamed shoe material and preparation method thereof |
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