CN113549339B - Leisure shoe sole and preparation method thereof - Google Patents
Leisure shoe sole and preparation method thereof Download PDFInfo
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- CN113549339B CN113549339B CN202110905041.5A CN202110905041A CN113549339B CN 113549339 B CN113549339 B CN 113549339B CN 202110905041 A CN202110905041 A CN 202110905041A CN 113549339 B CN113549339 B CN 113549339B
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the field of board shoe manufacturing technology, and particularly discloses a leisure shoe sole and a preparation method thereof. The sole of the leisure shoe comprises, by weight, 80-120 parts of TPR reclaimed materials, 20-40 parts of polypropylene, 15-30 parts of thermoplastic styrene-butadiene rubber, 0.05-0.15 part of cross-linking agents, 3-7 parts of polyacrylamide, 2-6 parts of polymethacrylate and 0.5-1.5 parts of amino modified polyacrylic acid; the preparation method comprises the following steps: s1, mixing the TPR reclaimed material, polypropylene, thermoplastic styrene-butadiene rubber and a cross-linking agent, banburying, adding polyacrylamide, polymethacrylate and amino modified polyacrylic acid, continuing banburying, and granulating to obtain granules; and S2, heating the granulated material to a molten state, and then extruding the granulated material into a sole mold to perform injection molding to obtain the leisure shoe sole. The utility model provides a playshoes sole has better ageing resistance under ultraviolet irradiation, and is friendly to the environment.
Description
Technical Field
The application relates to the field of board shoe manufacturing technology, in particular to a leisure shoe sole and a preparation method thereof.
Background
The leisure shoes are simple and comfortable in design concept, and can meet the daily life requirements of people. With the continuous development of the economic society, the living standard of people is gradually improved, so that higher living quality and living experience are pursued, the shape and the connotation of the leisure shoes can meet the requirements of people, and the aesthetic pleasure spirit is obtained.
The sole of leisure shoes is mostly rubber soles, and rubber soles are comparatively soft, have higher elasticity and shock resistance. China has huge leisure shoe market, a large amount of leisure shoes are produced every year, and a lot of leftover materials and waste soles of thermoplastic rubber soles are generated. The thermoplastic rubber is generally a high molecular polymer, has high molecular weight and strong intermolecular force, is difficult to degrade after being discarded, and is easy to cause environmental pollution after being accumulated for a long time.
Therefore, the recycled thermoplastic rubber sole waste is tried to be processed again to produce the rubber sole, for example, the Chinese patent with the application number of 2019110305155 uses the recycled TPR material and the polystyrene reclaimed material as main raw materials, and the environment-friendly rubber sole is prepared by adding starch grafted EVA and maleic anhydride grafted SBS.
With respect to the related art in the above, the inventors consider that: the prepared rubber sole has insufficient aging resistance under ultraviolet irradiation, and the service life of the sole after being aired for multiple times is shortened.
Disclosure of Invention
In order to prolong the service life of the soles of the casual shoes, the application provides the soles of the casual shoes and the preparation method thereof.
In a first aspect, the application provides a leisure shoe sole, which adopts the following technical scheme:
the leisure shoe sole comprises, by weight, 80-120 parts of TPR reclaimed materials, 20-40 parts of polypropylene, 15-30 parts of thermoplastic styrene-butadiene rubber, 0.05-0.15 part of a cross-linking agent, 3-7 parts of polyacrylamide, 2-6 parts of polymethacrylate and 0.5-1.5 parts of amino modified polyacrylic acid.
Through adopting above-mentioned technical scheme, this application has adjusted to the preparation raw materials of playshoes sole, the TPR reclaimed materials of this application is the stub bar in the TPR sole production, substandard product or waste product, TPR reclaimed materials and polypropylene, thermoplasticity butadiene styrene rubber mixes and forms crosslinked structure, polyacrylamide and the addition of amino modification polyacrylic acid can improve the compatibility of playshoes preparation system, polymethacrylate adds back and polyacrylamide interact, the stability of blending crosslinked system has been improved, thereby the ageing resistance of playshoes sole under ultraviolet irradiation has been improved, the life of playshoes sole has been prolonged. The TPR reclaimed material which is difficult to degrade is recycled, so that the cost can be reduced, and the environment protection is facilitated.
Preferably, the thermoplastic styrene-butadiene rubber has a star-shaped structure.
By adopting the technical scheme, the thermoplastic styrene butadiene rubber with the star-shaped structure has higher processing flowability, higher compatibility in a preparation system of the soles of the leisure shoes, and higher aging resistance of the soles of the prepared leisure shoes under the irradiation of ultraviolet light.
Preferably, the thermoplastic styrene-butadiene rubber with the star-shaped structure is a mixture of LG-475 type thermoplastic styrene-butadiene rubber and LG-411 type thermoplastic styrene-butadiene rubber.
Preferably, the weight ratio of the LG-475 type thermoplastic styrene-butadiene rubber to the LG-411 type thermoplastic styrene-butadiene rubber is (1-3): 1.
by adopting the technical scheme, the LG-475 type thermoplastic styrene-butadiene rubber and the LG-411 type thermoplastic styrene-butadiene rubber are compounded, and when the weight ratio of the LG-475 type thermoplastic styrene-butadiene rubber to the LG-411 type thermoplastic styrene-butadiene rubber is (1-3): 1, the aging resistance of the prepared leisure shoe sole under the irradiation of ultraviolet light is improved.
Preferably, the crosslinking agent is dicumyl peroxide.
Preferably, the polyacrylamide is a mixture of cationic polyacrylamide and anionic polyacrylamide; more preferably, the weight ratio of the cationic polyacrylamide to the anionic polyacrylamide is (2-3): 2.
by adopting the technical scheme, the cationic polyacrylamide and the anionic polyacrylamide are compounded and interact with each other, so that the stability of a blending crosslinking system is further improved, and the aging resistance of the soles of the leisure shoes under ultraviolet irradiation is improved.
Preferably, the polymethacrylate is sodium polymethacrylate.
In a second aspect, the application provides a method for preparing a sole of a casual shoe, which adopts the following technical scheme:
a preparation method of a leisure shoe sole comprises the following preparation steps:
s1, mixing the TPR reclaimed material, polypropylene, thermoplastic styrene-butadiene rubber and a cross-linking agent, banburying at 110-120 ℃, adding polyacrylamide, polymethacrylate and amino modified polyacrylic acid, continuing banburying for 3-7min, and granulating to obtain granules;
and S2, heating the granulated material to a molten state, and then extruding the granulated material into a sole mold to perform injection molding to obtain the leisure shoe sole.
Through adopting above-mentioned technical scheme, this application has adjusted to the preparation raw materials of playshoes sole, and TPR reclaimed materials and polypropylene, thermoplasticity butadiene styrene rubber blend and form crosslinked structure, and polymethacrylate adds back and polyacrylamide interact, has improved the stability of blending crosslinking system to improve the ageing resistance of playshoes sole under the ultraviolet irradiation, prolonged the life of playshoes sole.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the preparation method, the preparation raw materials of the soles of the casual shoes are adjusted, the TPR reclaimed materials, the polypropylene and the thermoplastic styrene-butadiene rubber are blended to form a cross-linking structure, and the polymethacrylate is added and then interacts with the polyacrylamide, so that the stability of the blending cross-linking system is improved, the ageing resistance of the soles of the casual shoes under ultraviolet irradiation is improved, and the service life of the soles of the casual shoes is prolonged; TPR reclaimed materials which are difficult to degrade can be recycled, so that the cost can be reduced, and the environment protection is facilitated; 2. the composite material is preferably compounded by LG-475 type thermoplastic styrene-butadiene rubber and LG-411 type thermoplastic styrene-butadiene rubber, so that the aging resistance of the soles of the leisure shoes under the irradiation of ultraviolet light is improved, and the service life of the soles of the leisure shoes is prolonged;
3. according to the application, cationic polyacrylamide and anionic polyacrylamide are preferably compounded, so that the stability of a blending crosslinking system is further improved, and the aging resistance of the soles of the leisure shoes under ultraviolet irradiation is improved.
Detailed Description
The present application is further described in detail with reference to the following examples, wherein the recycled TPR material used in the present application is a stub bar, a waste product, a defective product, a leftover material and a waste product generated in the production process of TPR shoe soles; the product number of the amino modified polyacrylic acid is 2342343453, and the amino modified polyacrylic acid is purchased from Xian Ruixi biological technology limited company; the remaining sources are shown in Table 1 unless otherwise specified.
TABLE 1 sources of raw materials used in the present application
Examples
Example 1
A preparation method of a leisure shoe sole comprises the following preparation steps:
s1, mixing 1kg of TPR reclaimed material, 0.3kg of polypropylene, 0.2kg of thermoplastic styrene-butadiene rubber and 0.001kg of cross-linking agent, banburying at 120 ℃ for 15min, adding 0.05kg of polyacrylamide, 0.04kg of polymethacrylate and 0.01kg of amino modified polyacrylic acid, continuing banburying for 5min, and then granulating to obtain granules;
s2, heating 0.8kg of the granulated material to a molten state, extruding the granulated material into a corresponding sole mold, and performing injection molding to obtain the sole of the casual shoe, wherein the injection molding temperature is 180 ℃, and the mold pressure maintaining time is 1S;
the thermoplastic styrene-butadiene rubber is of a linear structure and has the model of LG-604; the polyacrylamide is anionic polyacrylamide.
Examples 2 to 9
Examples 2 to 9 are based on example 1 and differ from example 1 only in that: the preparation conditions of the leisure shoe soles are different, and are specifically shown in table 2.
TABLE 2 preparation conditions of soles of casual shoes in examples 1 to 9
Example 10
Example 10 is based on example 1 and differs from example 1 only in that: the thermoplastic styrene-butadiene rubber is LG-475 type thermoplastic styrene-butadiene rubber with a star-shaped structure.
Example 11
Example 11 is based on example 1 and differs from example 1 only in that: the thermoplastic styrene-butadiene rubber is LG-411 type thermoplastic styrene-butadiene rubber with a star-shaped structure.
Example 12
Example 12 is based on example 1 and differs from example 1 only in that: the thermoplastic styrene-butadiene rubber is a mixture of LG-475 type thermoplastic styrene-butadiene rubber and LG-411 type thermoplastic styrene-butadiene rubber, and the weight ratio of the LG-475 type thermoplastic styrene-butadiene rubber to the LG-411 type thermoplastic styrene-butadiene rubber is 1: 1.
example 13
Example 13 is based on example 1 and differs from example 1 only in that: the thermoplastic styrene-butadiene rubber is a mixture of LG-475 type thermoplastic styrene-butadiene rubber and LG-411 type thermoplastic styrene-butadiene rubber, and the weight ratio of the LG-475 type thermoplastic styrene-butadiene rubber to the LG-411 type thermoplastic styrene-butadiene rubber is 3: 1.
example 14
Example 14 is based on example 1 and differs from example 1 only in that: the thermoplastic styrene-butadiene rubber is a mixture of LG-475 type thermoplastic styrene-butadiene rubber and LG-411 type thermoplastic styrene-butadiene rubber, and the weight ratio of the LG-475 type thermoplastic styrene-butadiene rubber to the LG-411 type thermoplastic styrene-butadiene rubber is 2: 1.
example 15
Example 15 is based on example 14 and differs from example 15 only in that: the polyacrylamide is cationic polyacrylamide.
Example 16
Example 16 is based on example 15 and differs from example 15 only in that: the polyacrylamide is a mixture of cationic polyacrylamide and anionic polyacrylamide, and the weight ratio of the cationic polyacrylamide to the anionic polyacrylamide is 1: 1.
example 17
Example 17 is based on example 15 and differs from example 15 only in that: the polyacrylamide is a mixture of cationic polyacrylamide and anionic polyacrylamide, and the weight ratio of the cationic polyacrylamide to the anionic polyacrylamide is 3: 2.
comparative example
Comparative example 1
Comparative example 1 is based on example 1 and differs from example 1 only in that: the TPR reclaimed material with equal mass is used for replacing polyacrylamide.
Comparative example 2
Comparative example 2 is based on example 1 and differs from example 1 only in that: the TPR reclaimed material with equal mass is used for replacing polymethacrylate.
Comparative example 3
Comparative example 3 is based on example 1 and differs from example 1 only in that: TPR reclaimed materials with equal mass are used for replacing amino modified polyacrylic acid.
Performance test
The aging resistance of the soles of the casual shoes prepared in examples 1 to 17 and comparative examples 1 to 3 was measured.
Aging resistance: the color difference between the soles of the leisure shoes prepared before and after the irradiation of the ultraviolet light is tested according to the specification of ASTM-D1148 (rubber ultraviolet light color changing standard), the lamp tube of the ultraviolet light is UVA-340 lamp tube during the test, the operation of the ultraviolet testing device complies with the specification of ASTM G154, and the test conditions are as follows: the lighting time of 8h, the temperature of the blackboard is 60 +/-3 ℃, the condensation time of 4h and the temperature of the blackboard is 50 +/-3 ℃, and the test results are shown in table 3.
And (3) testing the skid resistance: the slip resistance of the soles of the leisure shoes obtained in examples 1 to 17 and comparative examples 1 to 3 were tested according to ASTM F2913-2017, and the test results are shown in Table 3.
And (3) wear resistance test: the wear resistance of the soles prepared in the examples 1-17 and the comparative examples 1-4 is respectively tested by adopting a universal friction wear testing machine, the testing force is 30N, the rotating speed is 250r/min, the testing time is 30min, and the wear rate calculation formula is as follows: the wear rate (weight of sole before rubbing-weight of sole after rubbing)/weight of sole before rubbing x 100%, the smaller the wear rate of the sole, the better the wear resistance, and the test results are shown in table 3.
TABLE 3 test results of soles of casual shoes of examples 1 to 17 and comparative examples 1 to 3
| Examples | Color difference Δ E (NBS) | Coefficient of skid resistance | Wear rate (%) |
| Example 1 | 0.6 | 0.43 | 1.03 |
| Example 2 | 0.7 | 0.42 | 1.02 |
| Example 3 | 0.7 | 0.43 | 1.05 |
| Example 4 | 0.6 | 0.43 | 1.07 |
| Example 5 | 0.8 | 0.43 | 1.07 |
| Example 6 | 0.7 | 0.42 | 1.05 |
| Example 7 | 0.6 | 0.41 | 1.04 |
| Example 8 | 0.8 | 0.43 | 1.04 |
| Example 9 | 0.7 | 0.44 | 1.03 |
| Example 10 | 0.4 | 0.41 | 1.03 |
| Example 11 | 0.4 | 0.43 | 1.02 |
| Example 12 | 0.3 | 0.42 | 1.03 |
| Example 13 | 0.3 | 0.43 | 1.03 |
| Example 14 | 0.2 | 0.41 | 1.04 |
| Example 15 | 0.3 | 0.42 | 1.03 |
| Example 16 | 0.1 | 0.42 | 1.03 |
| Example 17 | 0.1 | 0.43 | 1.04 |
| Comparative example 1 | 1.2 | 0.42 | 1.05 |
| Comparative example 2 | 1.5 | 0.41 | 1.04 |
| Comparative example 3 | 1.3 | 0.42 | 1.04 |
The above data of analysis can know, the colour difference all is less than 1 behind the ultraviolet irradiation at this application leisure shoe sole, has higher ageing-resistant performance under the ultraviolet irradiation, and has better antiskid nature and wearability. The data of examples 1 to 9 were analyzed, and it was found that example 1 is the most preferable example among examples 1 to 9.
Analysis of the data in example 1, comparative examples 1 to 3, and table 3 shows that when any one of polyacrylamide, polymethacrylate, and amino-modified polyacrylic acid is not added to the raw materials for preparing the soles of the casual shoes, the aging resistance under ultraviolet light irradiation is lower than that in example 1, which is probably because the TPR recycled material, polypropylene, and thermoplastic styrene butadiene rubber are blended to form a cross-linked structure, the compatibility of the casual shoe preparation system can be improved by adding the polyacrylamide and the amino-modified polyacrylic acid, and the polymethacrylate interacts with the polyacrylamide after adding the polymethacrylate, so that the stability of the blended cross-linked system is improved, the aging resistance of the soles of the casual shoes under ultraviolet light irradiation is improved, and the service life of the soles of the casual shoes is prolonged. The TPR reclaimed material which is difficult to degrade can be reused, the cost can be reduced, and the environment protection is facilitated.
Analysis of the data of examples 10 to 11, example 1 and table 3 reveals that, when the soles of the casual shoes are made using the thermoplastic styrene-butadiene rubber with the star-shaped structure, the aging resistance under ultraviolet irradiation is higher than that of the soles of the casual shoes made using the thermoplastic styrene-butadiene rubber with the linear structure, which is probably because the thermoplastic styrene-butadiene rubber with the star-shaped structure has higher processing flowability and higher compatibility in the system for preparing the soles of the casual shoes, and thus the soles of the casual shoes made have higher aging resistance under ultraviolet irradiation.
As a result of analyzing the data of examples 10 to 11, examples 12 to 14 and Table 3, when the thermoplastic styrene-butadiene rubber of LG-475 type or the thermoplastic styrene-butadiene rubber of LG-411 type is added alone to the raw material for the production of soles for leisure shoes, the aging resistance under ultraviolet irradiation is lower than that of soles for leisure shoes produced by mixing the thermoplastic styrene-butadiene rubber of LG-475 type or the thermoplastic styrene-butadiene rubber of LG-411 type, which is probably because the thermoplastic styrene-butadiene rubber of LG-475 type and the thermoplastic styrene-butadiene rubber of LG-411 type have a compounding effect, and when the weight ratio of the thermoplastic styrene-butadiene rubber of LG-475 type to the thermoplastic styrene-butadiene rubber of LG-411 type is (1 to 3): 1, the aging resistance of the prepared leisure shoe sole under the irradiation of ultraviolet light is improved.
Analysis of the data of examples 16 to 17, examples 14 to 15 and table 3 shows that when cationic polyacrylamide or anionic polyacrylamide is added alone to the raw materials for producing the soles of casual shoes, the aging resistance under ultraviolet irradiation is lower than that of soles of casual shoes produced by mixing cationic polyacrylamide and anionic polyacrylamide, which may be because the cationic polyacrylamide and anionic polyacrylamide interact with each other to improve the stability of the cross-linking system and the aging resistance under ultraviolet irradiation.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. The leisure shoe sole is characterized by comprising 80-120 parts of TPR reclaimed materials, 20-40 parts of polypropylene, 15-30 parts of thermoplastic styrene-butadiene rubber, 0.05-0.15 part of cross-linking agent, 3-7 parts of polyacrylamide, 2-6 parts of polymethacrylate and 0.5-1.5 parts of amino modified polyacrylic acid, wherein the weight ratio of the polyacrylamide is (2-3): 2, the thermoplastic styrene-butadiene rubber has a star-shaped structure, and the star-shaped thermoplastic styrene-butadiene rubber is prepared from (1-3) by weight: 1 of a mixture of thermoplastic styrene-butadiene rubber of type LG-475 and thermoplastic styrene-butadiene rubber of type LG-411.
2. The leisure shoe sole according to claim 1, characterized in that: the cross-linking agent is dicumyl peroxide.
3. The leisure shoe sole according to claim 1, characterized in that: the polymethacrylate is sodium polymethacrylate.
4. The method of manufacturing a leisure shoe sole according to any one of claims 1 to 3, comprising the steps of:
s1, mixing the TPR reclaimed material, polypropylene, thermoplastic styrene-butadiene rubber and a cross-linking agent, banburying at 110-120 ℃, adding polyacrylamide, polymethacrylate and amino modified polyacrylic acid, continuing banburying for 3-7min, and granulating to obtain granules;
and S2, heating the granulated material to a molten state, and then extruding the granulated material into a sole mold to perform injection molding to obtain the leisure shoe sole.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AUPP750598A0 (en) * | 1998-12-04 | 1999-01-07 | Cromiac International Pte Ltd | Thermoplastic rubber composition |
| CN109608810A (en) * | 2018-10-31 | 2019-04-12 | 宁波万盛实业有限公司 | A kind of thermoplastic elastomer (TPE) |
| CN109517364A (en) * | 2018-11-26 | 2019-03-26 | 福建省晋江泉发骑士鞋业有限公司 | A kind of colour ETPU sole and preparation method thereof |
| CN110326845B (en) * | 2019-08-14 | 2022-08-02 | 安踏（中国）有限公司 | Elastomer material for sole, sneaker sole and sneaker |
| TW202124567A (en) * | 2019-12-27 | 2021-07-01 | 國立成功大學 | Shoe sole material composition, shoe sole material and method for producing the same |
| CN112341683B (en) * | 2020-11-19 | 2022-10-04 | 莆田市新元鞋业有限公司 | Environment-friendly reclaimed material for soles and preparation method |
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