CN114573904B - Foaming material for light high-elasticity compression-resistant shoes - Google Patents
Foaming material for light high-elasticity compression-resistant shoes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/0061—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2453/02—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 of vinyl aromatic monomers and conjugated dienes
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a light high-elasticity foam material for compression shoes, which comprises the following components in parts by weight: 30-60 parts of ethylene-octene random copolymer; 10-30 parts of hydrogenated styrene butadiene block copolymer; 5-30 parts of ethylene propylene diene monomer rubber; 0-20 parts of ethylene-octene block copolymer; 5-30 parts of polyether ester block copolymer; 0.1-10 parts of compatilizer; 1-10 parts of foaming agent; 0.1-3 parts of cross-linking agent; 0.1-1.5 parts of auxiliary cross-linking agent; 1-3 parts of zinc oxide; 0.1-2 parts of zinc stearate; 0.1-2 parts of stearic acid; 0-10 parts of filler; wherein the sum of the parts by weight of the ethylene-octene block copolymer, the polyether ester block copolymer, the hydrogenated styrene butadiene block copolymer, the ethylene propylene diene monomer and the ethylene-octene block copolymer is 100 parts. The invention has the advantages that: the foaming material for shoes prepared according to the material proportion has the advantages of light weight, high elasticity, low compression set and excellent dynamic fatigue property, and has higher cost performance.
Description
Technical Field
The invention belongs to the field of materials for shoes, and particularly relates to a foaming material for a light high-elasticity compression-resistant shoe.
Background
In order to reduce the physical energy consumption and improve the wearing comfort, the light high-elastic foaming material has become the main direction for developing the sports shoe material. With the improvement of living standard, sports fitness has become a common knowledge of people, so that the requirements on the light weight, elasticity and comfort of the sole material of shoes, especially sports shoes, are higher and higher. The light high-elasticity is a main characteristic of sports shoes, and especially professional sports such as basketball, running and the like have high requirements on the weight and rebound resilience of soles.
In recent years, a supercritical foaming process is adopted to prepare a lightweight high-elasticity high-performance sports midsole by using high-performance thermoplastic elastomers such as Polyamide Elastomer (PEBA), polyurethane elastomer (TPU), polyether ester elastomer (TPEE) and the like, so that the lightweight high-elasticity high-performance sports midsole occupies a main share of high-end sports shoes.
The thermoplastic elastomer contains hard segments and soft segments with different molecular structures in a polymer chain structure, and at room temperature, as the material is positioned between the glass transition temperatures of the soft segments and the hard segments, the hard segment micro-regions are in a glass state and serve as physical crosslinking points, the thermoplastic elastomer is endowed with certain strength, the soft segment micro-regions are in a high-elasticity state, and the material is endowed with good ductility and elasticity. Because of the characteristics of the hard segment similar to thermoplastic plastics, the physical crosslinking effect of the hard segment is melted and crystallized with the change of temperature, and the hard segment is changed reversibly.
After the thermoplastic elastomer material is foamed, the porous material with lighter weight and better elasticity is obtained, and the porous material can obtain excellent service performance when used for the midsole. For example, the midsole made by foaming thermoplastic polyurethane elastomer beads developed by Aldi-Dairy company and Basf company has a weight of 0.22-0.26g/cm 3 The rebound rate of more than 65 percent becomes a novel shoe material with revolutionary significance.
In recent years, pebax-type polyamide elastomer of Acinamar company is used for preparing novel high-performance midsole by using supercritical foaming technology under the domestic and foreign sports brands such as Naak, li Ning and the like, and the density of the sole finished product is as low as 0.10-0.18g/cm 3 The rebound performance of the novel mark post can reach more than 75%, and the novel mark post is a novel mark post in the shoe material field. However, the above materials need to be molded by a supercritical foaming process, the process is relatively complex, and the operation difficulty is high.
For the light high-elastic midsole prepared by the common chemical foaming process, ethylene-vinyl acetate resin is generally adopted(EVA) is used as a matrix and is blended with one or more copolymers, but the density is generally 0.20-0.26 g/cm 3 The rebound is less than 65%, the durability is poor, a plurality of folds appear on the side wall of the sole after the sole is worn for a period of time, the foot feeling is obviously reduced, and the hardness is obviously increased.
Therefore, the development process is relatively simple, and the shoe midsole material with the characteristics of light weight, high elasticity, low compression set and the like becomes the breakthrough direction of the sports shoe material.
Disclosure of Invention
Aiming at the problem that the sole material prepared by adopting a chemical foaming process in the prior art cannot realize the characteristics of light weight, high elasticity, low compression set and the like at the same time, the invention provides the foaming material for the light weight high elasticity compression-resistant shoes.
The technical scheme of the invention is as follows: the light high-elasticity compression-resistant foaming material for the shoes comprises the following components in parts by weight:
30-60 parts of ethylene-octene random copolymer;
10-30 parts of hydrogenated styrene butadiene block copolymer;
5-30 parts of ethylene propylene diene monomer rubber;
0-20 parts of ethylene-octene block copolymer;
5-30 parts of polyether ester block copolymer;
0.1-10 parts of compatilizer;
1-10 parts of foaming agent;
0.1-3 parts of cross-linking agent;
0.1-1.5 parts of auxiliary cross-linking agent;
1-3 parts of zinc oxide;
0.1-2 parts of zinc stearate;
0.1-2 parts of stearic acid;
0-10 parts of filler.
Wherein the sum of the parts by weight of the ethylene-octene random copolymer, the polyether ester block copolymer, the hydrogenated styrene butadiene block copolymer, the ethylene propylene diene monomer and the ethylene-octene block copolymer is 100 parts.
Further, the compatibilizer is selected from one or more of a maleic anhydride grafted ethylene-octene block copolymer, a maleic anhydride grafted ethylene-octene random copolymer, a maleic anhydride grafted hydrogenated styrene butadiene block copolymer, a maleic anhydride grafted ethylene-vinyl acetate resin, and a maleic anhydride grafted low density polyethylene resin.
Further, the foaming agent is one or more of azodicarbonamide, N-dinitroso pentamethylene tetramine, 4' -oxybisbenzene sulfonyl hydrazide, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonium nitrite.
Further, the cross-linking agent is one or two of dicumyl peroxide and 1, 4-di-tert-butyl peroxyisopropyl benzene; the auxiliary cross-linking agent is one or a combination of more of triallyl isocyanurate, trimethacrylate and trimethylolpropane triacrylate.
Further, the filler is one or a combination of more of talcum powder, titanium dioxide, calcium carbonate, white carbon black and montmorillonite.
Further, the lightweight high-elastic compression-resistant foaming material for shoes further comprises: one or more of antioxidants, antiwear agents, coupling agents, and pigments.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
60 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
15 parts of ethylene propylene diene monomer;
5 parts of polyether ester block copolymer;
4 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 part of stearic acid.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
50 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
10 parts of ethylene-octene block copolymer;
10 parts of polyether ester block copolymer;
6 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
40 parts of ethylene-octene random copolymer;
10 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
8 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
10 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
30 parts of polyether ester block copolymer;
10 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
8 parts of maleic anhydride grafted hydrogenated styrene butadiene block copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
Preferably, the lightweight high-elasticity compression-resistant foaming material for shoes comprises the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
4 parts of maleic anhydride grafted ethylene-octene random copolymer;
4 parts of maleic anhydride grafted hydrogenated styrene butadiene block copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
The invention has the advantages that: the chemical foaming process is adopted, POE, EBS, OBCs, EPDM is taken as a main base material, TPEE blending and graft copolymer adding are added as a compatibilizer, the effects of increasing the melt strength and foaming performance of sizing materials and improving the compatibility between materials can be comprehensively realized, and the prepared foaming material for the shoes has the advantages of light weight, high elasticity, low compression set rate, excellent dynamic fatigue performance and higher cost performance.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a foaming material for a light high-elasticity compression-resistant shoe, which is prepared from four main base materials: ethylene-octene random copolymer (POE), hydrogenated styrene butadiene block copolymer (SEBS), ethylene Propylene Diene Monomer (EPDM), ethylene-Octene Block Copolymer (OBCs), and polyether ester block copolymer (TPEE) are added for blending modification to increase the melt strength and foaming property of the rubber material; and adding a graft copolymer compatilizer into the auxiliary agent to improve the compatibility among materials, so as to prepare the shoe foaming material with high cost performance of the shoe material sample.
The raw materials of the invention are as follows in parts by weight:
30-60 parts of ethylene-octene random copolymer (POE);
10-30 parts of hydrogenated styrene butadiene block copolymer (SEBS);
5-30 parts of Ethylene Propylene Diene Monomer (EPDM);
0-20 parts of ethylene-Octene Block Copolymers (OBCs);
5-30 parts of polyether ester block copolymer (TPEE);
and (3) a compatilizer: 0.1-10 parts;
foaming agent: 1-10 parts;
crosslinking agent: 0.1-3 parts;
auxiliary crosslinking agent: 0.1-1.5 parts;
zinc oxide: 1-3 parts;
zinc stearate: 0.1-2 parts;
stearic acid: 0.1-2 parts;
and (3) filling: 0-10 parts.
The total weight of the ethylene-octene block copolymer (POE), the polyether ester block copolymer (TPEE), the hydrogenated styrene butadiene block copolymer (SEBS), the Ethylene Propylene Diene Monomer (EPDM) and the ethylene-Octene Block Copolymer (OBCs) is 100 parts.
The foaming agent is Azodicarbonamide (AC), N-dinitroso pentamethylene tetramine (foaming agent H), 4' -oxybisphenylsulfonyl hydrazine (OBSH), sodium bicarbonate (NaHCO) 3 ) At least one of ammonium carbonate, ammonium bicarbonate and ammonium nitrite or a combination of two or more of them.
The cross-linking agent is one or a combination of dicumyl peroxide (DCP) and 1, 4-di-tert-butyl peroxyisopropyl benzene (BIPB).
The auxiliary cross-linking agent is at least one or a combination of more than two of triallyl isocyanurate (TAIC), trimethyl acrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA).
The compatilizer is at least one or a combination of more than two of maleic anhydride grafted ethylene-octene segmented copolymer (OBCs-g-MAH), maleic anhydride grafted ethylene-octene random copolymer (POE-g-MAH), maleic anhydride grafted hydrogenated styrene butadiene segmented copolymer (SEBS-g-MAH), maleic anhydride grafted ethylene-vinyl acetate resin (EVA-g-MAH) and maleic anhydride grafted low density polyethylene resin (LDPE-g-MAH).
The filler is at least one or a combination of more than two selected from talcum powder, titanium dioxide, calcium carbonate, white carbon black and montmorillonite.
The foaming material for the light high-elasticity compression-resistant shoes further comprises: one or more of antioxidants, antiwear agents, coupling agents and pigments.
Examples 1-6 and comparative examples 1-2 the components of the light weight, high elastic and compression resistant foam materials for shoes are shown in the following table:
table 1 components of examples of foaming materials for lightweight, high-elastic and compression-resistant shoes
| Component (A) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 (comparative example 2) | Comparative example 2 (comparative example 3) |
| Ethylene-octene random copolymer (POE) | 60 | 50 | 40 | 30 | 30 | 30 | 50 | 40 |
| Hydrogenated styrene butadiene block copolymer (SEBS) | 20 | 20 | 10 | 10 | 20 | 20 | 20 | 10 |
| Polyether ester block copolymer (TPEE) | 5 | 10 | 20 | 30 | 20 | 20 | 0 | 20 |
| Ethylene Propylene Diene Monomer (EPDM) | 15 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| ethylene-Octene Block Copolymers (OBCs) | 0 | 10 | 20 | 20 | 20 | 20 | 20 | 20 |
| Compatibilizer 1 (POE-g-MAH) | 4 | 6 | 8 | 10 | 0 | 4 | 8 | 0 |
| Compatibilizer 2 (SEBS-g-MAH) | 0 | 0 | 0 | 0 | 8 | 4 | 0 | 0 |
| Foaming Agent (AC) | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 |
| Crosslinking agent (BIPB) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Auxiliary crosslinking agent (TAIC) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Zinc oxide | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Zinc stearate | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Stearic acid | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Filler (talcum powder) | 0 | 10 | 10 | 10 | 10 | 10 | 0 | 0 |
In each example, example 1 was free of added host substrate ethylene-Octene Block Copolymers (OBCs); comparative example 1 comparative example 2 without polyetherester block copolymer (TPEE), comparative example 3 without compatibilizing agent.
The sole samples prepared according to the preparation method of chemical foaming in each example were subjected to performance measurement such as tensile strength, 180-degree tear strength, hardness, density, impact resilience, compression set, energy regression, etc., and the measurement results are shown in table 2.
The specific preparation method can adopt a secondary film pressing process, an injection molding process and the like for chemical foaming, for example, the secondary film pressing process is adopted, and the preparation method comprises the following steps:
step S1, adding an ethylene-octene random copolymer (POE), a polyether ester block copolymer (TPEE), a hydrogenated styrene butadiene block copolymer (SEBS), ethylene Propylene Diene Monomer (EPDM) and an ethylene-Octene Block Copolymer (OBCs) into an internal mixer according to the component proportion of the foaming material in the table 1, and blending for 10-12min at the blending set temperature of 100-120 ℃;
s2, putting the blend and the compatilizer obtained in the step 1 into an internal mixer, banburying for 4-5min at 110-120 ℃, then putting the cross-linking agent, the auxiliary cross-linking agent, stearic acid, zinc stearate, zinc oxide, the foaming agent and the filler into the internal mixer, and continuously banburying for 4-5min at 110-120 ℃ to form a mixture;
s3, transferring the mixture in the step S2 into an open mill to form a sheet, carrying out thick pass for 2 times, mixing for 3min, carrying out thin pass for 2 times, and mixing for 1min;
s4, pouring the shoe material copolymer particles in the step S3 into a foaming mold for foaming, wherein the foaming temperature is as follows: 170-175 ℃, foaming time: 800-1000 seconds; obtaining a sole rough blank, and polishing, peeling and the like after the rough blank is cooled; then placing the mixture into a forming die for heating, cooling and shaping treatment, wherein the heating temperature is as follows: 170-175 ℃, heating time: 300-400 seconds, cooling for 450-500 seconds, shaping at 8-15MPa, foaming multiplying power of 1.70-1.75, and shaping to obtain the sole material.
Injection molding processes may also be employed, including the steps of:
S1-S3 are carried out by a secondary film pressing process;
step S4, conveying the flaky materials in the step S3 to a granulator for granulation to obtain shoe material copolymers;
and S5, pouring the shoe material copolymer particles in the step S4 into a charging barrel of an injection molding machine, molding at 170-175 ℃ for 400-450 seconds, and molding with a foaming multiplying power of 1.60-1.65 to obtain the sole material.
Table 2 performance measurements for various examples
| Performance measurement | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Tensile Strength (MPa) | 3.3 | 3.2 | 3.2 | 3.6 | 3.0 | 3.4 | 2.5 | 2.1 |
| 180 degree tear Strength (N/cm) | 2.4 | 2.3 | 2.3 | 2.5 | 2.3 | 2.5 | 2.0 | 1.8 |
| Hardness (Shore C) | 49 | 47 | 44 | 48 | 46 | 45 | 40 | 41 |
| Density (g/cm) 3 ） | 0.234 | 0.183 | 0.161 | 0.192 | 0.178 | 0.158 | 0.242 | 0.273 |
| Impact resilience (%) | 62 | 65 | 67 | 65 | 65 | 68 | 60 | 58 |
| Compression set (23 ℃,24h, 50%) | 21 | 18 | 13 | 12 | 15 | 14 | 16 | 28 |
| Energy regression (%) | 68 | 70 | 74 | 71 | 71 | 75 | 63 | 61 |
As can be seen from Table 2, examples 1 to 6, density 0.158g/cm 3 -0.234g/cm 3 The rebound can reach 68% at most, the tensile strength is above 3.0MPa, the energy regression is 75% at most, and the compression set can reach 12% at least.
Example 1 without the addition of the major substrate component ethylene-Octene Block Copolymer (OBCs), the sole sample had a higher density, indicating that the addition of OBCs is beneficial to achieving better compatibility between materials; in the comparative example 1, TPEE is not added, the density of the material is higher, the elasticity is lower, and the material has insufficient melt strength in the foaming process and cannot well lock gas in a matrix; comparative example 2 has a significantly higher density than example 3 and also has significantly lower tensile, tear, elastic and compression permanent properties than example 3, indicating poor compatibility between several materials.
The conventional EVA chemical foaming shoe material has the conventional performance range generally as follows: hardness is 45-50C, rebound is 50-60%, energy regression is 55-65%, compression set is 18-25%, density is 0.21-0.24g/cm 3 The light EVA can reach 0.18g/cm 3 The tensile strength is 2.0-2.5MPa, and the tearing strength is 2.0-2.5kg/cm.
Compared with the shoe material prepared by the traditional EVA chemical foaming process, the shoe material has the advantages of lower measured average density, higher tensile strength, higher rebound rate, lower compression set and higher energy regression on the basis of ensuring hardness and tearing strength; has better performances of lighter weight, high elasticity, low compression set and excellent dynamic fatigue property in practical sense.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (8)
1. The foaming material for the light high-elasticity compression-resistant shoes is characterized by comprising the following components in parts by weight:
30-50 parts of ethylene-octene random copolymer;
10-20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
10-20 parts of ethylene-octene block copolymer;
10-30 parts of polyether ester block copolymer;
6-10 parts of compatilizer;
6.5-10 parts of foaming agent;
1-3 parts of a cross-linking agent;
0.5-1.5 parts of auxiliary cross-linking agent;
2-3 parts of zinc oxide;
0.5-2 parts of zinc stearate;
0.5-2 parts of stearic acid;
0-10 parts of filler;
wherein the sum of the parts by weight of the ethylene-octene random copolymer, the polyether ester block copolymer, the hydrogenated styrene butadiene block copolymer, the ethylene propylene diene monomer and the ethylene-octene block copolymer is 100 parts;
the compatilizer is one or a combination of more than one of maleic anhydride grafted ethylene-octene segmented copolymer, maleic anhydride grafted ethylene-octene random copolymer, maleic anhydride grafted hydrogenated styrene butadiene segmented copolymer, maleic anhydride grafted ethylene-vinyl acetate resin and maleic anhydride grafted low-density polyethylene resin;
the foaming agent is one or a combination of more of azodicarbonamide, N-dinitroso pentamethylene tetramine, 4' -oxybisbenzene sulfonyl hydrazide, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonium nitrite;
the cross-linking agent is one or two of dicumyl peroxide and 1, 4-di-tert-butyl peroxyisopropyl benzene; the auxiliary cross-linking agent is one or a combination of more of triallyl isocyanurate, trimethacrylate and trimethylolpropane triacrylate.
2. The foaming material for the lightweight high-elastic compression-resistant shoes according to claim 1, wherein the filler is one or a combination of more of talcum powder, titanium dioxide, calcium carbonate, white carbon black and montmorillonite.
3. The lightweight, high-elastic, compression-resistant foam material for shoes according to claim 1, characterized in that the lightweight, high-elastic, compression-resistant foam material for shoes further comprises: one or more of antioxidants, antiwear agents, coupling agents, and pigments.
4. The foaming material for the light high-elasticity compression shoes according to any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight:
50 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
10 parts of ethylene-octene block copolymer;
10 parts of polyether ester block copolymer;
6 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
5. The foaming material for the light high-elasticity compression shoes according to any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight:
40 parts of ethylene-octene random copolymer;
10 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
8 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
6. The foaming material for the light high-elasticity compression shoes according to any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
10 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
30 parts of polyether ester block copolymer;
10 parts of maleic anhydride grafted ethylene-octene random copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
7. The foaming material for the light high-elasticity compression shoes according to any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
8 parts of maleic anhydride grafted hydrogenated styrene butadiene block copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
8. The foaming material for the light high-elasticity compression shoes according to any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight:
30 parts of ethylene-octene random copolymer;
20 parts of hydrogenated styrene butadiene block copolymer;
10 parts of ethylene propylene diene monomer;
20 parts of ethylene-octene block copolymer;
20 parts of polyether ester block copolymer;
4 parts of maleic anhydride grafted ethylene-octene random copolymer;
4 parts of maleic anhydride grafted hydrogenated styrene butadiene block copolymer;
6.5 parts of azodicarbonamide;
1 part of 1, 4-di-tert-butyl peroxyisopropyl benzene;
0.5 parts of triallyl isocyanurate;
2 parts of zinc oxide;
0.5 parts of zinc stearate;
0.5 parts of stearic acid;
10 parts of talcum powder.
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| CN116656035B (en) * | 2023-06-25 | 2024-05-10 | 安踏（中国）有限公司 | Injection high-magnification modified polyester TPEE foaming material |
| CN117844098B (en) * | 2024-03-07 | 2024-04-30 | 比音勒芬服饰股份有限公司 | Lightweight high-elastic environment-friendly leisure shoe midsole and preparation process thereof |
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