CN113462070A

CN113462070A - Super-absorption impact high-resilience foam material, and preparation method and application thereof

Info

Publication number: CN113462070A
Application number: CN202110907782.7A
Authority: CN
Inventors: 朱小平; 李忠德; 林宗隆; 周剑锋; 欧阳继承; 雷世源
Original assignee: Anta China Co Ltd
Current assignee: Anta China Co Ltd
Priority date: 2021-08-09
Filing date: 2021-08-09
Publication date: 2021-10-01
Anticipated expiration: 2041-08-09
Also published as: WO2023015693A1; CN113462070B

Abstract

The invention provides a super-absorption high-resilience foam material which is formed by a foam composition: the foaming composition comprises: 10-35 parts by weight of a copolymer of isoolefin and linear chain terminal olefin; 40-60 parts by weight of an ethylene-vinyl acetate copolymer; 5-20 parts by weight of a polyolefin elastomer; 5-10 parts of ethylene propylene diene monomer; 5-15 parts of styrene polymer; 0.1-1 part by weight of peroxide crosslinking agent; 1-5 parts by weight of a foaming agent; 1-5 parts by weight of a foaming auxiliary agent; the number of carbon atoms of the isoolefin is 5-8; the number of carbon atoms of the linear chain terminal olefin is 2-4. Compared with the prior art, the invention adopts the stress absorbing polymer isoolefin with larger steric hindrance and the copolymer of the straight chain terminal olefin and the high elastic polymer to blend and foam to obtain the foaming material which not only has excellent stress absorbing property, stress relaxation property and damping and shock absorption effect at room temperature, but also keeps the rebound rate of more than 50 percent.

Description

Super-absorption impact high-resilience foam material, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of foaming materials, and particularly relates to a super-suction high-resilience foaming material, and a preparation method and application thereof.

Background

Newton's third law states that when a force is applied to something, a force of the same magnitude and opposite direction must be obtained, which is called a reaction force. In contrast to running, when falling on the ground, the ground will give a vertical downward impact force due to gravity, and the ground will give us an upward reaction force. This reaction force is dissipated through the cushioning of the muscles and joints. However, if the impact force is too large or the cushioning is not proper, the reaction force may cause damage to the bone and joints. In the motion process, along with the difference of moving speed, the foot can receive the impact force of 1.3 ~ 3 times gravity size, and the higher the moving speed, runner's weight is bigger, and buffering ability can be poor, and the loading rate of the power that certainly receives is bigger, and the impact force that receives is bigger. Therefore, it is imperative to develop a midsole material with ultra-high absorption and impact capability.

However, the polymer with excellent shock absorption and damping performance has poor resilience, and whether running shoes or basketball shoes are used, the resilience of the foamed midsole is pursued more and more, so that consumers can easily feel a laxative feeling when wearing sports shoes with poor resilience, and the sports shoes not only affect sports performances but also are easy to fatigue, and the sports experience is affected because the consumers do not have sufficient energy feedback and run or bounce.

Chinese patent with application number 201210170635.7 discloses an EVA (ethylene vinyl acetate) foaming damping material and a preparation method thereof, wherein the EVA foaming damping material is prepared from the following components in parts by weight: 10-30 parts of EVA; 10-30 parts of NBR; 30-50 parts of PVC; 10-20 parts of epoxidized soybean oil; 10-20 parts of calcium carbonate; 1-3 parts of a foaming agent; 0.5-1 part of a crosslinking agent; 0.5-1 part of barium stearate; 1-3 parts of zinc oxide; 10-15 parts of a plasticizer; 0.5-1 part of accelerator, but the rebound rate of the final foaming material is only 14%.

Chinese patent with application number 201611170471.2 discloses an EVA foaming damping shock-absorbing material, which comprises the following components in parts by weight: 40-80 parts of styrene butadiene rubber, 5-10 parts of EVA (ethylene-vinyl acetate), 2-5 parts of azobisisobutyronitrile, 0.1-0.5 part of dibenzoyl peroxide, 1-3 parts of polyethylene glycol 4001, 20-40 parts of PVC (polyvinyl chloride) and 0.1-0.5 part of 2-mercaptobenzothiazole. However, the final foam material has a resilience of only 11% to 15%.

Chinese patent with application number 201811288316.X discloses an EVA-based cushioning and shock-absorbing material and a preparation method thereof, and the material comprises the following raw materials: 60-100 parts of EVA, 1-0 part of silicon boron shear thickening gel, 2-40 parts of filler, 1-10 parts of foaming agent, 0.2-2 parts of bridging agent, 0.6-6 parts of accelerator and 0.5-2 parts of lubricant. However, the foam of the final example had a rebound resilience of only 40% to 52%, a tensile strength of 0.89 to 1.22MPa, and a falling ball impact force of 468 to 827 kg.

It can be seen that in the published patents or documents, if NBR/PVC is added to improve the damping performance of the foam material or SBR/PVC is added to improve the damping performance of the foam material, the resilience of the foam material is greatly reduced, the resilience rate is lower than 16%, which is not in accordance with the requirement of high resilience of the current consumers for sports shoes, and carbon in the molecular structure of PVC belongs to tertiary carbon group, and in the peroxide crosslinking system, the molecular chain breaking degradation speed is higher than the crosslinking speed of the molecular chain, so that PVC cannot be crosslinked in the formula, resulting in the reduction of mechanical properties of the final foam material. If the silicon boron shear thickening gel is added to improve the buffering and damping performance, although the resilience performance is kept, from the falling ball impact test data of the embodiment and the comparative example, the damping effect after the silicon boron shear thickening gel is added is not obvious, and the silicon boron shear thickening gel in the system can not generate foaming and crosslinking as EVA, only plays the role of a filling agent in the formula, so that the mechanical property of the final foaming material is greatly reduced, the tensile strength is only about 1.0MPa, and the basic requirement of the mechanical property of sports shoes can not be met.

Disclosure of Invention

In view of this, the technical problem to be solved by the present invention is to provide a super-absorbent high-resilience foam material, a preparation method thereof, and an application thereof.

The invention provides a super-absorbent high-resilience foam material which is formed by a foam composition;

the foaming composition comprises:

the number of carbon atoms of the isoolefin is 5-8; the number of carbon atoms of the linear chain terminal olefin is 2-4.

Preferably, the number of carbon atoms of the isoolefin is 5-6; the number of carbon atoms of the linear terminal olefin is 3;

the molar content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 18 to 40 percent;

the polyolefin elastomer has a crystallinity of 20% or less;

the crystallinity of the ethylene propylene diene monomer is less than or equal to 4 percent;

the styrene polymer is selected from one or more of styrene-ethylene-butylene-styrene copolymer, hydrogenated styrene-ethylene-butylene-styrene copolymer, styrene-butylene-styrene copolymer and hydrogenated styrene-butylene-styrene copolymer.

Preferably, the isoolefin is 1-isohexane and/or 4-methyl-2-pentene; the linear terminal olefin is propylene;

the styrene-ethylene-butylene-styrene copolymer has a styrene molar content of less than 33%;

the styrene-butylene-styrene copolymer has a styrene content of 20% or less by mole.

Preferably, the copolymer of isoolefin and linear terminal olefin has a glass transition temperature of 25 ℃ to 35 ℃;

the ethylene-vinyl acetate copolymer comprises EVA with the hardness of 82-90A and EVA with the hardness of 60-65A;

the hardness of the polyolefin elastomer is 52-70A;

the styrene polymer has a hardness of 40-60A.

Preferably, the mass ratio of the EVA with the hardness of 82-90A to the EVA with the hardness of 60-65A is (3-5): 1.

preferably, the copolymer of isoolefin and linear terminal olefin is selected from the group consisting of Absortimer EP-1001;

the ethylene-vinyl acetate copolymer is selected from one or more of EVA7350M, EVA7470M and EVA 33121;

the polyolefin elastomer is selected from one or more of POE 8180, POE8150 and POE 7467;

the ethylene propylene diene monomer is selected from EODM 5565;

the styrene polymer is selected from SEBS YH688 and/or SBBS P1083.

Preferably, the peroxide crosslinking agent is selected from dicumyl peroxide and/or 1, 4-di-tert-butylperoxyisopropyl benzene;

the foaming agent is selected from one or more of azodicarbonamide, expanded microspheres and 4,4' -oxo-bis-benzenesulfonyl hydrazide;

the foaming auxiliary agent is selected from zinc oxide, stearic acid and zinc stearate;

the mass ratio of the zinc oxide to the stearic acid to the zinc stearate is (1-1.5): (0.8-1.2): 0.8.

the invention also provides a preparation method of the super-absorption high-resilience foam material, which comprises the following steps:

the copolymer of isoolefin and straight-chain terminal olefin, ethylene-vinyl acetate copolymer, polyolefin elastomer, ethylene propylene diene monomer, styrene polymer, peroxide cross-linking agent, foaming agent and foaming auxiliary agent are mixed, granulated and foamed to obtain the foam material with super-impact absorption and high resilience.

Preferably, the mixing is specifically as follows: mixing a peroxide cross-linking agent and a foaming agent, adding a foaming auxiliary agent for mixing when the temperature is raised to 80-85 ℃, adding a copolymer of isoolefin and linear chain terminal olefin, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, ethylene propylene diene monomer and a styrene polymer for mixing when the temperature is raised to 90-95 ℃, and obtaining a mixed material when the temperature is raised to 100-110 ℃;

the granulation specifically comprises the following steps: granulating the mixed materials to obtain granules; the heating temperature of the granulation is 75-90 ℃; the rotating speed of the screw is 40-50 revolutions per minute during granulation; the material cutting speed is 15-20 r/min;

the foaming is injection foaming molding or secondary compression molding foaming;

the injection foaming molding specifically comprises the following steps: injecting the granules into a forming die, and heating, foaming and forming to obtain a foamed and formed material; baking the foamed and molded material to obtain a super-suction impact high-resilience foamed material; the injection temperature is 80-95 ℃; the temperature for heating, foaming and molding is 160-180 ℃; the heating foaming molding time is 500-700 s; the baking temperature is 80-100 ℃; the baking speed is 60-70 r/min; the baking time is 30-40 min;

the secondary compression molding forming foaming specifically comprises the following steps: adding the granules into a mould for mould pressing foaming to obtain a mould pressing foaming semi-finished product; carrying out flat foaming on the semi-finished product subjected to mould pressing foaming to obtain a super-suction impact high-resilience foaming material; the temperature of the mould pressing foaming is 170-180 ℃; the time for mould pressing and foaming is 600-700 s; the temperature of the flat plate foaming is 170-180 ℃; the time for foaming the flat plate is 350-500 s.

The invention also provides application of the super-absorbent high-resilience foam material as a midsole material of sports shoes.

The invention provides a super-absorption high-resilience foam material which is formed by a foam composition: the foaming composition comprises: 10-35 parts by weight of a copolymer of isoolefin and linear chain terminal olefin; 40-60 parts by weight of an ethylene-vinyl acetate copolymer; 5-20 parts by weight of a polyolefin elastomer; 5-10 parts of ethylene propylene diene monomer; 5-15 parts of styrene polymer; 0.1-1 part by weight of peroxide crosslinking agent; 1-5 parts by weight of a foaming agent; 1-5 parts by weight of a foaming auxiliary agent; the number of carbon atoms of the isoolefin is 5-8; the number of carbon atoms of the linear chain terminal olefin is 2-4. Compared with the prior art, the invention adopts a stress absorbing polymer isoolefin and straight chain terminal olefin copolymer which is generated by controlling the molecular structure by adopting a nanotechnology and has larger steric hindrance, the polymer has ultrahigh damping factor under the room temperature condition, and the polymer is blended and foamed with high-elasticity polymers such as EVA, POE, EPDM, styrene-butadiene elastomers and the like to obtain a foamed material which not only has excellent stress absorbing property, stress relieving property and damping and shock absorption effects under the room temperature condition, but also keeps the rebound rate of more than 50 percent; the polymer of low crystallinity or high compliance of collocation simultaneously to promote expanded material's resilience, make this expanded material have super absorption simultaneously and dash and high resilience, and then make this expanded material when receiving impact force or vibration, the material can turn into impact energy automatically and absorb heat energy, and the counter impact force that can make the motion in-process foot receive reduces 32% ~ 57% as sports shoes insole material, thereby reduces the motion harm, is favorable to that the consumer is healthy.

Drawings

FIG. 1 is a schematic flow diagram of an injection foam molding process;

FIG. 2 is a schematic flow chart of a two-step molding foaming process.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

the foaming composition comprises:

It is well known that the most important thing for a material to obtain excellent shock absorption capability is strong shock absorption capability, and the shock absorption performance of a high molecular material is closely related to the dynamic viscoelasticity of a polymer. The deformation of the polymer under alternating stress is generated by the movement of chain segments, the chain segments are subjected to the action of internal friction resistance when moving, and the movement of the chain segments cannot follow the change of external force when the external force changes, so that the deformation lags behind the stress, a phase difference delta is generated, the larger the delta is, the harder the chain segment moves, and the deformation cannot follow the change of the external force, and the phenomenon is called as a hysteresis phenomenon. If the change in deformation cannot follow the change in stress and hysteresis occurs, then each cyclic change will result in a loss of work (heat energy), called mechanical loss, also called internal loss. This ability to generate hysteresis loss by friction and thus convert mechanical energy into thermal energy is referred to as the damping capacity of the material. The hysteresis and internal loss characteristics of a polymer are generally expressed by a loss factor tan delta, and the greater the loss factor tan delta, the greater the hysteresis and internal loss of the polymer, and the more significant the damping effect. The loss factor tan delta of the high polymer material is related to the structure of the material, and the group contribution theory shows that the high polymer material with large size of side groups on a molecular chain, large quantity, large polarity, large intermolecular hydrogen bonds and strong action has large internal rotation activation energy and intermolecular acting force, and large internal friction resistance of chain segment movement, thereby having large hysteresis, large internal consumption and good shock absorption performance.

Therefore, the invention selects a stress absorbing polymer with larger steric hindrance generated by controlling a molecular structure by a nanotechnology, namely a copolymer of isoolefin and linear terminal olefin, wherein the polymer maximizes the viscosity property of the polymer at room temperature and has a higher damping factor at room temperature, so that when the material receives impact force or vibration at room temperature, the material can automatically convert the impact energy into heat energy for absorption, and macroscopically shows excellent stress absorbability, stress relaxation property and damping and shock absorption effects. Wherein the number of carbon atoms of the isoolefin is 5-8, preferably 5-7, and more preferably 5-6; the number of carbon atoms of the linear chain terminal olefin is 2-4, preferably 3-4, and more preferably 3; further preferably, the isoolefin is 1-isohexane and/or 4-methyl-2-pentene; the linear terminal olefin is propylene; the glass transition temperature of the copolymer of isoolefin and linear terminal olefin is preferably 25 ℃ to 35 ℃, and more preferably 30 ℃; the glass transition temperature of the polymer is in the room temperature range, so that the polymer has good stress absorbability at room temperature. In the present invention, most preferably, the isoolefin/linear terminal olefin copolymer is Absortomer EP-1001; in the examples provided by the present invention, the content of the copolymer of isoolefin and linear terminal olefin is specifically 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or 35 parts by weight.

In the foaming composition provided by the invention, the molar content of the vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 18-40%, more preferably 18-35%, and still more preferably 18-33%; the ethylene-vinyl acetate copolymer preferably comprises EVA with the hardness of 82-90A and EVA with the hardness of 60-65A, and more preferably comprises EVA with the hardness of 82-90A and EVA with the hardness of 62-63A; the high-hardness EVA has low VA content, and can provide mechanics and good formability in a formula; and VA content in the EVA of low rigidity is high, and the content is higher, and the elasticity is better, and polarity is higher moreover, is favorable to promoting the laminating nature of material. The mass ratio of the EVA with the hardness of 82-90A to the EVA with the hardness of 60-65A is preferably (3-5): 1; in the embodiment provided by the invention, the mass ratio of the EVA with the hardness of 82-90A to the EVA with the hardness of 60-65A is specifically 5: 1. 4.5: 1. 4: 1. 3.5: 1 or 3: 1; in the present invention, most preferably, the ethylene-vinyl acetate copolymer is one or more, more preferably two or more, of EVA7350M, EVA7470M and EVA 33121; in the examples provided by the present invention, the content of the vinyl acetate in the ethylene-vinyl acetate copolymer in the foaming composition is specifically 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, or 40 parts by weight.

In order to enable the foaming material to have better shock absorption and shock absorption performance and better elasticity, the low-crystallinity or high-flexibility polymer polyolefin elastomer, the ethylene propylene diene monomer and the styrene polymer are scientifically matched in the composition.

Wherein the polyolefin elastomer preferably has a crystallinity of 20% or less; the hardness of the polyolefin elastomer is preferably 52-70A; in the present invention, most preferably, the polyolefin elastomer is one or more of POE 8180, POE8150 and POE 7467; in the examples provided herein, the polyolefin elastomer is specifically present in the foamed composition in an amount of 10 parts by weight, 20 parts by weight, 5 parts by weight, or 15 parts by weight.

The crystallinity of the ethylene propylene diene monomer is preferably less than or equal to 4 percent, and more preferably 1 to 4 percent; in the present invention, most preferably, the ethylene propylene diene monomer is EODM 5565; in the embodiment provided by the invention, the content of the ethylene propylene diene monomer in the foaming composition is specifically 10 parts by weight or 5 parts by weight.

The hardness of the styrene polymer is preferably 40-60A, and more preferably 43-56A; the styrene polymer is preferably one or more of styrene-ethylene-butylene-styrene copolymer, hydrogenated styrene-ethylene-butylene-styrene copolymer, styrene-butylene-styrene copolymer and hydrogenated styrene-butylene-styrene copolymer; wherein the styrene-ethylene-butylene-styrene copolymer preferably has a styrene molar content of less than 33%, more preferably less than or equal to 30%, still more preferably less than or equal to 20%; the styrene-butylene-styrene copolymer preferably has a styrene content of 20% or less by mole; in the present invention, most preferably, the styrenic polymer is SEBS YH688 and/or SBBS P1083; in the examples provided herein, the styrenic polymer is specifically 10 parts by weight, 5 parts by weight, or 15 parts by weight in the foamed composition.

The foaming composition provided by the invention takes a peroxide crosslinking agent as a vulcanizing agent; the peroxide crosslinking agent is preferably dicumyl peroxide and/or 1, 4-di-tert-butylperoxyisopropyl benzene, more preferably DCP PERKADOX BC-FF and/or BIBP PERKADOX 14S-FL; the content of the peroxide crosslinking agent is preferably 0.4-0.8 part by weight, and more preferably 0.6-0.7 part by weight; in the examples provided herein, the peroxide crosslinking agent was specifically present in the foaming composition at 0.65 parts by weight.

The foaming agent is preferably one or more of azodicarbonamide, expanded microspheres and 4,4' -oxybis-benzenesulfonylhydrazide; in the embodiment provided by the invention, the foaming agent is specifically a foaming agent AC 6000H; the content of the foaming agent is preferably 1 to 4 parts by weight, more preferably 2 to 3 parts by weight, and still more preferably 2.5 parts by weight.

The foaming auxiliary agent is preferably zinc oxide, stearic acid and zinc stearate; the mass ratio of the zinc oxide to the stearic acid to the zinc stearate is preferably (1-1.5): (0.8-1.2): 0.8, more preferably (1 to 1.4): (0.9-1.1): 0.8, more preferably 1.2: 1: 0.8; the content of the foaming aid in the foaming composition provided by the invention is preferably 1-4 parts by weight, and more preferably 2-3 parts by weight.

The invention adopts a copolymer of stress absorbing polymer isoolefin and linear chain terminal olefin with larger steric hindrance generated by controlling a molecular structure by a nanotechnology, the polymer has ultrahigh damping factor at room temperature, and the polymer is blended and foamed with high-elasticity polymers such as EVA, POE, EPDM, styrene-butadiene elastomers and the like to obtain a foamed material which not only has excellent stress absorbing property, stress relieving property and damping and shock absorption effects at room temperature, but also keeps the resilience rate more than 50%; the polymer of low crystallinity or high compliance of collocation simultaneously to promote expanded material's resilience, make this expanded material have super absorption simultaneously and dash and high resilience, and then make this expanded material when receiving impact force or vibration, the material can turn into impact energy automatically and absorb heat energy, and the counter impact force that can make the motion in-process foot receive reduces 32% ~ 57% as sports shoes insole material, thereby reduces the motion harm, is favorable to that the consumer is healthy.

The invention also provides a preparation method of the super-absorption high-resilience foam material, which comprises the following steps: the copolymer of isoolefin and straight-chain terminal olefin, ethylene-vinyl acetate copolymer, polyolefin elastomer, ethylene propylene diene monomer, styrene polymer, peroxide cross-linking agent, foaming agent and foaming auxiliary agent are mixed, granulated and foamed to obtain the foam material with super-impact absorption and high resilience.

In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available. The contents and types of the isoolefin and linear chain terminal olefin copolymer, the ethylene-vinyl acetate copolymer, the polyolefin elastomer, the ethylene-propylene-diene monomer, the styrene polymer, the peroxide crosslinking agent, the foaming agent and the foaming auxiliary agent are the same as those described above, and are not described again.

Mixing a copolymer of isoolefin and straight-chain terminal olefin, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, ethylene propylene diene monomer, a styrene polymer, a peroxide cross-linking agent, a foaming agent and a foaming auxiliary agent; in the present invention, this step is preferably embodied as follows: mixing a peroxide cross-linking agent and a foaming agent, adding a foaming auxiliary agent for mixing when the temperature is raised to 80-85 ℃, adding a copolymer of isoolefin and linear chain terminal olefin, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, ethylene propylene diene monomer and a styrene polymer for mixing when the temperature is raised to 90-95 ℃, and obtaining a mixed material when the temperature is raised to 100-110 ℃; the mixing is preferably carried out in an internal mixer.

Granulating the mixed materials to obtain granules; the granulation is preferably carried out in a granulator; the heating temperature of the granulation is preferably 75-90 ℃; in the present invention, it is preferable to divide into four heating zones; the temperature of the first heating zone is preferably 75 ℃, the temperature of the second heating zone is preferably 80 ℃, the temperature of the third heating zone is preferably 85 ℃, and the temperature of the fourth heating zone is preferably 95 ℃; the rotating speed of the screw is preferably 40-50 revolutions per minute during granulation; the material cutting rotating speed is preferably 15-20 revolutions per minute; cooling is needed in the granulation process, if water cooling is adopted, the prepared granules need to be added into a dryer for drying and dehydration, and if air cooling is adopted, the granules can be directly used.

Foaming the granules obtained by granulation to obtain the super-absorption high-resilience foam material; in the invention, injection foaming molding (IP process) or secondary compression molding foaming (MD process) can be adopted; referring to fig. 1 and 2, fig. 1 is a schematic flow chart of an injection foaming molding process, and fig. 2 is a schematic flow chart of a two-step compression molding foaming process.

When the foaming is injection foam molding, it is preferable to specifically: injecting the granules into a forming die, and heating, foaming and forming to obtain a foamed and formed material; baking the foamed and molded material to obtain a super-suction impact high-resilience foamed material; the forming mold and the injection amount can be set according to the foaming ratio, and in the invention, the foaming ratio is preferably 1.2-2, more preferably 1.4-1.8, and still more preferably 1.5; the injection temperature is preferably 80-95 ℃; in the present invention, the injected heating zone is preferably divided into four; the temperature of the first zone is preferably 80 ℃, the temperature of the second zone is preferably 85 ℃, the temperature of the third zone is preferably 90 ℃, and the temperature of the fourth zone is preferably 95 ℃; the temperature for heating, foaming and molding is preferably 160-180 ℃, more preferably 165-175 ℃, and further preferably 170 ℃; the time for heating, foaming and forming is preferably 500-700 s; the baking temperature is preferably 80-100 ℃; in the invention, the baking is preferably divided into four temperature zones, the temperature of the first zone is preferably 80 ℃ which is the temperature of the first zone, the temperature of the second zone is preferably 90 ℃, the temperature of the third zone is preferably 95 ℃, and the temperature of the fourth zone is preferably 100 ℃; the baking speed is preferably 60-70 r/min; the baking time is preferably 30-40 min; the baking is preferably carried out in an oven; the length of the oven is preferably 30-40 meters.

When the foaming is two-stage compression molding foaming, it is preferably specifically: adding the granules into a mould for mould pressing foaming to obtain a mould pressing foaming semi-finished product; carrying out flat foaming on the semi-finished product subjected to mould pressing foaming to obtain a super-suction impact high-resilience foaming material; the temperature of the mould pressing foaming is preferably 170-180 ℃, and more preferably 175 ℃; the time for mould pressing and foaming is preferably 600-700 s, more preferably 640-680 s, and further preferably 660 s; the temperature of the flat plate foaming is preferably 170-180 ℃, and more preferably 175 ℃; the time for foaming the flat plate is preferably 350-500 s, more preferably 400-450 s, and further preferably 420-430 s; in the present invention, it is preferable to further cool the plate after foaming; the cooling is preferably carried out by using cooling water; the temperature of the cooling water is preferably 20-30 ℃, and more preferably 25 ℃; the cooling time is preferably 350-500 s, more preferably 400-450 s, and still more preferably 420-430 s.

In order to further illustrate the present invention, the following will describe in detail a super-absorbent high resilience foam material, its preparation method and application in combination with the examples.

The reagents used in the following examples are all commercially available.

Examples 1 to 11 and comparative examples 1 to 7

Weighing: weighing DCP and a foaming agent as a first component according to the types and the dosage of the formulas in the tables 1 and 2; weighing stearic acid, zinc stearate and zinc oxide as a second component; the rest material is weighed out as the third group material.

Mixing: firstly, pouring the third group of materials into an internal mixer, opening the internal mixer, and heating to 80-85 ℃; pouring a second group of materials; when the temperature is raised to 90-95 ℃, pouring a third group of materials; when the temperature rises to 100-110 ℃, the mixed material is poured out.

Material preparation: mixing the materials; pouring into a material making machine, and respectively adjusting the temperatures of the first zone, the second zone, the third zone and the fourth zone as follows: 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C. And adjusting the rotation speed of the screw to 40-50 rpm, and adjusting the rotation speed of the cutting material to 15-20 rpm.

Foaming: pouring the manufactured granules into an injection foaming molding machine, and respectively adjusting the temperatures of a first feeding area, a second feeding area, a third feeding area and a fourth feeding area as follows: the temperature of the upper and lower templates of the forming die are respectively adjusted to be as follows: 170 ℃ and 170 ℃. The amount of the material was set in accordance with the amount of the mold (mold size 18cm x 10cm x 1cm, material amount was 120g depending on expansion ratio 1.5), and the vulcanization time was 600 seconds.

Baking: the temperature of the first, second, third and fourth zones is adjusted as follows: 80 ℃, 90 ℃, 95 ℃, 100 ℃ and 60 revolutions per minute; feeding the foamed material into an oven opening, wherein the oven length is 30 meters; the baking time is 40min from beginning to end.

TABLE 1 kinds and amounts (parts by weight) of the formulations of comparative examples and examples

TABLE 2 kinds and amounts (parts by weight) of the formulations of comparative examples and examples

Among them, EP-1001: hardness 92A, Tg 30 ℃, peak tan δ 2.7 at 30 ℃, mitsui chemical company.

EVA 7350M: hardness 90A, VA content 18%, crystallinity 36.5%, Tg-18 ℃, tan. delta. 0.23 at 30 ℃, Tamopsis company.

EVA 33121: hardness 63A, VA content 33%, crystallinity 14.5%, Tg-22 ℃, tan. delta. 0.21 at 30 ℃, Tamopsis Co.

POE 8180: hardness 63A, crystallinity 16%, Tg-55 ℃, tan δ 0.12 at 30 ℃, dow.

POE 8150: hardness 70A, crystallinity 16%, Tg-52 ℃, tan δ 0.14 at 30 ℃, dow.

EPDM 5565 has a crystallinity of 1%, a Tg of-35 ℃ and a tan delta of 0.16 at 30 ℃ from Dow.

SEBS YH 688: hardness 43A, S content 13%, Tg-65 ℃, tan δ 0.10 at 30 ℃, tombstone.

SBBS J1083: hardness 56A, S content 20%, Tg-60 ℃ and tan. delta. 0.11 at 30 ℃ Asahi Kasei corporation.

SOE L609: hardness 76A, S content 33%, Tg 19 ℃, tan. delta. 0.8 at 30 ℃, Asahi Kasei corporation.

ZnO 997: the white stone zinc oxide has a relative density of 4.42-4.45.

DCP: and (3) petrifaction in China.

Stearic acid 1801: indonedulada.

Zinc stearate: lake, new chemical Limited.

Foaming agent AC 6000H: hangzhou Haihong Fine chemical Co., Ltd.

The performance of the foamed materials obtained in examples 1 to 11 and comparative examples 1 to 7 was examined, and the results are shown in tables 3 to 5.

TABLE 3 detection results of the properties of the foamed materials

TABLE 4 detection results of the properties of the foamed materials

TABLE 5 detection results of the properties of the foamed materials

Serial number	Detecting items	Test method	Example 8	Example 9	Example 10	Example 11
							1	Density g/cm³	DIN 53479	0.172	0.170	0.179	0.167
2	Hardness C	DIN 55305	48	47	49	49
							3	Rebound after the first time	DIN 53512	59	60	59	56
4	Impact force KN of falling ball	EN1621-1:2012	2.9	2.7	3.2	3.0
							5	Impact force kg of falling ball	EN1621-1:2012	295.9	275.5	326.5	306.1
6	Damping G value	ASTM F1614-99	11.4	11.3	11.5	11.1
							7	N/CM for delamination tear	DIN 53507-B	24	25	26	24
8	Tensile strength MPa	DIN 53543	2.5	2.4	2.9	2.8
							9	Compression set%	ASTM-D.395-B	35	34	32	30

And (4) conclusion:

(1) from the test results of comparative example 1, it is seen that: the pure EVA foaming has poor rebound and large falling ball impact force, which shows that the shock absorption and impact absorption effects are poor.

(2) From a comparison of the test data of comparative examples 1, 2: the low-crystallinity or high-flexibility polymer is added into the formula, so that the resilience of the foaming material can be improved.

(3) From the test results of comparative examples 1, 3, 4, 5, it can be seen that: after the large steric hindrance polymer EP-1001 is added into the formula, the falling ball impact force and the shock absorption G value are reduced, and the reduction is more obvious along with the increase of the addition amount, which shows that the large steric hindrance polymer EP-1001 can play a good role in shock absorption and shock absorption; however, the rebound rate of the foaming material is greatly reduced after the same EP-1001 is added, and the rebound rate is only 20% when 30 parts of the foaming material are added, so that the comprehensive conclusion (2) is that the rebound rate of the foaming material is improved by adding the polymer with low crystallinity or high flexibility.

(4) From the test results of comparative examples 6, 7, it can be seen that: compared with the existing damping polymer SOE L609, the large steric hindrance polymer EP-1001 has more obvious effects on the reduction of the falling ball impact force and the damping G value than the SOE L609 under the same addition amount, and has lower influence on the reduction of the rebound than the SOE L609, thereby showing that the large steric hindrance polymer EP-1001 selected by the invention has more advantages.

(5) The following conclusions are also obtained from the test results of examples 1, 2, 3, 4, 5, 6: the falling ball impact force and the damping G value decrease amplitude are increased along with the increase of the addition amount after EP-1001 in the formula; when the EP-1001 is added in the same amount, the rebound rate of the formula matched with the polymer with low crystallinity or high flexibility is far higher than that of the comparative examples 3, 4 and 5 without the polymer with low crystallinity or high flexibility.

(5) As can be seen from the test data of comparative example 6 and examples 1 to 11, when the addition amount of EP-1001 is 40 parts, the rebound rate is 39%, and the rebound requirement of the insole of the sports shoe is not satisfied; in the examples 1-11, the EP-1001 is added in 10-35 parts, and the tests show that the ball-falling impact force is respectively reduced by 32.8%, 37.7%, 45.9%, 52.5%, 55.8% and 57.3% when the EP-1001 is added in 10, 15, 20, 25, 30 and 35 parts, compared with 0 part, the rebound rate is reduced by 7.4%, 10.3%, 11.8%, 14.7%, 19.2% and 25%, but basically kept above 50%, thus the rebound requirement of the insole of the sports shoe can be met. In order to integrate the dual effects of impact absorption and rebound, the addition amount of the large steric hindrance polymer disclosed by the invention is preferably 15-30 parts.

Thus illustrating that:

1) compared with the existing EVA shock absorption foaming material, the shock absorption and shock absorption foaming material prepared by the invention adopts the high-steric hindrance polymer with high damping factor, so that the foaming material with excellent stress absorbability and damping shock absorption at room temperature is obtained, the falling ball impact force of the foaming material is tested to be less than 4.1KN (or less than 418kg), and compared with the foaming material of a comparative example which is not added, the impact force is reduced by 32-57%; compared with the existing EVA damping material, the amplitude of the impact force reduction is more obvious.

2) Compared with the existing EVA shock absorption foaming material, the shock absorption and shock absorption foaming material prepared by the invention adopts the polymer with low crystallinity or high flexibility to improve the resilience of the foaming material, so that the super shock absorption high resilience foaming material is obtained, and the resilience rate of the foaming material is more than 50%. Compared with the prior art that the rebound rate of the damping material is lower than 16%, the rebound rate is improved by more than 34%, and the rebound performance requirements of consumers on sports shoes and excellent sports experience are completely met.

3) Compared with the existing EVA shock-absorbing foam material, the foam material with super-absorption impact and high resilience prepared by the invention has excellent absorption impact effect and good resilience, and various polymers adopted in the formula have foamability and can be crosslinked by peroxide, so that various physical properties of the final foam material completely meet the mechanical requirements of the insole of sports shoes.

Claims

1. A super absorbent high resilience foam material is characterized by being formed from a foam composition;

the foaming composition comprises:

2. The superabsorbent high-resilience foam material according to claim 1, wherein the number of carbon atoms of the isoolefin is 5 to 6; the number of carbon atoms of the linear terminal olefin is 3;

the polyolefin elastomer has a crystallinity of 20% or less;

3. The superabsorbent high-resilience foam material of claim 2, wherein the isoolefin is 1-isohexane and/or 4-methyl-2-pentene; the linear terminal olefin is propylene;

4. The superabsorbent high resilience foam of claim 2, wherein the copolymer of isoolefin and linear terminal olefin has a glass transition temperature of 25 ℃ to 35 ℃;

the hardness of the polyolefin elastomer is 52-70A;

the styrene polymer has a hardness of 40-60A.

5. The superabsorbent high-resilience foam material according to claim 4, wherein the mass ratio of the EVA with the hardness of 82-90A to the EVA with the hardness of 60-65A is (3-5): 1.

6. the superabsorbent high resilience foam of claim 1, wherein the copolymer of isoolefin and linear terminal olefin is selected from the group consisting of Absortomer EP-1001;

the ethylene propylene diene monomer is selected from EODM 5565;

the styrene polymer is selected from SEBS YH688 and/or SBBS P1083.

7. The superabsorbent high resilience foam of claim 1, wherein the peroxide crosslinking agent is selected from dicumyl peroxide and/or 1, 4-di-t-butylperoxyisopropyl benzene;

8. a method for preparing the superabsorbent high-resilience foam material of claim 1, comprising:

9. The method according to claim 8, wherein the mixing is specifically: mixing a peroxide cross-linking agent and a foaming agent, adding a foaming auxiliary agent for mixing when the temperature is raised to 80-85 ℃, adding a copolymer of isoolefin and linear chain terminal olefin, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, ethylene propylene diene monomer and a styrene polymer for mixing when the temperature is raised to 90-95 ℃, and obtaining a mixed material when the temperature is raised to 100-110 ℃;

10. Use of the foam material with super-suction impact and high resilience of any one of claims 1 to 7 or the foam material with super-suction impact and high resilience prepared by the preparation method of claim 8 or 9 as a material of a middle sole of sports shoes.