CN107698860B

CN107698860B - High-resilience composition foaming material for soles and preparation method thereof

Info

Publication number: CN107698860B
Application number: CN201711033480.1A
Authority: CN
Inventors: 宋红玮; 王光阜; 战振生; 张生; 王仁鸿
Original assignee: Miracll Chemicals Co Ltd
Current assignee: Miracll Chemicals Co Ltd
Priority date: 2017-10-30
Filing date: 2017-10-30
Publication date: 2020-09-08
Anticipated expiration: 2037-10-30
Also published as: CN107698860A; WO2019085008A1

Abstract

The invention relates to a high-resilience composition foaming material for soles and a preparation method thereof, wherein the high-resilience composition foaming material comprises the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer EVA; 1-70 parts of thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy; 0.1-10 parts of foaming agent; 0.01-10 parts of a crosslinking agent; 0-20 parts of a filler; the high-resilience composition foaming material for the soles, disclosed by the invention, utilizes the TPU/EVA alloy to play a role of a compatibilizer, so that an EVA/TPU interpenetrating network structure (IPN) is formed, and a TPU component is introduced into a conventional EVA foaming system, so that the problem that the performance of the final composition foaming material is reduced due to poor compatibility of the two is solved.

Description

High-resilience composition foaming material for soles and preparation method thereof

Technical Field

The invention relates to a foaming material and a preparation method thereof, in particular to a high-resilience composition foaming material for soles and a preparation method thereof, and belongs to the technical field of lightweight materials.

Background

Ethylene-vinyl acetate copolymers are prepared by copolymerizing ethylene (E) and Vinyl Acetate (VA), known by the English name of ethylene vinyl acetate, EVA for short. The foamed EVA has the advantages of light weight, softness and comfortable wearing as the main material of the existing sole material, especially the sole material of sports shoes, but after the EVA sole foamed material with high foaming rate is worn for a long time, the resilience loss of the foamed EVA material is very large, the permanent deformation is large, the mechanical property is seriously reduced, the wear resistance is poor and the like, and the application of the foamed EVA sole foamed material in the field of shoe materials is seriously influenced. Therefore, developing an EVA foam material for shoe soles, which has excellent resilience and a high expansion ratio, is a goal pursued by many colleges and enterprises.

Disclosure of Invention

The invention provides a high-resilience composition foaming material for soles and a preparation method thereof, aiming at the defects of an EVA sole material with high foaming ratio.

The technical scheme for solving the technical problems is as follows:

the high-resilience composition foaming material for the shoe sole is characterized by comprising the following components in parts by weight:

wherein, the thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy can be prepared by any one of the following methods:

the first method, see patent No. 201710058676X, comprises the steps of 1) premixing 100 weight parts of TPU raw material, adding into the feed inlet of a double screw extruder, injecting 5-95 weight parts of ethylene-vinyl acetate copolymer and 0.1-10 weight parts of double active substance into the double screw extruder through side feeding, wherein the two are not in sequence, and 0.1-5 weight parts of auxiliary agent is added into the TPU raw material or the mixture of the ethylene-vinyl acetate copolymer and the double active substance;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 50-250 ℃ and granulating;

3) drying the granulated product obtained in the step 2) to obtain the granulated product;

the second method comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an extruder, and granulating to obtain the compound;

the third method comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an open mill, and granulating to obtain the high-performance thermoplastic polyurethane elastomer;

the method IV comprises the following steps: uniformly mixing 100 parts by weight of TPU, 5-95 parts by weight of EVA, 0.1-10 parts by weight of double-active substance and 0.1-5 parts by weight of auxiliary agent, processing the mixture by an internal mixer, and granulating to obtain the thermoplastic polyurethane elastomer;

the double active substance is a compound containing acid anhydride group, carboxyl-COOH, hydroxyl-OH, amino-NH or-NH₂A compound of one or more of an isocyanate group-NCO, an epoxy group, and the auxiliary agent comprises an initiator.

EVA materials of the present invention are well known and are conventional for use in the foamed shoe material art, such as those available from DuPont

Further, the double-active substance is one of maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid and epoxy resin.

Further, the TPU raw material in the first method comprises polymer polyol, chain extender and isocyanate, the polymer polyol is one or a compound of more of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and hydroxyl-terminated polybutadiene diol, the chain extender is micromolecular dihydric alcohol or diamine containing less than 12 carbon atoms, the isocyanate is one or a compound of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate H12MDI, isophorone diisocyanate IPDI and xylylene diisocyanate XDI, the hardness of the TPU in the second method, the third method and the fourth method is 40-95Shore A, preferably 60-90Shore A, particularly preferably 70-85Shore A, as measured according to ASTM D2240; melt flow rate of 5-100g/10min, measured according to ASTM-1238 at 200 ℃ with 5Kg weight applied.

Further, the ethylene-vinyl acetate copolymer in the thermoplastic polyurethane/ethylene-vinyl acetate alloy has a vinyl acetate content of 10 to 80 wt%, preferably a vinyl acetate content of 20 to 50 wt%, and most preferably a vinyl acetate content of 25 to 45 wt%.

Further, the foaming agent is one or a mixture of several of exothermic foaming agent, endothermic foaming agent and foaming microsphere, preferably, the foaming agent is one or a mixture of several of azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate, 4, 4' -oxybis-benzenesulfonylhydrazide, p-toluene sulfonyl hydrazide, sodium bicarbonate, sodium citrate, ammonium bicarbonate and expandable microsphere, wherein the expandable microsphere is well known and available from AKZO Nobel Industries expand

And (4) series.

Further, the crosslinking agent is one or a mixture of more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, azobisisobutyronitrile, azoisobutyronitrile formamide, azodicyclohexyl cyanogen and dimethyl azodiisobutyrate.

Further, the filler is one or a mixture of more of talcum powder, calcium carbonate, argil, sulfate and toner.

Furthermore, the composition foaming material also comprises an antioxidant, a lubricant, a UV resistant auxiliary agent, an auxiliary crosslinking agent and a foaming promoter, wherein the auxiliary crosslinking agent is a compound containing 2 or more carbon-carbon double bonds, and the foaming promoter is any one of zinc oxide and zinc stearate.

The invention also claims a preparation method of the high-resilience composition foaming material, which comprises the following steps:

1) weighing 100 parts by weight of EVA, 1-70 parts by weight of thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy, 0.1-10 parts by weight of foaming agent, 0.01-10 parts by weight of cross-linking agent and 0-20 parts by weight of filler, and putting into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture obtained in the step 1) into an internal mixer for mixing uniformly, controlling the mixing time to be 5-25 minutes, and the mixing temperature to be 100-150 ℃ to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, controlling the mixing time to be 5-30 minutes and the mixing temperature to be 80-200 ℃ to obtain a second-stage mixed material; 4) foaming and shaping: placing the second-stage mixed material obtained in the step 3) into a sole product mold, then placing the mold into a flat vulcanizing machine for mold pressing foaming, wherein the foaming temperature is 100-200 ℃, the foaming time is 1-10 minutes, and then cooling the mold to 10-50 ℃ to obtain the high-resilience EVA composition foamed sole material; or putting the second-stage mixed material obtained in the step 3) into a foaming shoe material device for primary injection foaming, wherein the injection temperature is controlled at 120-180 ℃, and the high-resilience EVA composition foaming sole material is obtained.

Further, the foamed shoe material device with one-time injection in the step 4) is an injection foaming molding machine.

Compared with the prior art, the high-resilience composition foaming material and the preparation method thereof provided by the invention have the following beneficial effects:

1) according to the high-resilience composition foaming material for the soles, the TPU/EVA alloy is used as a compatibilizer, an EVA/TPU interpenetrating network structure (IPN) is formed, and a TPU component is introduced into a conventional EVA foaming system, so that the problem that the performance of the final composition foaming material is reduced due to poor compatibility of the two components is solved;

2) by utilizing the excellent rebound resilience, wear resistance and mechanical property of the TPU, the rebound resilience, compression set and other properties of the foamed EVA sole material are greatly improved;

3) the process flow is simple, and the EVA foaming shoe material can be directly used in the existing mould pressing EVA foaming shoe material equipment or one-time injection EVA foaming shoe material equipment without equipment transformation or research, development and investment of new process equipment.

Detailed Description

The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.

Preparation of TPU/EVA alloy material

Example 1:

a process for preparing a TPU alloy material comprises the following steps:

1) 68 parts of polyester polyol with the molecular weight of 2000g/mol, 6 parts of BDO and 26 parts of diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate), and injecting 95 parts of EVA, 10 parts of MAH (maleic anhydride) and 5 parts of initiator DCP (dicumyl peroxide) into a double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-200 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 2:

a process for preparing a TPU alloy material comprises the following steps:

1) 55 parts of polyester polyol with the molecular weight of 1500g/mol, 7 parts of BDO and 38 parts of diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate) are added into a feed port of a double-screw extruder, and 75 parts of EVA (ethylene vinyl acetate), 5 parts of MAH (maleic anhydride) and 0.2 part of initiator DCP (dicumyl peroxide) are injected into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 50-250 ℃ and the temperature of a cooling zone to be 90-110 ℃, and cutting and granulating the extruded material under water;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 3:

a process for preparing a TPU alloy material comprises the following steps:

1) 70 parts by weight of a polyether polyol having a molecular weight of 1800g/mol, 5 parts of BDO and 25 parts of toluene diisocyanate TDI were added to the feed inlet of a twin-screw extruder, and 65 parts of EVA (Tri-well chemical)

150Y), 0.1 part of acrylic acid and 0.1 part of initiator DCP (dicumyl peroxide) are injected into a twin-screw extruder by side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 4:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1000g/mol, 8 parts of BDO and 47 parts of toluene diisocyanate TDI into a feed port of a double-screw extruder, and injecting 34 parts of EVA, 0.5 part of acrylamide and 0.15 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃, controlling the temperature of a cooling zone to be 90-110 ℃, and carrying out underwater cutting granulation on the extruded material;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 5:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed port of a double-screw extruder, and injecting 45 parts of EVA, 1.5 parts of acrylamide and 0.25 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 6:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed port of a double-screw extruder, and injecting 5 parts of EVA, 0.1 part of methyl methacrylate and 1 part of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 7:

a process for preparing a TPU alloy material comprises the following steps:

1) adding 45 parts by weight of polyether polyol with the molecular weight of 1800g/mol, 8 parts of BDO and 47 parts of hexamethylene diisocyanate HDI into a feed inlet of a double-screw extruder, and injecting 75 parts of EVA, 6 parts of butyl acrylate and 2 parts of initiator DCP (dicumyl peroxide) into the double-screw extruder through side feeding;

3) drying the granulated product obtained in the step 2) to obtain the product.

Example 8:

a process for preparing a TPU alloy material comprises the following steps:

1) 100 parts by weight of polyether type TPU elastomer

M70, 90 parts of EVA with 40 percent of VA, 1.5 parts of maleic anhydride and 0.25 part of initiator DCP (dicumyl peroxide) are placed in a high-speed mixer for premixing;

2) controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃ and the temperature of a cooling zone to be 90-110 ℃, extruding the mixture obtained in the step 1) by the extruder, and cutting and granulating the extruded material under water; 3) drying the granulated product obtained in the step 2) to obtain the product.

The TPU/EVA alloy materials obtained in the examples 7 and 8 are applied to a high-resilience composition, and the specific composition, the preparation method and the properties of the composition are as follows:

high-resilience composition foaming material for soles

Example 9:

a high-resilience composition foaming material for soles comprises the following components in parts by weight:

the preparation process of the foaming material is as follows:

1) weighing EVA, TPU/EVA alloy, Azodicarbonamide (AC) and di-tert-butylperoxyisopropyl benzene (DCP) with corresponding weight, and putting the weighed materials into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer for mixing uniformly, setting the mixing temperature to be 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 100 ℃, and mixing is carried out for 5 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, then placing the sole product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 100 ℃, and then cooling the mold to 10 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition sole foaming material prepared by the steps and the existing EVA foaming products on the market are shown in Table 1.

TABLE 1

Item	Test standard	Unit of	Example 9 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.2	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.0	1.5
Elongation at break	ISO1798-2008	％	500	300
					Tear strength	GB/T10808-2006	N/mm	8	4.2
Rebound resilience	GB/T6670-2008	％	60	50
					Compression set	GB/T6669-2008	％	25	35
Wear resistance	DIN53516	Mm³	400	500

Example 10:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, azodicarbonamide and dicumyl peroxide (DCP) with corresponding weight and VA content of 20% and putting the EVA, the TPU/EVA alloy, the azodicarbonamide and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer for mixing uniformly, setting the mixing temperature at 150 ℃, and mixing for 15 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 10 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into an injection foaming forming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and the high-resilience EVA composition foamed sole material is obtained.

The data of the physical property test results of the composition foam material prepared by the above steps and the existing EVA foam products on the market are shown in Table 2.

TABLE 2

Item	Test standard	Unit of	EXAMPLE 10 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.21	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	6	1.5
Elongation at break	ISO1798-2008	％	550	300
					Tear strength	GB/T10808-2006	N/mm	10.4	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	58	50
					Compression set	GB/T6669-2008	％	20	35
Wear resistance	DIN53516	Mm³	380	500

Example 11:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, sodium bicarbonate and dicumyl peroxide (DCP) with corresponding weight and the VA content of 20 percent, and putting the EVA, the TPU/EVA alloy, the sodium bicarbonate and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 120 ℃, and mixing for 25 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 110 ℃, and mixing is carried out for 30 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) into a sole product mold, then placing the sole product mold into a flat vulcanizing machine for mold foaming, wherein the foaming time is 10 minutes, the foaming temperature is 130 ℃, and then cooling the mold to 30 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition sole foaming material prepared by the steps and the existing EVA foaming products on the market are shown in Table 3.

TABLE 3

Item	Test standard	Unit of	EXAMPLE 11 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.22	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.5	1.5
Elongation at break	ISO1798-2008	％	510	300
					Tear strength	GB/T10808-2006	N/mm	8.8	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	61	50
					Compression set	GB/T6669-2008	％	22	35
Wear resistance	DIN53516	Mm³	350	500

Example 12:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, Azodicarbonamide (AC) and dicumyl peroxide (DCP) with corresponding weight and 25 percent of VA content, and putting the EVA, the TPU/EVA alloy, the Azodicarbonamide (AC) and the DCP into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 140 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 15 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared by the above steps and the existing EVA foam products on the market are shown in Table 4.

TABLE 4

Item	Test standard	Unit of	EXAMPLE 12 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.22	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	9.2	1.5
Elongation at break	ISO1798-2008	％	480	300
					Tear strength	GB/T10808-2006	N/mm	10.4	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	62	50
					Compression set	GB/T6669-2008	％	18	35
Wear resistance	DIN53516	Mm³	400	500

Example 13:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, p-toluenesulfonyl hydrazide, di-tert-butylperoxyisopropyl benzene and calcium carbonate with corresponding weight and 25 percent of VA content, and putting the EVA, the TPU/EVA alloy, the p-toluenesulfonyl hydrazide, the di-tert-butylperoxyisopropyl benzene and the calcium carbonate into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature at 100 ℃, and mixing for 10 minutes to obtain a first-stage mixed material;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 20 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 120 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 5.

TABLE 5

Item	Test standard	Unit of	EXAMPLE 13 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.23	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	3.8	1.5
Elongation at break	ISO1798-2008	％	500	300
					Tear strength	GB/T10808-2006	N/mm	6.0	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	62	50
					Compression set	GB/T6669-2008	％	20	35
Wear resistance	DIN53516	Mm³	410	500

Example 14:

a high-resilience EVA composition foaming material for soles comprises the following components in parts by weight:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, sodium citrate, di-tert-butylperoxyisopropyl benzene and titanium dioxide with corresponding weight and VA content of 25 percent, and putting the EVA, the TPU/EVA alloy, the sodium citrate, the di-tert-butylperoxyisopropyl benzene and the titanium dioxide into a high-speed mixer for primary mixing;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, then placing the sole product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 200 ℃, and then cooling the mold to 30 ℃ to obtain the high-resilience EVA composition sole foaming material.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 6.

TABLE 6

Item	Test standard	Unit of	EXAMPLE 14 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.24	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	3.0	1.5
Elongation at break	ISO1798-2008	％	450	300
					Tear strength	GB/T10808-2006	N/mm	6.0	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	62	50
					Compression set	GB/T6669-2008	％	18	35
Wear resistance	DIN53516	Mm³	380	500

Example 15:

the preparation method of the foaming material comprises the following steps:

1) weighing EVA, TPU/EVA alloy, barium azodicarboxylate, di-tert-butylperoxyisopropyl benzene and pottery clay with corresponding weight and 25 percent of VA content, and putting the EVA, TPU/EVA alloy, barium azodicarboxylate, di-tert-butylperoxyisopropyl benzene and pottery clay into a high-speed mixer for primary mixing;

3) and (3) mixing for the second time: putting the first-stage mixed material obtained in the step 2) into an open mill for second mixing, wherein the mixing temperature is set to be 120 ℃, and mixing is carried out for 25 minutes to obtain a second-stage mixed material;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into a rotary disc type injection foaming machine for primary injection foaming, wherein the injection temperature is controlled at 180 ℃, and finally the high-resilience EVA composition sole foaming material is obtained.

The data of the physical property test results of the composition foam material prepared through the above steps and the existing EVA foam products on the market are shown in Table 7.

TABLE 7

Item	Test standard	Unit of	EXAMPLE 15 product	Market EVA foaming product
					Density of	ASTM-D792	g/cm³	0.18	0.25
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	2.8	1.5
Elongation at break	ISO1798-2008	％	420	300
					Tear strength	GB/T10808-2006	N/mm	5.5	4.2
Rebound resilience of ball drop	GB/T6670-2008	％	62	50
					Compression set	GB/T6669-2008	％	20	35
Wear resistance	DIN53516	Mm³	380	500

Comparative example 1:

1) weighing 100 parts by weight of EVA with the VA content of 10%, 1 part by weight of TPU and 1 part by weight of azodicarbonamide AC, and putting the EVA, the TPU and the azodicarbonamide AC into a high-speed mixer for preliminary mixing;

2) mixing for the first time: putting the mixture subjected to preliminary mixing in the step 1) into an internal mixer, setting the mixing temperature to be 100 ℃, and mixing for 5 minutes to obtain a first-stage mixed material;

4) foaming and shaping: and (3) placing the second mixed material obtained in the step 3) in a sole product mold, placing the product mold in a flat vulcanizing machine for mold foaming, wherein the foaming time is 1 minute, the foaming temperature is 100 ℃, and then cooling the mold to 10 ℃ to obtain the EVA composition sole foaming material.

The physical property test data of the composition foam obtained in comparative example 1 and the product obtained in example 9 were compared, and the results are shown in Table 8:

TABLE 8

Item	Test standard	Unit of	Example 9	Comparative example 1
					Density of	ASTM-D792	g/cm³	0.2	0.24
Hardness of	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.0	0.8
Elongation at break	ISO1798-2008	％	500	220
					Tear strength	GB/T10808-2006	N/mm	8	3.5
Rebound resilience of ball drop	GB/T6670-2008	％	60	52
					Compression set	GB/T6669-2008	％	25	48
Wear resistance	DIN53516	Mm³	400	550

As can be seen from the data in tables 1 to 8, the product performance prepared by the technical scheme of the invention is obviously superior to the product performance prepared by directly mixing and foaming EVA and TPU or the conventional EVA foaming system; on the other hand, the invention greatly improves the performances of rebound resilience, compression set and the like of the existing foaming EVA material by utilizing the excellent wear resistance and mechanical property of the TPU, simplifies the process flow, does not need equipment modification or equipment research and development and investment, and reduces the production cost.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The high-resilience composition foaming material for the shoe sole is characterized by comprising the following components in parts by weight:

the preparation method of the TPU/EVA alloy comprises the following steps: a. 100 parts by weight of polyether type TPU elastomer

M70, 90 parts by weight of EVA with 40% of VA, 1.5 parts by weight of maleic anhydride and 0.25 part by weight of initiator dicumyl peroxide are placed in a high-speed mixer for premixing; b. controlling the temperature of a reaction zone of the double-screw extruder to be 140-170 ℃ and the temperature of a cooling zone to be 90-110 ℃, extruding the mixture obtained in the step a by the extruder, and cutting and granulating the extruded material under water; c. drying the granulated product obtained in the step b to obtain the product;

the preparation method of the high-resilience composition foaming material for the shoe sole comprises the following steps:

1) weighing EVA, TPU/EVA alloy, azodicarbonamide and dicumyl peroxide with corresponding weight and the VA content of 20 percent, and putting the EVA, the TPU/EVA alloy, the azodicarbonamide and the dicumyl peroxide into a high-speed mixer for primary mixing;

4) foaming and shaping: and (3) putting the second mixed material obtained in the step 3) into an injection foaming forming machine for primary injection foaming, wherein the injection temperature is controlled at 150 ℃, and the material is obtained.