CN107698860A

CN107698860A - A kind of sole high resilience composition expanded material and preparation method thereof

Info

Publication number: CN107698860A
Application number: CN201711033480.1A
Authority: CN
Inventors: 王光阜; 战振生; 宋红玮; 张生; 王仁鸿
Original assignee: Miracll New Material Co Ltd
Current assignee: Miracll New Material Co Ltd; Miracll Chemicals Co Ltd
Priority date: 2017-10-30
Filing date: 2017-10-30
Publication date: 2018-02-16
Anticipated expiration: 2037-10-30
Also published as: WO2019085008A1; CN107698860B

Abstract

The present invention relates to a kind of sole high resilience composition expanded material and preparation method thereof, by weight, including following component：100 parts of ethylene-vinyl acetate copolymer EVA；Thermoplastic polyurethane/1 70 parts of ethylene-vinyl acetate copolymer alloy；0.1 10 parts of foaming agent；0.01 10 parts of crosslinking agent；0 20 parts of filler；Sole of the present invention high resilience composition expanded material, the effect of bulking agent is served using TPU/EVA alloys, form EVA/TPU inierpeneirating network structures (IPN), TPU components are introduced in conventional EVA foaming systems, solve the problems, such as that both cause final composition foaming material performance to decline due to poor compatibility.

Description

A kind of sole high resilience composition expanded material and preparation method thereof

Technical field

The present invention relates to a kind of expanded material and preparation method thereof, more particularly to a kind of sole to be foamed with high resilience composition Material and preparation method thereof, belong to lightweighting materials technical field.

Background technology

Ethylene-vinyl acetate copolymer is to be copolymerized by ethene (E) and vinyl acetate (VA) and be made, English name EthyleneVinylAcetate, abbreviation EVA.Foam masters of the EVA as current material for sole of shoe, especially sport shoe sole material Want material, there is lightweight, it is soft, it is comfortable and easy to wear the advantages of, but the EVA shoe bottom expanded material of high foamability is worn for a long time After, the resilience loss for the EVA material that foams is very big, and it is big to be permanently deformed, and mechanical properties decrease is serious, and exists wear-resisting The problems such as property difference, have a strong impact on its application in footwear material field.Thus, exploitation one kind has excellent resiliency, compared with high-foaming times The sole of rate EVA expanded materials turn into the target that many colleges and universities and enterprise are pursued.

The content of the invention

The present invention is for deficiency existing for the EVA shoe bottom material of high foamability, there is provided a kind of sole is combined with high resilience Thing expanded material and preparation method thereof.

The technical scheme that the present invention solves above-mentioned technical problem is as follows：

A kind of high resilience composition expanded material of sole, it is characterised in that by weight, including following component：

Wherein, the thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy can use any one following method to enter It is prepared by row：

Method one, see the process disclosed in patent No. 201710058676X, comprise the following steps:1) by 100 weight The TPU raw materials of part are added to the charging aperture of double screw extruder after premix, and the ethene-vinyl acetate of 5-95 parts by weight is copolymerized Thing and the double activated material of 0.1-10 parts by weight are injected into double screw extruder by side feeding, the two without sequencing, The auxiliary agent of 0.1-5 parts by weight be added in TPU raw materials or ethylene-vinyl acetate copolymer with the mixture of double activated material；

2) reaction zone temperature for controlling double screw extruder is 50-250 DEG C, is granulated；

3) by the product drying after the granulation obtained by step 2), produce；

Method two, comprises the following steps：By the double of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Active material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and by mixture by being granulated after extruding machining, are produced；

Method three, comprises the following steps：By the double of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Active material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and are granulated, produced after mixture is machined by mill；

Method four, comprises the following steps：By the double of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Active material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and are granulated, produced after mixture is machined by banburying；

The double activated material is to contain anhydride group, carboxyl-COOH, hydroxyl-OH, amino-NH or-NH₂, isocyanates One or more compounds in base-NCO, epoxide group, the auxiliary agent include initiator.

EVA material in the present invention is well-known and is to be applied to the conventional trade mark in foaming shoe material field, such as can Purchased from Du Pont (DuPont)

Further, described double activated material is maleic anhydride, GMA, acrylic acid, methyl-prop One kind in e pioic acid methyl ester, butyl acrylate, acrylic acid amides, allyl polyglycol, amino acid, epoxy resin.

Further, the TPU raw materials described in method one include polymer polyatomic alcohol, chain extender and isocyanates, described poly- Compound polyalcohol is PEPA, PPG, polycaprolactone polyol, polycarbonate polyol, terminal hydroxy group polybutadiene One or more compoundings in enediol, described chain extender are small molecule dihydric alcohol or binary containing less than 12 carbon atoms Amine, the isocyanates is toluene di-isocyanate(TDI) TDI, methyl diphenylene diisocyanate MDI, the isocyanide of hexa-methylene two Acid esters HDI, dicyclohexyl methyl hydride diisocyanate H12MDI, isofoer diisocyanate IPDI, the isocyanide of phenylenedimethylidyne two One or more compoundings in acid esters XDI, method two, method three, the hardness of TPU described in method four are 40-95Shore A, preferably 60-90ShoreA, particularly preferred 70-85ShoreA, it is measured according to ASTM D2240；Melt flow rate (MFR) is 5- 100g/10min, it applies 5Kg weight at 200 DEG C according to ASTM-1238 and measured.

Further, in thermoplastic polyurethane/ethene-vinyl acetate alloy ethylene-vinyl acetate copolymer vinyl acetate Content is 10-80wt%, it is preferable that the content of vinyl acetate is 20-50wt%, and most preferably the content of vinyl acetate is 25- 45%.

Further, the foaming agent is one or more of in heat release type foaming agent, endothermic blowing agent, foam microspheres Mixture, it is preferable that the foaming agent refers to azodicarbonamide, azodiisobutyronitrile, Barium azodicarboxylate, 4,4 '-oxo Double benzene sulfonyl hydrazides, unifor, sodium acid carbonate, sodium citrate, ammonium hydrogen carbonate are one or more in expended microsphere Mixture, wherein, expended microsphere is well-known for example purchased from AKZO Nobel Industries ExpanceSystem Row.

Further, the crosslinking agent is cumyl peroxide, dual-tert-butyl cumene hydroperoxide, the isobutyl of azo two Nitrile, azo isobutyl cyano group formamide, azo dicyclohexyl first cyanogen, one or more of mixing in azo-bis-iso-dimethyl Thing.

Further, the filler is talcum powder, calcium carbonate, clay, sulfate, one or more of mixing in toner Thing.

Further, antioxidant, lubricant, the auxiliary agent of resistance to UV, assistant crosslinking agent and hair are also included in the composition expanded material Steep accelerator, the assistant crosslinking agent be the compound containing 2 and above carbon-carbon double bond, the foamed promoter be zinc oxide, Any one in zinc stearate.

The preparation method of above-mentioned high resilience composition expanded material is also claimed in the present invention, comprises the following steps：

1) 100 parts of EVA, thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy 1-70 by weight, are weighed Part, foaming agent 0.1-10 parts, crosslinking agent 0.01-10 parts, filler 0-20 parts are put into and preliminary mixing are carried out in high mixer；

2) it is kneaded for the first time：Uniform, control mixing time 5- will be kneaded in mixture input banbury obtained by step 1) 25 minutes, 100-150 DEG C of melting temperature, obtain first order mixture；

3) second of mixing：First order mixture obtained by step 2) is put into mill and carries out second of mixing, Mixing time 5-30 minutes are controlled, 80-200 DEG C of melting temperature, obtain second level mixture；4) foaming and sizing：By step 3) The second level mixture of gained is placed in shoe sole article mould, after be placed in vulcanizing press and carry out moulded from foam, foam Temperature is 100-200 DEG C, and foamed time is 1-10 minutes, and mould then is cooled into 10-50 DEG C, obtains high resilience EVA groups Compound foaming sole material；Or the second level mixture obtained by step 3) is put into the foaming shoe material equipment once projected Carry out it is one-shot foamed, project temperature control at 120-180 DEG C, obtain high resilience EVA composition foaming sole materials.

Further, the foaming shoe material equipment once projected described in step 4) refers to injection-expansion molded machine.

Compared with prior art, the beneficial effect of high resilience composition expanded material provided by the invention and preparation method thereof Fruit is as follows：

1) sole of the present invention high resilience composition expanded material, increase-volume is served using TPU/EVA alloys The effect of agent, EVA/TPU inierpeneirating network structures (IPN) are formd, TPU components are introduced in conventional EVA foaming systems, solved Both are due to the problem of poor compatibility causes final composition foaming material performance to decline；

2) using excellent TPU resilience, wearability and mechanical performance, returning for foaming EVA shoe bottom material is substantially improved The performances such as elasticity, compression set；

3) technological process is simple, can it is existing molding EVA foam shoe material equipment or once project EVA foam shoe material equipment it is straight Use is connect, without scrap build or the research and development of new technology equipment and investment.

Embodiment

The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.

First, the preparation of TPU/EVA alloy materials

Embodiment 1：

A kind of technique for preparing TPU alloy materials, comprises the following steps：

1) 6 parts of 68 parts of PEPA, BDO, the methyl diphenylene diisocyanate MDI by molecular weight for 2000g/mol 26 parts of charging apertures for being added to double screw extruder, by 10 parts of 95 parts of EVA, MAH (maleic anhydride) and initiator DCP (peroxidating Diisopropylbenzene (DIPB)) 5 parts be injected into by side feeding in double screw extruder；

2) reaction zone temperature for controlling double screw extruder is 140-200 DEG C, and cooling area temperature is 90-110 DEG C, after extrusion Material be granulated through imderwater cutting；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 2：

1) 7 parts of 55 parts of PEPA, BDO, the methyl diphenylene diisocyanate MDI by molecular weight for 1500g/mol 38 parts of charging apertures for being added to double screw extruder, by 5 parts of 75 parts of EVA, MAH (maleic anhydride) and initiator DCP (peroxidating two Isopropylbenzene) 0.2 part be injected into by side feeding in double screw extruder；

2) reaction zone temperature for controlling double screw extruder is 50-250 DEG C, and cooling area temperature is 90-110 DEG C, after extrusion Material be granulated through imderwater cutting；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 3：

1) PPG and 5 parts of BDO, toluene di-isocyanate(TDI) for being 1800g/mol by the molecular weight of 70 parts by weight 25 parts of charging apertures for being added to double screw extruder of TDI, by 65 parts of EVA (Mitsui Chemicals150Y), acrylic acid 0.1 part is injected into double screw extruder with 0.1 part of initiator DCP (cumyl peroxide) by side feeding；

2) reaction zone temperature for controlling double screw extruder is 140-180 DEG C, and cooling area temperature is 90-110 DEG C, after extrusion Material be granulated through imderwater cutting；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 4：

1) PPG and 8 parts of BDO, toluene di-isocyanate(TDI) for being 1000g/mol by the molecular weight of 45 parts by weight 47 parts of charging apertures for being added to double screw extruder of TDI, by 34 parts of EVA, 0.5 part of acrylic acid amides and initiator DCP (peroxide Change diisopropylbenzene (DIPB)) 0.15 part be injected into by side feeding in double screw extruder；

2) reaction zone temperature for controlling double screw extruder is 140-170 DEG C, and cooling area temperature is 90-110 DEG C, after extrusion Material be granulated through imderwater cutting；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 5：

1) PPG and 8 parts of BDO, the isocyanic acid of hexa-methylene two for being 1800g/mol by the molecular weight of 45 parts by weight 47 parts of charging apertures for being added to double screw extruder of ester HDI, by 45 parts of EVA, 1.5 parts of acrylic acid amides and initiator DCP (mistake Oxidation diisopropylbenzene (DIPB)) 0.25 part be injected into by side feeding in double screw extruder；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 6：

1) PPG and 8 parts of BDO, the isocyanic acid of hexa-methylene two for being 1800g/mol by the molecular weight of 45 parts by weight 47 parts of charging apertures for being added to double screw extruder of ester HDI, by 5 parts of EVA, 0.1 part of methyl methacrylate and initiator DCP 1 part of (cumyl peroxide) is injected into double screw extruder by side feeding；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 7：

1) PPG and 8 parts of BDO, the isocyanic acid of hexa-methylene two for being 1800g/mol by the molecular weight of 45 parts by weight 47 parts of charging apertures for being added to double screw extruder of ester HDI, by 75 parts of EVA, 6 parts of butyl acrylate and initiator DCP (peroxide Change diisopropylbenzene (DIPB)) 2 parts be injected into by side feeding in double screw extruder；

3) by the product drying after the granulation obtained by step 2), produce.

Embodiment 8：

1) by the polyether-type TPU elastomers of 100 parts by weightM70, the EVA that 90 parts of VA contents are 40%, 0.25 part of 1.5 parts of maleic anhydride and initiator DCP (cumyl peroxide), which are placed in high mixer, to be pre-mixed；

2) reaction zone temperature for controlling double screw extruder is 140-170 DEG C, and cooling area temperature is 90-110 DEG C, by step 1) the extruded machine of the mixture of gained is extruded in, and the material after extrusion is granulated through imderwater cutting；3) by the granulation obtained by step 2) Product drying afterwards, is produced.

The TPU/EVA alloy materials of embodiment 7 and the gained of embodiment 8 are applied in high resilience composition by we, group The concrete composition of compound, preparation method and performance are as follows：

2nd, sole high resilience composition expanded material

Embodiment 9：

A kind of high resilience composition expanded material of sole, by weight, including following component：

The preparation process of above-mentioned expanded material is as follows：

1) EVA of corresponding weight, TPU/EVA alloys, azodicarbonamide (AC), dual-tert-butyl isopropyl peroxide are weighed Preliminary mixing is carried out in benzene DCP input high mixers；

2) it is kneaded for the first time：Will be uniform by the interior mixing of mixture input banbury tentatively mixed in step 1), it is kneaded Temperature is set as 100 DEG C, is kneaded 10 minutes, obtains first order mixture；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, refining Temperature is set as 100 DEG C, is kneaded 5 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture be placed in shoe sole article mould, then will Shoe sole article mould, which is placed in vulcanizing press, carries out mould hair foaming, and foamed time is 1 minute, and blowing temperature is 100 DEG C, then Mould is cooled to 10 DEG C, obtains high resilience EVA composition Foamed Sole Materials.

Pass through composition Foamed Sole Materials prepared by above-mentioned steps and the physical property measurement of the existing EVA foamed products of in the market Result data is as shown in table 1.

Table 1

Project	Testing standard	Unit	The product of embodiment 9	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.2	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.0	1.5
Elongation at break	ISO1798-2008	%	500	300
					Tearing strength	GB/T10808-2006	N/mm	8	4.2
Resilience	GB/T6670-2008	%	60	50
					Compression set	GB/T6669-2008	%	25	35
Wearability	DIN53516	Mm³	400	500

Embodiment 10：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are different for 20% EVA, TPU/EVA alloys, azodicarbonamide, peroxidating two Preliminary mixing is carried out in propyl benzene (DCP) input high mixer；

2) it is kneaded for the first time：Will be uniform by the interior mixing of mixture input banbury tentatively mixed in step 1), it is kneaded Temperature is set as 150 DEG C, is kneaded 15 minutes, obtains first order mixture；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, refining Temperature is set as 120 DEG C, is kneaded 10 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture put into injection-expansion molded machine and carry out once Shooting foaming, temperature control is projected at 150 DEG C, obtains high resilience EVA composition foaming sole materials.

Pass through the physical property measurement result of composition expanded material prepared by above-mentioned steps and the existing EVA foamed products of in the market Data are as shown in table 2.

Table 2

Project	Testing standard	Unit	The product of embodiment 10	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.21	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	6	1.5
Elongation at break	ISO1798-2008	%	550	300
					Tearing strength	GB/T10808-2006	N/mm	10.4	4.2
Ball falling resiliency	GB/T6670-2008	%	58	50
					Compression set	GB/T6669-2008	%	20	35
Wearability	DIN53516	Mm³	380	500

Embodiment 11：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are 20% EVA, TPU/EVA alloys, sodium acid carbonate, cumyl peroxide (DCP) put into high mixer and carry out preliminary mixing；

2) it is kneaded for the first time：It will be put into step 1) by the mixture tentatively mixed in banbury, melting temperature setting For 120 DEG C, it is kneaded 25 minutes, obtains first order mixture；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, refining Temperature is set as 110 DEG C, is kneaded 30 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture be placed in shoe sole article mould, then will Shoe sole article mould, which is placed in vulcanizing press, carries out mould hair foaming, and foamed time is 10 minutes, and blowing temperature is 130 DEG C, so Mould is cooled to 30 DEG C afterwards, obtains high resilience EVA composition Foamed Sole Materials.

Pass through composition Foamed Sole Materials prepared by above-mentioned steps and the physical property measurement of the existing EVA foamed products of in the market Result data is as shown in table 3.

Table 3

Project	Testing standard	Unit	The product of embodiment 11	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.22	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.5	1.5
Elongation at break	ISO1798-2008	%	510	300
					Tearing strength	GB/T10808-2006	N/mm	8.8	4.2
Ball falling resiliency	GB/T6670-2008	%	61	50
					Compression set	GB/T6669-2008	%	22	35
Wearability	DIN53516	Mm³	350	500

Embodiment 12：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are 25% EVA, TPU/EVA alloys, azodicarbonamide (AC), peroxidating Preliminary mixing is carried out in diisopropylbenzene (DIPB) (DCP) input high mixer；

2) it is kneaded for the first time：It will be put into step 1) by the mixture tentatively mixed in banbury, melting temperature setting For 140 DEG C, it is kneaded 10 minutes, obtains first order mixture；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, refining Temperature is set as 120 DEG C, is kneaded 15 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture input the injection-expansion molded machine of rotating disc type enter Row is one-shot foamed, projects temperature control at 150 DEG C, finally gives high resilience EVA composition Foamed Sole Materials.

Pass through the physical property measurement result of composition expanded material prepared by above-mentioned steps and the existing EVA foamed products of in the market Data are as shown in table 4.

Table 4

Project	Testing standard	Unit	The product of embodiment 12	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.22	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	9.2	1.5
Elongation at break	ISO1798-2008	%	480	300
					Tearing strength	GB/T10808-2006	N/mm	10.4	4.2
Ball falling resiliency	GB/T6670-2008	%	62	50
					Compression set	GB/T6669-2008	%	18	35
Wearability	DIN53516	Mm³	400	500

Embodiment 13：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are 25% EVA, TPU/EVA alloys, unifor, dual-tert-butyl mistake Preliminary mixing is carried out in oxidation cumene and calcium carbonate input high mixer；

2) it is kneaded for the first time：It will be put into step 1) by the mixture tentatively mixed in banbury, melting temperature setting For 100 DEG C, it is kneaded 10 minutes, obtains first order mixture；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, refining Temperature is set as 120 DEG C, is kneaded 20 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture input the injection-expansion molded machine of rotating disc type enter Row is one-shot foamed, projects temperature control at 120 DEG C, finally gives high resilience EVA composition Foamed Sole Materials.

Pass through the physical property measurement result of composition expanded material prepared by above-mentioned steps and the existing EVA foamed products of in the market Data are as shown in table 5.

Table 5

Project	Testing standard	Unit	The product of embodiment 13	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.23	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	3.8	1.5
Elongation at break	ISO1798-2008	%	500	300
					Tearing strength	GB/T10808-2006	N/mm	6.0	4.2
Ball falling resiliency	GB/T6670-2008	%	62	50
					Compression set	GB/T6669-2008	%	20	35
Wearability	DIN53516	Mm³	410	500

Embodiment 14：

A kind of high resilience EVA composition expanded materials of sole, by weight, including following component：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are 25% EVA, TPU/EVA alloys, sodium citrate, dual-tert-butyl peroxidating Preliminary mixing is carried out in cumene and titanium dioxide input high mixer；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture be placed in shoe sole article mould, then will Shoe sole article mould, which is placed in vulcanizing press, carries out mould hair foaming, and foamed time is 1 minute, and blowing temperature is 200 DEG C, then Mould is cooled to 30 DEG C, obtains high resilience EVA composition Foamed Sole Materials.

Pass through the physical property measurement result of composition expanded material prepared by above-mentioned steps and the existing EVA foamed products of in the market Data are as shown in table 6.

Table 6

Project	Testing standard	Unit	The product of embodiment 14	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.24	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	3.0	1.5
Elongation at break	ISO1798-2008	%	450	300
					Tearing strength	GB/T10808-2006	N/mm	6.0	4.2
Ball falling resiliency	GB/T6670-2008	%	62	50
					Compression set	GB/T6669-2008	%	18	35
Wearability	DIN53516	Mm³	380	500

Embodiment 15：

The preparation method of above-mentioned expanded material is as follows：

1) the VA contents for weighing corresponding weight are 25% EVA, TPU/EVA alloys, azo dipotassium acid barium, dual-tert-butyl mistake Preliminary mixing is carried out in oxidation cumene and clay input high mixer；

3) second of mixing：The first order mixture input mill of gained in step 2) is carried out into second to be kneaded, mixed Refining temperature is set as 120 DEG C, is kneaded 25 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture input the injection-expansion molded machine of rotating disc type enter Row is one-shot foamed, projects temperature control at 180 DEG C, finally gives high resilience EVA composition Foamed Sole Materials.

Pass through the physical property measurement result of composition expanded material prepared by above-mentioned steps and the existing EVA foamed products of in the market Data are as shown in table 7.

Table 7

Project	Testing standard	Unit	The product of embodiment 15	Market EVA foamed products
					Density	ASTM-D792	g/cm³	0.18	0.25
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	2.8	1.5
Elongation at break	ISO1798-2008	%	420	300
					Tearing strength	GB/T10808-2006	N/mm	5.5	4.2
Ball falling resiliency	GB/T6670-2008	%	62	50
					Compression set	GB/T6669-2008	%	20	35
Wearability	DIN53516	Mm³	380	500

Comparative example 1：

1) EVA, 1 parts by weight TPU, the 1 parts by weight azodicarbonamide AC that 100 parts by weight VA contents are 10% are weighed, is thrown Enter and preliminary mixing is carried out in high mixer；

2) it is kneaded for the first time：It will be put into step 1) by the mixture tentatively mixed in banbury, melting temperature setting For 100 DEG C, it is kneaded 5 minutes, obtains first order mixture；

3) second of mixing：The first order mixture obtained in step 2) input mill is carried out into second to be kneaded, mixed Refining temperature is set as 100 DEG C, is kneaded 5 minutes and obtains second level mixture；

4) foaming and sizing：By above-mentioned steps 3) obtained by second of mixture be placed in shoe sole article mould, by product Mould, which is placed in vulcanizing press, carries out mould hair foaming, and foamed time is 1 minute, and blowing temperature is 100 DEG C, then that mould is cold But to 10 DEG C, EVA composition Foamed Sole Materials are obtained.

By the resulting composition expanded material of comparative example 1 compared with the physical property measurement data of the products obtained therefrom of embodiment 9, knot Fruit is as shown in table 8：

Table 8

Project	Testing standard	Unit	Embodiment 9	Comparative example 1
					Density	ASTM-D792	g/cm³	0.2	0.24
Hardness	GB/T10807-2006	Shore	45	45
					Tensile strength	ISO1798-2008	MPa	5.0	0.8
Elongation at break	ISO1798-2008	%	500	220
					Tearing strength	GB/T10808-2006	N/mm	8	3.5
Ball falling resiliency	GB/T6670-2008	%	60	52
					Compression set	GB/T6669-2008	%	25	48
Wearability	DIN53516	Mm³	400	550

It can be seen that from the data in table 1- tables 8 and be substantially better than using the properties of product prepared by technical solution of the present invention Properties of product of the EVA prepared by with the direct mixed foamings of TPU or existing conventional EVA foaming systems；The another side present invention utilizes TPU Excellent wearability, mechanical performance, substantially improve it is existing foaming EVA material the performance such as resilience, compression set, and And simplification of flowsheet, reduced without carrying out scrap build or equipment research and development, investment, production cost.

The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims

A kind of 1. high resilience composition expanded material of sole, it is characterised in that by weight, including following component：

Wherein, the thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy can use one of following four kinds of methods to be made It is standby, method one, comprise the following steps:

1) the TPU raw materials of 100 parts by weight are added to the charging aperture of double screw extruder after premix, by the second of 5-95 parts by weight Alkene-acetate ethylene copolymer and the double activated material of 0.1-10 parts by weight are injected into extruder by side feeding, and the two is without elder generation Order afterwards, the auxiliary agents of 0.1-5 parts by weight be added in TPU raw materials or ethylene-vinyl acetate copolymer and double activated material it is mixed In compound；

2) reaction zone temperature for controlling extruder is 50-250 DEG C, and the material after extrusion is dried, produced through being granulated；

Method two, comprises the following steps：By the double activated of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and by mixture by being granulated after extruding machining, are produced；

Method three, comprises the following steps：By the double activated of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and are granulated, produced after mixture is machined by mill；

Method four, comprises the following steps：By the double activated of EVA, 0.1-10 parts by weight of TPU, 5-95 parts by weight of 100 parts by weight Material and the auxiliary agent of 0.1-5 parts by weight are well mixed, and are granulated, produced after mixture is machined by banburying；

The double activated material is to contain anhydride group, carboxyl-COOH, hydroxyl-OH, amino-NH or-NH₂, NCO- One or more compounds in NCO, epoxide group, the auxiliary agent include initiator.
2. the high resilience composition expanded material of sole according to claim 1, it is characterised in that described double activated thing Matter is maleic anhydride, GMA, acrylic acid, methyl methacrylate, butyl acrylate, acrylic acid acyl One kind in amine, allyl polyglycol, amino acid, epoxy resin.
3. the high resilience composition expanded material of sole according to claim 1 or 2, it is characterised in that institute in method one The TPU raw materials stated include polymer polyatomic alcohol, chain extender and isocyanates, and the polymer polyatomic alcohol is PEPA, gathered One or more in ethoxylated polyhydric alcohol, polycaprolactone polyol, polycarbonate polyol, end hydroxy butadiene glycol answer Match somebody with somebody, described chain extender is small molecule dihydric alcohol or binary amine containing less than 12 carbon atoms, and the isocyanates is first Phenylene diisocyanate TD I, methyl diphenylene diisocyanate MD I, hexamethylene diisocyanate HD I, dicyclohexyl methyl hydride Diisocyanate H12MD I, isofoer diisocyanate I PD I, one kind in XDI XD I or A variety of compoundings, method two, method three, the hardness of TPU described in method four are 40-95Shore A, melt flow rate (MFR) 5- 100g/10mi n, it applies 5Kg weight at 200 DEG C according to ASTM-1238 and measured.
4. the high resilience composition expanded material of sole according to claim 1 or 2, it is characterised in that the thermoplasticity The vinyl acetate content of ethylene-vinyl acetate copolymer is 10-80wt% in polyurethane/ethene-vinyl acetate alloy, preferably Ground, the content of vinyl acetate is 20-50wt%, and most preferably the content of vinyl acetate is 25-45%.
5. the high resilience composition expanded material of sole according to claim 1 or 2, it is characterised in that the foaming agent For one or more of mixtures in heat release type foaming agent, endothermic blowing agent, foam microspheres, it is preferable that the foaming agent Refer to azodicarbonamide, azodiisobutyronitrile, Barium azodicarboxylate, 4,4 '-OBSH, unifor, Sodium acid carbonate, sodium citrate, ammonium hydrogen carbonate, one or more mixtures in expended microsphere.
6. the high resilience composition expanded material of sole according to claim 1 or 2, it is characterised in that the crosslinking agent For cumyl peroxide, dual-tert-butyl cumene hydroperoxide, azodiisobutyronitrile, azo isobutyl cyano group formamide, azo Dicyclohexyl first cyanogen, one or more of mixtures in azo-bis-iso-dimethyl.
7. the high resilience EVA composition expanded materials of sole according to claim 1 or 2, it is characterised in that the filler For talcum powder, calcium carbonate, clay, sulfate, one or more of mixtures in toner.
8. the high resilience composition expanded material of sole according to claim 1 or 2, it is characterised in that the composition Also include antioxidant, lubricant, the auxiliary agent of resistance to UV, assistant crosslinking agent and foamed promoter in expanded material, the assistant crosslinking agent be containing There are the compound of 2 and above carbon-carbon double bond, the foamed promoter is any one in zinc oxide, zinc stearate.
9. the preparation method of the high resilience composition expanded material of sole any one of claim 1-8, its feature exist In comprising the following steps：

1) 100 parts of EVA, thermoplastic polyurethane/ethylene-vinyl acetate copolymer alloy 1-70 parts, hair by weight, are weighed Infusion 0.1-10 parts, crosslinking agent 0.01-10 parts, filler 0-20 parts are put into and preliminary mixing are carried out in high mixer；

2) it is kneaded for the first time：Uniform, 5-25 points of control mixing time will be kneaded in mixture input banbury obtained by step 1) Clock, 100-150 DEG C of melting temperature, obtain first order mixture；

3) second of mixing：First order mixture obtained by step 2) is put into mill and carries out second of mixing, control Mixing time 5-30 minutes, 80-200 DEG C of melting temperature, obtain second level mixture；4) foaming and sizing：By obtained by step 3) Second level mixture be placed in shoe sole article mould, after be placed in vulcanizing press and carry out moulded from foam, blowing temperature For 100-200 DEG C, foamed time is 1-10 minutes, and mould then is cooled into 10-50 DEG C, obtains high resilience EVA compositions Foaming sole material；Or the second level mixture obtained by step 3) is put into the foaming shoe material equipment once projected and carried out It is one-shot foamed, temperature control is projected at 120-180 DEG C, obtains high resilience EVA composition foaming sole materials.
10. preparation method according to claim 9, it is characterised in that the foaming shoe once projected described in step 4) Material equipment refers to injection-expansion molded machine.