CN110054831A - A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof - Google Patents
A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof Download PDFInfo
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- CN110054831A CN110054831A CN201910380845.0A CN201910380845A CN110054831A CN 110054831 A CN110054831 A CN 110054831A CN 201910380845 A CN201910380845 A CN 201910380845A CN 110054831 A CN110054831 A CN 110054831A
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of graphene regeneration EVA foamed shoe sole micelles and preparation method thereof, are made of the raw material for including following parts by weight: 22~28 parts of ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 45~50 parts, 13~17 parts of oxidic polyethylene, 4~7 parts of graphene, 1~2 part of carboxylated graphene, 2~4 parts of antioxidant, 1.5~3 parts of light stabilizer, 3~5 parts of zinc stearate.Graphene regeneration EVA foamed shoe sole micelle of the invention is made up of selected raw material, and rational formula, so that graphene of the invention is regenerated EVA foamed shoe sole micelle as EVA foaming sole material, has many advantages, such as that tensile strength and tearing strength are high, resistance to bend(ing) energy is good, rebound degree is larger, resilience is good, dimensional contraction rate is small；Performance is close compared with commercially available EVA shoe bottom material, even better than commercially available EVA shoe bottom material；The recycling for realizing EVA improves the utilization rate of EVA, reduces cost of material, and more environmentally-friendly.
Description
Technical field
The present invention relates to EVA shoe bottom technical fields, and in particular to a kind of graphene regeneration EVA foamed shoe sole micelle and its system
Preparation Method.
Background technique
Graphene (Graphene) be one kind by carbon atom with sp2Hybridized orbit forms the two dimension that hexangle type is in honeycomb lattice
Carbon nanomaterial.Graphene has excellent optics, electricity, mechanical characteristic, in materialogy, micro-nano technology, the energy, biomedicine
It is with important application prospects with drug delivery etc., it is considered to be a kind of future revolutionary material.Graphene is common
The method of power production is mechanical stripping method, oxidation-reduction method, SiC epitaxial growth method, and film production method is chemical vapor deposition
Area method (CVD).
Ethylene-vinyl acetate copolymer (EVA) is used as a kind of macromolecule polymeric material, has good plasticity, elasticity
And machinability, and by foaming, treated that EVA material has many advantages, such as that density is small, mechanical property is good, easy coloring, because
This, EVA is often widely used in various sole materials.
Such as, Chinese patent CN103951872A discloses a kind of lightweight EVA shoe bottom material and preparation method thereof, the material packet
Include following component: EVA7350, light silicon dioxide filler, POE8003 micelle, industrial calomel mercurous chloride, foaming agent, coupling agent, zinc oxygen
Powder, stearic acid are in parts by weight.Preparation method includes mixing, mill, granulation, cooling, foaming.Chinese patent
CN107236183A discloses a kind of preparation method of heat-resistant, wear-resistant EVA material sole, comprising the following steps: (1) raw material weigh,
(2) mixing processing, the processing of (3) mill, (4) are granulated foaming processing.Chinese patent CN102993545A discloses a kind of for shoes
The light anti-skidding high wear-resistant rubber material at bottom and preparation method thereof.The present invention is used for the light anti-skidding high wear-resistant rubber material of sole
Material, is made: EVA, NR, SBR, CaCO3, anti-wear agent, ZnO, ZnST, ST, DCP, AC by the raw material of following weight.
But it there is problems in the use of EVA foamed shoe sole at present:
1, can not to ethylene-vinyl acetate copolymer leftover pieces carry out reasonably, the recycling of high value, because of second
Alkene-acetate ethylene copolymer leftover pieces reuse can enable tensile strength and tearing strength, resistance to bend(ing), rebound degree and size
The comprehensive service performance such as shrinking percentage is deteriorated, and short as sole material service life, comfort level is poor；
2, at high cost to the recycling of ethylene-vinyl acetate copolymer leftover pieces.
Summary of the invention
Based on the above situation, the purpose of the present invention is to provide a kind of graphene regeneration EVA foamed shoe sole micelle and its systems
Preparation Method can effectively solve problem above.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of graphene regeneration EVA foamed shoe sole micelle, is made: ethyl vinyl acetate second of the raw material for including following parts by weight
22~28 parts of alkene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 45~50 parts, 13~17 parts of oxidic polyethylene, stone
4~7 parts of black alkene, 1~2 part of carboxylated graphene, 2~4 parts of antioxidant, 1.5~3 parts of light stabilizer, 3~5 parts of zinc stearate.
Preferably, the graphene regeneration EVA foamed shoe sole micelle is by including that the raw material of following parts by weight is made: ethylene-
25 parts of acetate ethylene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 48 parts, 15.5 parts of oxidic polyethylene, graphene
6.3 parts, 1.6 parts of carboxylated graphene, 3.1 parts of antioxidant, 2.7 parts of light stabilizer, 4.4 parts of zinc stearate.
Preferably, the antioxidant is the compound antioxidant of antioxidant 4010NA-M and antioxidant B900.
It is furthermore preferred that antioxidant 4010NA-M in the compound antioxidant of the antioxidant 4010NA-M and antioxidant B900
Mass ratio with antioxidant B900 is 1:(0.5~0.7).
Preferably, the compounding light that the light stabilizer is light stabilizer HS-508 and light stabilizer UV-3853PP5 is stablized
Agent.
It is furthermore preferred that light is stablized in the compounding light stabilizer of the light stabilizer HS-508 and light stabilizer UV-3853PP5
The mass ratio of agent HS-508 and light stabilizer UV-3853PP5 are 1:(0.65~0.75).
Preferably, the diameter of the graphene is 1~2um, and with a thickness of 1.5~2.5nm, purity is greater than 99%, moisture content
Less than 1.5%, bulk density is 0.01~0.03g/ml.
Preferably, the diameter of the carboxylated graphene is 1~4um, with a thickness of 0.8~1.2nm, carboxyl ratio is 4~
6%, purity is greater than 99%, and for moisture content less than 2%, bulk density is 0.01~0.04g/ml.
Preferably, the granularity of the ethylene-vinyl acetate copolymer leftover pieces milling is 30~40 mesh.
The present invention also provides the preparation methods of the graphene regeneration EVA foamed shoe sole micelle described in one kind, including following step
It is rapid:
A, weigh respectively by weight ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling,
Oxidic polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphite
Alkene and carboxylated graphene are sent into high-speed mixer, and revolving speed control mixes 5~10min, obtain in 3000~5000r/min
EVA mixture；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 80 in temperature
Then 5~10min of mixing under the conditions of~85 DEG C, then 8~14min of mixing under the conditions of temperature is 95~100 DEG C are in temperature
5~8min of mixing, finally discharges under the conditions of 110~115 DEG C, obtains primary mix；
D, the primary mix obtained step C is sent into open mill, and be added the other half zinc stearate, antioxidant and
Light stabilizer, 10~20min of mill under the conditions of temperature is 70~75 DEG C；
E, it is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 80~85 DEG C when granulation, mould
Head temperature is set as 85~95 DEG C, and it is 2~4mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
Compared with prior art, the present invention have the following advantages that and the utility model has the advantages that
Graphene regeneration EVA foamed shoe sole micelle of the invention is made up of selected raw material, and rational formula, makes the present invention
Graphene regeneration EVA foamed shoe sole micelle be used as EVA foaming sole material, have tensile strength and tearing strength height, bending resistance
The advantages that Qu Xingneng is good, rebound degree is larger, resilience is good, dimensional contraction rate is small；Graphene of the invention regenerates EVA foamed shoe sole
Micelle performance compared with commercially available EVA shoe bottom material is close, even better than commercially available EVA shoe bottom material；Graphene regeneration of the invention
EVA foamed shoe sole micelle realizes the recycling of EVA, improves the utilization rate of EVA, reduces cost of material, and more ring
It protects.
The graphene and carboxylated graphene of proper proportion in graphene regeneration EVA foamed shoe sole micelle of the invention, with
The component compatibilities such as ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling are good, and cooperate, and rise
To good synergistic effect, greatly improves tensile strength and tearing strength is high, ensure that rebound degree is larger, resilience is good, ruler
Very little shrinking percentage is small.
The compounding of antioxidant 4010NA-M and antioxidant B900 are anti-in graphene regeneration EVA foamed shoe sole micelle of the invention
The addition of oxidant, for ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling based on system,
It can guarantee good ageing-resistant performance, and use single antioxidant, ageing-resistant performance is poor, or even is not able to satisfy sole material
The requirement of material.
Light stabilizer HS-508 and light stabilizer UV-3853PP5 in graphene regeneration EVA foamed shoe sole micelle of the invention
Compounding light stabilizer addition, for ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling be
Main system can guarantee good photostability, and (generation) xanthochromia is not susceptible in use process, can satisfy sole material
Requirement, and use single light stabilizer, photostability is poor, or even is not able to satisfy the requirement of sole material.
Preparation method simple process of the invention, it is easy to operate, it ensure that graphene regeneration EVA foamed shoe sole of the invention
Micelle is as EVA foaming sole material, with tensile strength and tearing strength are high, resistance to bend(ing) energy is good, rebound degree is larger, rebound
The advantages that property is good, dimensional contraction rate is small.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The preferred embodiments of the invention are described, but should not be understood as the limitation to this patent.
Test method described in following embodiments or test method are unless otherwise specified conventional method；The reagent
And material is obtained from routine business approach, or prepare in conventional manner unless otherwise specified.
Embodiment 1:
A kind of graphene regeneration EVA foamed shoe sole micelle, is made: ethyl vinyl acetate second of the raw material for including following parts by weight
22~28 parts of alkene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 45~50 parts, 13~17 parts of oxidic polyethylene, stone
4~7 parts of black alkene, 1~2 part of carboxylated graphene, 2~4 parts of antioxidant, 1.5~3 parts of light stabilizer, 3~5 parts of zinc stearate.
The present invention also provides the preparation methods of the graphene regeneration EVA foamed shoe sole micelle described in one kind, including following step
It is rapid:
A, weigh respectively by weight ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling,
Oxidic polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphite
Alkene and carboxylated graphene are sent into high-speed mixer, and revolving speed control mixes 5~10min, obtain in 3000~5000r/min
EVA mixture；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 80 in temperature
Then 5~10min of mixing under the conditions of~85 DEG C, then 8~14min of mixing under the conditions of temperature is 95~100 DEG C are in temperature
5~8min of mixing, finally discharges under the conditions of 110~115 DEG C, obtains primary mix；
D, the primary mix obtained step C is sent into open mill, and be added the other half zinc stearate, antioxidant and
Light stabilizer, 10~20min of mill under the conditions of temperature is 70~75 DEG C；
E, it is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 80~85 DEG C when granulation, mould
Head temperature is set as 85~95 DEG C, and it is 2~4mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
Embodiment 2:
A kind of graphene regeneration EVA foamed shoe sole micelle, is made: ethyl vinyl acetate second of the raw material for including following parts by weight
22 parts of alkene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 45 parts, 13 parts of oxidic polyethylene, 4 parts of graphene, carboxyl
1 part of graphite alkene, 2 parts of antioxidant, 1.5 parts of light stabilizer, 3 parts of zinc stearate.
In the present embodiment, the antioxidant is the compound antioxidant of antioxidant 4010NA-M and antioxidant B900.
In the present embodiment, anti-aging agent in the compound antioxidant of the antioxidant 4010NA-M and antioxidant B900
The mass ratio of 4010NA-M and antioxidant B900 are 1:0.5.
In the present embodiment, the light stabilizer is the compounding light of light stabilizer HS-508 and light stabilizer UV-3853PP5
Stabilizer.
In the present embodiment, light in the compounding light stabilizer of the light stabilizer HS-508 and light stabilizer UV-3853PP5
The mass ratio of stabilizer HS-508 and light stabilizer UV-3853PP5 are 1:0.65.
In the present embodiment, the diameter of the graphene is 1um, and with a thickness of 1.5nm, purity 99.5%, moisture content is
1.2%, bulk density 0.01g/ml.
In the present embodiment, the diameter of the carboxylated graphene is 1um, and with a thickness of 0.8nm, carboxyl ratio 4% is pure
Degree is 99.6%, moisture content 1.6%, bulk density 0.01g/ml.
In the present embodiment, the granularity of the ethylene-vinyl acetate copolymer leftover pieces milling is 30 mesh.
In the present embodiment, the preparation method of graphene regeneration EVA foamed shoe sole micelle, including the following steps:
A, weigh respectively by weight ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling,
Oxidic polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphite
Alkene and carboxylated graphene are sent into high-speed mixer, and revolving speed control mixes 10min, obtain EVA mixture in 3000r/min；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 80 in temperature
Mixing 10min under the conditions of DEG C, then mixing 14min under the conditions of temperature is 95 DEG C, then mixing under the conditions of temperature is 110 DEG C
8min finally discharges, and obtains primary mix；
D, the primary mix obtained step C is sent into open mill, and be added the other half zinc stearate, antioxidant and
Light stabilizer, mill 20min under the conditions of temperature is 70 DEG C；
E, it is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 80 DEG C when granulation, die head temperature
Degree is set as 85 DEG C, and it is 2mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
Embodiment 3:
A kind of graphene regeneration EVA foamed shoe sole micelle, is made: ethyl vinyl acetate second of the raw material for including following parts by weight
28 parts of alkene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 50 parts, 17 parts of oxidic polyethylene, 7 parts of graphene, carboxyl
2 parts of graphite alkene, 4 parts of antioxidant, 3 parts of light stabilizer, 5 parts of zinc stearate.
In the present embodiment, the antioxidant is the compound antioxidant of antioxidant 4010NA-M and antioxidant B900.
In the present embodiment, anti-aging agent in the compound antioxidant of the antioxidant 4010NA-M and antioxidant B900
The mass ratio of 4010NA-M and antioxidant B900 are 1:0.7.
In the present embodiment, the light stabilizer is the compounding light of light stabilizer HS-508 and light stabilizer UV-3853PP5
Stabilizer.
In the present embodiment, light in the compounding light stabilizer of the light stabilizer HS-508 and light stabilizer UV-3853PP5
The mass ratio of stabilizer HS-508 and light stabilizer UV-3853PP5 are 1:0.75.
In the present embodiment, the diameter of the graphene is 2um, and with a thickness of 2.5nm, purity 99.5%, moisture content is
1.2%, bulk density 0.03g/ml.
In the present embodiment, the diameter of the carboxylated graphene is 4um, and with a thickness of 1.2nm, carboxyl ratio 6% is pure
Degree is 99.5%, moisture content 1.7%, bulk density 0.04g/ml.
In the present embodiment, the granularity of the ethylene-vinyl acetate copolymer leftover pieces milling is 40 mesh.
In the present embodiment, the preparation method of graphene regeneration EVA foamed shoe sole micelle, including the following steps:
A, weigh respectively by weight ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling,
Oxidic polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphite
Alkene and carboxylated graphene are sent into high-speed mixer, and revolving speed control mixes 5min, obtain EVA mixture in 5000r/min；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 85 in temperature
Mixing 5min under the conditions of DEG C, then mixing 8min under the conditions of temperature is 100 DEG C, then mixing under the conditions of temperature is 115 DEG C
5min finally discharges, and obtains primary mix；
D, the primary mix obtained step C is sent into open mill, and be added the other half zinc stearate, antioxidant and
Light stabilizer, mill 10min under the conditions of temperature is 75 DEG C；
E, it is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 85 DEG C when granulation, die head temperature
Degree is set as 95 DEG C, and it is 4mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
Embodiment 4:
A kind of graphene regeneration EVA foamed shoe sole micelle, is made: ethyl vinyl acetate second of the raw material for including following parts by weight
25 parts of alkene copolymer, ethylene-vinyl acetate copolymer leftover pieces be milled 48 parts, 15.5 parts of oxidic polyethylene, 6.3 parts of graphene,
1.6 parts of carboxylated graphene, 3.1 parts of antioxidant, 2.7 parts of light stabilizer, 4.4 parts of zinc stearate.
In the present embodiment, the antioxidant is the compound antioxidant of antioxidant 4010NA-M and antioxidant B900.
In the present embodiment, anti-aging agent in the compound antioxidant of the antioxidant 4010NA-M and antioxidant B900
The mass ratio of 4010NA-M and antioxidant B900 are 1:0.6.
In the present embodiment, the light stabilizer is the compounding light of light stabilizer HS-508 and light stabilizer UV-3853PP5
Stabilizer.
In the present embodiment, light in the compounding light stabilizer of the light stabilizer HS-508 and light stabilizer UV-3853PP5
The mass ratio of stabilizer HS-508 and light stabilizer UV-3853PP5 are 1:0.7.
In the present embodiment, the diameter of the graphene is 1.5um, and with a thickness of 2nm, purity 99.8%, moisture content is
1.1%, bulk density 0.02g/ml.
In the present embodiment, the diameter of the carboxylated graphene is 2um, and with a thickness of 1.1nm, carboxyl ratio 5% is pure
Degree is 99.8%, moisture content 1.5%, bulk density 0.02g/ml.
In the present embodiment, the granularity of the ethylene-vinyl acetate copolymer leftover pieces milling is 35 mesh.
In the present embodiment, the preparation method of graphene regeneration EVA foamed shoe sole micelle, including the following steps:
A, weigh respectively by weight ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling,
Oxidic polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphite
Alkene and carboxylated graphene are sent into high-speed mixer, and revolving speed control mixes 7min, obtain EVA mixture in 4000r/min；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 83 in temperature
Mixing 8min under the conditions of DEG C, then mixing 11min under the conditions of temperature is 98 DEG C, then mixing under the conditions of temperature is 112 DEG C
7min finally discharges, and obtains primary mix；
D, the primary mix obtained step C is sent into open mill, and be added the other half zinc stearate, antioxidant and
Light stabilizer, mill 16min under the conditions of temperature is 73 DEG C；
E, it is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 82 DEG C when granulation, die head temperature
Degree is set as 89 DEG C, and it is 3mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
Batten is made to the graphene regeneration EVA foamed shoe sole micelle that the embodiment of the present invention 2 to embodiment 4 obtains below
(sample) and commercially available EVA shoe bottom material are tested for the property respectively, and test result is as shown in table 1:
Table 1
As can be seen from the above table, graphene of the invention regeneration EVA foamed shoe sole micelle has the advantage that as EVA
Foaming sole material, tensile strength and tearing strength are high, and resistance to bend(ing) can be good, and rebound degree is larger, and resilience is good, dimensional contraction rate
It is small；Performance is close compared with commercially available EVA shoe bottom material, even better than commercially available EVA shoe bottom material.
In addition, the graphene regeneration EVA foamed shoe sole micelle that the embodiment of the present invention 2 to embodiment 4 obtains after tested is resistance to
Ageing properties are good, good light stability, and (generation) xanthochromia is not susceptible in use process, can satisfy the requirement of sole material；And
Using single antioxidant and light stabilizer, ageing-resistant performance is poor, and photostability is poor, or even is not able to satisfy sole material
It is required that.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of graphene regenerates EVA foamed shoe sole micelle, which is characterized in that be made of the raw material for including following parts by weight: second
22~28 parts of alkene-acetate ethylene copolymer, ethylene-vinyl acetate copolymer leftover pieces milling 45~50 parts, oxidic polyethylene 13
~17 parts, 4~7 parts of graphene, 1~2 part of carboxylated graphene, 2~4 parts of antioxidant, 1.5~3 parts of light stabilizer, stearic acid
3~5 parts of zinc.
2. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the graphene regeneration
EVA foamed shoe sole micelle is by including that the raw material of following parts by weight is made: 25 parts of ethylene-vinyl acetate copolymer, ethyl vinyl acetate second
Alkene copolymer leftover pieces be milled 48 parts, it is 15.5 parts of oxidic polyethylene, 6.3 parts of graphene, 1.6 parts of carboxylated graphene, anti-oxidant
3.1 parts of agent, 2.7 parts of light stabilizer, 4.4 parts of zinc stearate.
3. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the antioxidant is
The compound antioxidant of antioxidant 4010NA-M and antioxidant B900.
4. graphene according to claim 3 regenerates EVA foamed shoe sole micelle, which is characterized in that the anti-aging agent
The mass ratio of antioxidant 4010NA-M and antioxidant B900 are 1 in the compound antioxidant of 4010NA-M and antioxidant B900:
(0.5~0.7).
5. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the light stabilizer is
The compounding light stabilizer of light stabilizer HS-508 and light stabilizer UV-3853PP5.
6. graphene according to claim 5 regenerates EVA foamed shoe sole micelle, which is characterized in that the light stabilizer HS-
The matter of light stabilizer HS-508 and light stabilizer UV-3853PP5 in the compounding light stabilizer of 508 and light stabilizer UV-3853PP5
The ratio between amount is 1:(0.65~0.75).
7. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the graphene it is straight
Diameter is 1~2um, and with a thickness of 1.5~2.5nm, purity is greater than 99%, moisture content less than 1.5%, bulk density is 0.01~
0.03g/ml。
8. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the carboxyl graphite
The diameter of alkene is 1~4um, and with a thickness of 0.8~1.2nm, carboxyl ratio is 4~6%, and purity is greater than 99%, moisture content less than 2%,
Bulk density is 0.01~0.04g/ml.
9. graphene according to claim 1 regenerates EVA foamed shoe sole micelle, which is characterized in that the ethyl vinyl acetate second
The granularity of alkene copolymer leftover pieces milling is 30~40 mesh.
10. a kind of preparation method of graphene regeneration EVA foamed shoe sole micelle as described in any one of claim 1 to 9, special
Sign is, including the following steps:
A, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidation are weighed respectively by weight
Polyethylene, graphene, carboxylated graphene, antioxidant, light stabilizer and zinc stearate；
B, by ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer leftover pieces milling, oxidic polyethylene, graphene and
Carboxylated graphene is sent into high-speed mixer, and revolving speed control mixes 5~10 min, obtain EVA in 3000~5000r/min
Mixture；
C, the EVA mixture for obtaining step B is sent into mixer, and the zinc stearate of half is added, and is first 80~85 in temperature
Then 5~10 min of mixing under the conditions of DEG C, then 8~14 min of mixing under the conditions of temperature is 95~100 DEG C are 110 in temperature
5~8 min of mixing, finally discharges under the conditions of~115 DEG C, obtains primary mix；
D, the primary mix for obtaining step C is sent into open mill, and zinc stearate, antioxidant and light that the other half is added are steady
Determine agent, 10~20 min of mill under the conditions of temperature is 70~75 DEG C；
It is finally sent into pelletizer, is granulated, the expects pipe temperature of control pelletizer is set as 80~85 DEG C when granulation, die head temperature
It is set as 85~95 DEG C, it is 2~4mm that control, which is granulated length, obtains the graphene regeneration EVA foamed shoe sole micelle.
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| CN201910380845.0A CN110054831A (en) | 2019-05-08 | 2019-05-08 | A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof |
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| CN201910380845.0A CN110054831A (en) | 2019-05-08 | 2019-05-08 | A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof |
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| CN110818990A (en) * | 2019-10-28 | 2020-02-21 | 茂泰(福建)鞋材有限公司 | Preparation method of light slow-running shoe sole |
| CN110885487A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Preparation method of biodegradable foamed sole |
| CN110885486A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Method for manufacturing foamed sole |
| KR102185829B1 (en) * | 2020-04-23 | 2020-12-02 | 채건하 | Waste midsole member and eva foam mixing midsole fabric manufacturing equipment |
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| CN110818990A (en) * | 2019-10-28 | 2020-02-21 | 茂泰(福建)鞋材有限公司 | Preparation method of light slow-running shoe sole |
| CN110885487A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Preparation method of biodegradable foamed sole |
| CN110885486A (en) * | 2019-10-28 | 2020-03-17 | 茂泰(福建)鞋材有限公司 | Method for manufacturing foamed sole |
| KR102185829B1 (en) * | 2020-04-23 | 2020-12-02 | 채건하 | Waste midsole member and eva foam mixing midsole fabric manufacturing equipment |
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Application publication date: 20190726 |