CN109265808A - Sole low compression deformation sheet material and its preparation process - Google Patents
Sole low compression deformation sheet material and its preparation process Download PDFInfo
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- CN109265808A CN109265808A CN201810885685.0A CN201810885685A CN109265808A CN 109265808 A CN109265808 A CN 109265808A CN 201810885685 A CN201810885685 A CN 201810885685A CN 109265808 A CN109265808 A CN 109265808A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
The present invention relates to sole low compression deformation sheet materials and its preparation process, comprising steps of stock, mixing, vulcanization test, plasma treatment and moulded from foam, wherein weigh multiple groups respectively by different ratio, be respectively formulated in addition to the different outer other components contents of ethylene-propylene diene copolymer, zinc oxide and blowing agent AC content are consistent；Multiple molded tablets superposition that density is successively increased carries out one-step mould foaming.Using sheet material compressive deformation≤10% produced by the present invention, it is layered tearing >=25N/mm, compression resilience >=70% is heat-shrinked≤1.2%, impact strength >=4.5MPa, and mechanical performance is splendid.The present invention reduces external force to the impact side effect of rubber and plastic matrix by layered laminate functionalization graphene and assigns support toughness well, due to the gradually changeable of density, stress, which is concentrated, to be mitigated, the material of preparation does not generate buckling deformation, each density layer is mutually supported to cooperate, it is restored after facilitating compression, efficacy lasting stabilization.
Description
Technical field
The present invention relates to footwear technologies, more particularly to a kind of sole low compression deformation sheet material and its preparation work
Skill.
Background technique
It is well known that the elastic force of sole and the height of energy back value play the movenent performance of sole in important work
With, if the energy back value of sole is not high, after dress campaign a period of time of the sole, the consumption of kinergety is too big,
It can not be converted into the power of movement, thus can not easily be moved for a long time, comfort level substantially reduces.For the energy for improving sole
Value of feedback can generally select to be embedded in an elastomer block, other projecting materials of the rebound degree of the elastomer block in half sole portion top surface
The rebound degree of material provides power-assisted screen resilience by the elastomer block and promotes wearing comfort.But existing elastomer block makes
Rebound effect is lost with easily occurring weak after a period of time.
Summary of the invention
To overcome technological deficiency of the existing technology, the present invention provides a kind of sole low compression deformation sheet material and its system
Preparation Method, compression set rate is low, shrinks small, efficacy lasting stabilization.
The technical solution that the present invention uses is:
A kind of sole preparation process of low compression deformation sheet material, specifically comprises the following steps:
Step 1), stock: weighed respectively by different ratio EVA, OBC, LLDPE, ethylene-propylene diene copolymer, isoprene rubber, benzophenone,
Layered laminate functionalization graphene SF-GNRs, zinc stearate, gas-phase silica, atoleine, crosslink agent DCP, blowing agent AC, oxygen
Change zinc to constitute multiple groups formula, be respectively formulated in addition to the different outer other components of ethylene-propylene diene copolymer, zinc oxide and blowing agent AC content
Content is consistent；
Step 2, mixing: each raw material in each formula other than blowing agent AC and crosslink agent DCP is poured into mixer respectively
It is kneaded, first time stirring is carried out when temperature reaches 95 DEG C~96 DEG C；Second is carried out when temperature reaches 104~105 DEG C
Secondary stirring；Third time stirring is carried out when temperature reaches 110 DEG C~111 DEG C, while blowing agent AC and crosslink agent DCP progress is added
It is kneaded；The 4th stirring is carried out when temperature reaches 118 DEG C~120 DEG C；When temperature reach 125 DEG C~126 DEG C when can batch turning,
Then upper open mill thins at least twice, 2mm~3mm slice, be stored at room temperature 24 hours or more it is spare；
Step 3), vulcanization test: vulcanized and foamed test using no rotor foaming fluidisation instrument, it is consistent to filter out conditions of vulcanization
Material piece, so as to integrated molding of the multilayer material under the same conditions of vulcanization；The conditions of vulcanization of screening are as follows: curing temperature
It is 160 DEG C~180 DEG C, vulcanization time is 6min~12min；Sample progress density measurement obtained, sieve after vulcameter is tested
Density difference is selected in 0.2g/cm3~0.3g/cm3In the range of material piece, as mold pressing procedure select different densities layer, system
The reference frame of standby density gradient material；
Step 4), plasma treatment: the material piece of the different densities of screening is cut into, difference consistent with mold shape and size
Material piece surface handle with argon plasma and exposes a period of time in air, to be formed on material piece surface
Oxide and hydrogen peroxide, supply frequency are 40kHz~50kHz, and power is 30W~40W, and argon pressure is 6Pa~8Pa；
Step 5), moulded from foam: density is successively increased into 0.03g/cm3~0.04g/cm3Multiple molded tablets be added to it is same
In mold, thus the assembly that composition density gradually changes；Then it is forced into 8Mpa~10Mpa, molding temperature is 160 DEG C~
180 DEG C, clamp time is 6min~12min, after compression molding with after constant temperature flowing water linear shrinkage cooling and shaping up to dimensionally stable
Low compression deformation sheet material.
Preferably, the VA content in the EVA is between 26%~40%.
Preferably, the hardness range of the ethylene-propylene diene copolymer is 60A~70A.
The present invention also provides soles made from a kind of preparation process according to above-mentioned sole with low compression deformation sheet material with low
Compressive deformation sheet material, the low compression deformation sheet material is interior to be had density gradient and combines closely in sizing material matrix and in layered laminate
Equally distributed graphene two-dimensional slice structure.
Beneficial effects of the present invention:
1, the layered laminate functionalization graphene SF-GNRs in inventive formulation is in EVA, OBC, LLDPE, ethylene-propylene diene copolymer, isoamyl
Intercalation stripping and there are the binding forces such as hydrogen bond therebetween in the rubber and plastic matrix of rubber composition, thus enable SF-GNRs with
Layered laminate, firm and equally distributed special construction mode are firmly present in rubber and plastic matrix, and since graphene has
Unique two-dimensional slice structure due to its high radius-thickness ratio, shows soft form, is easy to generate under external force
Deformation, large area solution cluster and Relative sliding deformation between graphene can generate energy dissipation, to reduce external force to rubber and plastic
The impact side effect of matrix, and layered laminate functionalization graphene SF-GNRs intensity is high, and toughness is strong, can assign good support
Toughness.
2, the present invention is foamed by strict control expansion ratio and the density difference of every layer of material using one-step mould
Type preparation process realizes density gradient difference, and due to the gradually changeable of density, stress, which is concentrated, to be mitigated, and the material of preparation does not generate
Buckling deformation, and it is conducive to the resilience of reinforcing sheet, the effect of spring-like rebound can be presented, each density layer is mutually supported
Cooperation is restored, efficacy lasting stabilization after facilitating compression.
3, the present invention carries out plasma treatment to each material piece respectively before moulded from foam, and has two in each material piece
Benzophenone is enabled between the material piece of adjacent layer after plasma treatment to be covalently keyed, and is generated in situ freely
Base initiator and generate polymerization reaction so that the stronger stabilization of combination between adjacent sheet, avoids using rear delamination.
4, the VA content in EVA of the invention is between 26%~40%, such as platform poly- 3312, tension, tearing strength compared with
It is good；OBCS is to be alternately arranged composed copolymer by hard segment (high rigidity) and soft chain segment (high resiliency) rule, unique
Molecular structure, composition possess pole low compression set value, splendid heat resistance, wearability, elastic material；Linea low density
Polyethylene LLDPE molecular weight is big, has great help to the resistance to shrinkage of foaming body, is compressed and is become using sheet material produced by the present invention
Shape≤10% is layered tearing >=25N/mm, compression resilience >=70%, thermal contraction≤1.2%, impact strength >=4.5MPa, machine
Tool performance is splendid.
Specific embodiment
Embodiment 1:
The present embodiment provides a kind of sole preparation processes of low compression deformation sheet material, specifically comprise the following steps:
Step 1), stock: being weighed each raw material by different ratio respectively, be respectively formulated in addition to ethylene-propylene diene copolymer, zinc oxide and foaming
The different outer other components contents of agent AC content are consistent.Successively be set as from lower to upper according to low compression deformation sheet material first layer,
The second layer, third layer, the 4th layer and layer 5 material piece, the formula of each material piece specifically:
First layer material piece is grouped as by the group of following parts by weight: 45 parts of EVA, 3 parts of isoprene rubber, 12 OBC, 5 parts
LLDPE, 2.0 parts of benzophenone, 4 parts of layered laminate functionalization graphene SF-GNRs, 1 part of crosslink agent DCP, 3 gas phase
White carbon black, 1.5 parts of zinc stearate, 1 part of atoleine, 3.0 parts of blowing agent AC, 1.8 parts of zinc oxide, 8 parts of ternary
The third glue of second；
Second layer material piece is grouped as by the group of following parts by weight: 45 parts of EVA, 3 parts of isoprene rubber, 12 OBC, 5 parts
LLDPE, 2.0 parts of benzophenone, 4 parts of layered laminate functionalization graphene SF-GNRs, 1 part of crosslink agent DCP, 3 gas phase
White carbon black, 1.5 parts of zinc stearate, 1 part of atoleine, 2.8 parts of blowing agent AC, 1.5 parts of zinc oxide, 8 parts of ternary
The third glue of second；
Third layer material piece is grouped as by the group of following parts by weight: 45 parts of EVA, 3 parts of isoprene rubber, 12 OBC, 5 parts
LLDPE, 2.0 parts of benzophenone, 4 parts of layered laminate functionalization graphene SF-GNRs, 1 part of crosslink agent DCP, 3 gas phase
White carbon black, 1.5 parts of zinc stearate, 1 part of atoleine, 2.5 parts of blowing agent AC, 1.5 parts of zinc oxide, 10 parts of ternary
The third glue of second；
4th layer material piece is grouped as by the group of following parts by weight: 45 parts of EVA, 3 parts of isoprene rubber, 12 OBC, 5 parts
LLDPE, 2.0 parts of benzophenone, 4 parts of layered laminate functionalization graphene SF-GNRs, 1 part of crosslink agent DCP, 3 gas phase
White carbon black, 1.5 parts of zinc stearate, 1 part of atoleine, 2.5 parts of blowing agent AC, 1.3 parts of zinc oxide, 11 parts of ternary
The third glue of second；
Layer 5 material piece is grouped as by the group of following parts by weight: 45 parts of EVA, 3 parts of isoprene rubber, 12 OBC, 5 parts
LLDPE, 2.0 parts of benzophenone, 4 parts of layered laminate functionalization graphene SF-GNRs, 1 part of crosslink agent DCP, 3 gas phase
White carbon black, 1.5 parts of zinc stearate, 1 part of atoleine, 2.0 parts of blowing agent AC, 1.0 parts of zinc oxide, 12 parts of ternary
The third glue of second；
VA content in the EVA is between 26%~40%, for example platform poly- 3312, the hardness range of the ethylene-propylene diene copolymer are
60A~70A.
Step 2, mixing: each raw material in each formula other than blowing agent AC and crosslink agent DCP is poured into respectively close
Mill is kneaded, and first time stirring is carried out when temperature reaches 95 DEG C~96 DEG C；It is carried out when temperature reaches 104~105 DEG C
Second of stirring；Third time stirring is carried out when temperature reaches 110 DEG C~111 DEG C, while blowing agent AC and crosslink agent DCP is added
It is kneaded；The 4th stirring is carried out when temperature reaches 118 DEG C~120 DEG C；When temperature reaches 125 DEG C~126 DEG C
Batch turning, then upper open mill thins at least twice, 2mm~3mm slice, be stored at room temperature 24 hours or more it is spare；
Step 3), vulcanization test: vulcanized and foamed test using no rotor foaming fluidisation instrument, it is consistent to filter out conditions of vulcanization
Material piece, so as to integrated molding of the multilayer material under the same conditions of vulcanization；The conditions of vulcanization of screening are as follows: curing temperature
It is 175 DEG C, vulcanization time 8min；Sample progress density measurement obtained, filters out density difference and exists after vulcameter is tested
0.2g/cm3~0.3g/cm3In the range of material piece, as mold pressing procedure select different densities layer, prepare density gradient material
Reference frame；
Step 4), plasma treatment: the material piece of the different densities of screening is cut into, difference consistent with mold shape and size
Material piece surface handle with argon plasma and exposes a period of time in air, to be formed on material piece surface
Oxide and hydrogen peroxide, supply frequency 40kHz, power 40W, argon pressure 7Pa；
Step 5), moulded from foam: density is successively increased into 0.03g/cm3~0.04g/cm3Multiple molded tablets be added to it is same
In mold, thus the assembly that composition density gradually changes；Then it is forced into 8Mpa, molding temperature is 180 DEG C, and clamp time is
6min, with the low compression deformation sheet material after constant temperature flowing water linear shrinkage cooling and shaping up to dimensionally stable after compression molding.
Using in sole low compression deformation sheet material made from the preparation process have density gradient and combine closely in
It in sizing material matrix and is in the equally distributed graphene two-dimensional slice structure of layered laminate.
Embodiment 2:
The present embodiment provides a kind of sole preparation processes of low compression deformation sheet material, specifically comprise the following steps:
Step 1), stock: being weighed each raw material by different ratio respectively, be respectively formulated in addition to ethylene-propylene diene copolymer, zinc oxide and foaming
The different outer other components contents of agent AC content are consistent.Successively be set as from lower to upper according to low compression deformation sheet material first layer,
The second layer, third layer, the 4th layer and layer 5 material piece, the formula of each material piece specifically:
First layer material piece is grouped as by the group of following parts by weight: 40 parts of EVA, 3 parts of isoprene rubber, 15 OBC, 5 parts
LLDPE, 1.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 2.5
Gas-phase silica, 1.0 parts of zinc stearate, 1.5 parts of atoleine, 3.0 parts of blowing agent AC, 1.8 parts of zinc oxide, 8 parts
Ethylene-propylene diene copolymer；
Second layer material piece is grouped as by the group of following parts by weight: 40 parts of EVA, 3 parts of isoprene rubber, 15 OBC, 5 parts
LLDPE, 1.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 2.5
Gas-phase silica, 1.0 parts of zinc stearate, 1.5 parts of atoleine, 2.8 parts of blowing agent AC, 1.5 parts of zinc oxide, 8 parts
Ethylene-propylene diene copolymer；
Third layer material piece is grouped as by the group of following parts by weight: 40 parts of EVA, 3 parts of isoprene rubber, 15 OBC, 5 parts
LLDPE, 1.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 2.5
Gas-phase silica, 1.0 parts of zinc stearate, 1.5 parts of atoleine, 2.5 parts of blowing agent AC, 1.5 parts of zinc oxide, 10 parts
Ethylene-propylene diene copolymer；
4th layer material piece is grouped as by the group of following parts by weight: 40 parts of EVA, 3 parts of isoprene rubber, 15 OBC, 5 parts
LLDPE, 1.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 2.5
Gas-phase silica, 1.0 parts of zinc stearate, 1.5 parts of atoleine, 2.5 parts of blowing agent AC, 1.3 parts of zinc oxide, 11 parts
Ethylene-propylene diene copolymer；
Layer 5 material piece is grouped as by the group of following parts by weight: 40 parts of EVA, 3 parts of isoprene rubber, 15 OBC, 5 parts
LLDPE, 1.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 2.5
Gas-phase silica, 1.0 parts of zinc stearate, 1.5 parts of atoleine, 2.0 parts of blowing agent AC, 1.0 parts of zinc oxide, 12 parts
Ethylene-propylene diene copolymer；
VA content in the EVA is between 26%~40%, for example platform poly- 3312, the hardness range of the ethylene-propylene diene copolymer are
60A~70A.
Step 2, mixing: each raw material in each formula other than blowing agent AC and crosslink agent DCP is poured into respectively close
Mill is kneaded, and first time stirring is carried out when temperature reaches 95 DEG C~96 DEG C；It is carried out when temperature reaches 104~105 DEG C
Second of stirring；Third time stirring is carried out when temperature reaches 110 DEG C~111 DEG C, while blowing agent AC and crosslink agent DCP is added
It is kneaded；The 4th stirring is carried out when temperature reaches 118 DEG C~120 DEG C；When temperature reaches 125 DEG C~126 DEG C
Batch turning, then upper open mill thins at least twice, 2mm~3mm slice, be stored at room temperature 24 hours or more it is spare；
Step 3), vulcanization test: vulcanized and foamed test using no rotor foaming fluidisation instrument, it is consistent to filter out conditions of vulcanization
Material piece, so as to integrated molding of the multilayer material under the same conditions of vulcanization；The conditions of vulcanization of screening are as follows: curing temperature
It is 160 DEG C, vulcanization time 12min；Sample progress density measurement obtained, filters out density difference and exists after vulcameter is tested
0.2g/cm3~0.3g/cm3In the range of material piece, as mold pressing procedure select different densities layer, prepare density gradient material
Reference frame；
Step 4), plasma treatment: the material piece of the different densities of screening is cut into, difference consistent with mold shape and size
Material piece surface handle with argon plasma and exposes a period of time in air, to be formed on material piece surface
Oxide and hydrogen peroxide, supply frequency 45kHz, power 35W, argon pressure 6Pa；
Step 5), moulded from foam: density is successively increased into 0.03g/cm3~0.04g/cm3Multiple molded tablets be added to it is same
In mold, thus the assembly that composition density gradually changes；Then it is forced into 10Mpa, molding temperature is 160 DEG C, clamp time
For 6min, with the low compression deformation sheet material after constant temperature flowing water linear shrinkage cooling and shaping up to dimensionally stable after compression molding.
Using in sole low compression deformation sheet material made from the preparation process have density gradient and combine closely in
It in sizing material matrix and is in the equally distributed graphene two-dimensional slice structure of layered laminate.
Embodiment 3:
The present embodiment provides a kind of sole preparation processes of low compression deformation sheet material, specifically comprise the following steps:
Step 1), stock: being weighed each raw material by different ratio respectively, be respectively formulated in addition to ethylene-propylene diene copolymer, zinc oxide and foaming
The different outer other components contents of agent AC content are consistent.Successively be set as from lower to upper according to low compression deformation sheet material first layer,
The second layer, third layer, the 4th layer and layer 5 material piece, the formula of each material piece specifically:
First layer material piece is grouped as by the group of following parts by weight: 48 parts of EVA, 5 parts of isoprene rubber, 10 OBC, 6 parts
LLDPE, 2.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 3 gas
Phase white carbon black, 2.0 parts of zinc stearate, 1 part of atoleine, 3.0 parts of blowing agent AC, 1.8 parts of zinc oxide, the three of 8 parts
First the third glue of second；
Second layer material piece is grouped as by the group of following parts by weight: 48 parts of EVA, 5 parts of isoprene rubber, 10 OBC, 6 parts
LLDPE, 2.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 3 gas
Phase white carbon black, 2.0 parts of zinc stearate, 1 part of atoleine, 2.8 parts of blowing agent AC, 1.5 parts of zinc oxide, the three of 8 parts
First the third glue of second；
Third layer material piece is grouped as by the group of following parts by weight: 48 parts of EVA, 5 parts of isoprene rubber, 10 OBC, 6 parts
LLDPE, 2.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 3 gas
Phase white carbon black, 2.0 parts of zinc stearate, 1 part of atoleine, 2.5 parts of blowing agent AC, 1.5 parts of zinc oxide, the three of 10 parts
First the third glue of second；
4th layer material piece is grouped as by the group of following parts by weight: 48 parts of EVA, 5 parts of isoprene rubber, 10 OBC, 6 parts
LLDPE, 2.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 3 gas
Phase white carbon black, 2.0 parts of zinc stearate, 1 part of atoleine, 2.5 parts of blowing agent AC, 1.3 parts of zinc oxide, the three of 11 parts
First the third glue of second；
Layer 5 material piece is grouped as by the group of following parts by weight: 48 parts of EVA, 5 parts of isoprene rubber, 10 OBC, 6 parts
LLDPE, 2.5 parts of benzophenone, 5 parts of layered laminate functionalization graphene SF-GNRs, 1.5 parts of crosslink agent DCP, 3 gas
Phase white carbon black, 2.0 parts of zinc stearate, 1 part of atoleine, 2.0 parts of blowing agent AC, 1.0 parts of zinc oxide, the three of 12 parts
First the third glue of second；
VA content in the EVA is between 26%~40%, for example platform poly- 3312, the hardness range of the ethylene-propylene diene copolymer are
60A~70A.
Step 2, mixing: each raw material in each formula other than blowing agent AC and crosslink agent DCP is poured into respectively close
Mill is kneaded, and first time stirring is carried out when temperature reaches 95 DEG C~96 DEG C；It is carried out when temperature reaches 104~105 DEG C
Second of stirring；Third time stirring is carried out when temperature reaches 110 DEG C~111 DEG C, while blowing agent AC and crosslink agent DCP is added
It is kneaded；The 4th stirring is carried out when temperature reaches 118 DEG C~120 DEG C；When temperature reaches 125 DEG C~126 DEG C
Batch turning, then upper open mill thins at least twice, 2mm~3mm slice, be stored at room temperature 24 hours or more it is spare；
Step 3), vulcanization test: vulcanized and foamed test using no rotor foaming fluidisation instrument, it is consistent to filter out conditions of vulcanization
Material piece, so as to integrated molding of the multilayer material under the same conditions of vulcanization；The conditions of vulcanization of screening are as follows: curing temperature
It is 170 DEG C, vulcanization time 10min；Sample progress density measurement obtained, filters out density difference and exists after vulcameter is tested
0.2g/cm3~0.3g/cm3In the range of material piece, as mold pressing procedure select different densities layer, prepare density gradient material
Reference frame；
Step 4), plasma treatment: the material piece of the different densities of screening is cut into, difference consistent with mold shape and size
Material piece surface handle with argon plasma and exposes a period of time in air, to be formed on material piece surface
Oxide and hydrogen peroxide, supply frequency 50kHz, power 30W, argon pressure 8Pa；
Step 5), moulded from foam: density is successively increased into 0.03g/cm3~0.04g/cm3Multiple molded tablets be added to it is same
In mold, thus the assembly that composition density gradually changes；Then it is forced into 8Mpa, molding temperature is 170 DEG C, and clamp time is
10min, with the low compression deformation sheet material after constant temperature flowing water linear shrinkage cooling and shaping up to dimensionally stable after compression molding.
Using in sole low compression deformation sheet material made from the preparation process have density gradient and combine closely in
It in sizing material matrix and is in the equally distributed graphene two-dimensional slice structure of layered laminate.
The layered laminate functionalization graphene of the invention SF-GNRs's the preparation method comprises the following steps: by suitable GONRs be added nothing
In water-ethanol, the ratio of GONRs and dehydrated alcohol is 1 ︰ 500, and ultrasonic 1 hour formation uniform dispersion is then added a certain amount of
HCl regulation system pH=3~4；It weighs suitable KH-570 to be scattered in dehydrated alcohol, the ratio of KH-570 and dehydrated alcohol is
It is added in above-mentioned dispersion liquid after 3 ︰ 100, ultrasonic 30min, after mixing evenly, mixed system is warming up to 60 DEG C of reactions for 24 hours；Then
With dehydrated alcohol and deionized water on teflon membrane filter filtration washing repeatedly with the complete KH- of unreacted in removing system
570 and regulation system to neutrality, layered laminate functionalization graphene F-GONRs is dried to obtain in cooling driers；By F- obtained
GONRs is scattered in deionized water, and a certain amount of ammonia water conditioning system is then added in ultrasonic 1.5 hours formation uniform dispersions
PH=9~10, and stirred evenly under certain revolving speed.It is subsequently added into hydrazine hydrate and stirs 1 hour, it after mixing evenly, will be above-mentioned anti-
It answers system to move in 90 DEG C of oil bath pan to react 12 hours；Terminate and after cooled to room temperature wait react, with dehydrated alcohol and
Deionized water on teflon membrane filter filtration washing repeatedly with the trace impurity in sufficiently removing system and regulation system extremely
Neutrality is dried to obtain SF-GNRs in cooling driers.
The basic principles and main features and advantages of the present invention of the invention have been shown and described above, the industry
For technical staff it should be appreciated that the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only say
Bright the principle of the present invention, under the premise of not departing from the inventive spirit of the present invention and range, the present invention also has various change and changes
Into these changes and improvements all fall within the protetion scope of the claimed invention, and the claimed scope of the invention is by appended right
Claim and its equivalent thereof.
Claims (4)
1. a kind of sole preparation process of low compression deformation sheet material, which is characterized in that specifically comprise the following steps:
Step 1), stock: weighed respectively by different ratio EVA, OBC, LLDPE, ethylene-propylene diene copolymer, isoprene rubber, benzophenone,
Layered laminate functionalization graphene SF-GNRs, zinc stearate, gas-phase silica, atoleine, crosslink agent DCP, blowing agent AC, oxygen
Change zinc to constitute multiple groups formula, be respectively formulated in addition to the different outer other components of ethylene-propylene diene copolymer, zinc oxide and blowing agent AC content
Content is consistent；
Step 2, mixing: each raw material in each formula other than blowing agent AC and crosslink agent DCP is poured into mixer respectively
It is kneaded, first time stirring is carried out when temperature reaches 95 DEG C~96 DEG C；Second is carried out when temperature reaches 104~105 DEG C
Secondary stirring；Third time stirring is carried out when temperature reaches 110 DEG C~111 DEG C, while blowing agent AC and crosslink agent DCP progress is added
It is kneaded；The 4th stirring is carried out when temperature reaches 118 DEG C~120 DEG C；When temperature reach 125 DEG C~126 DEG C when can batch turning,
Then upper open mill thins at least twice, 2mm~3mm slice, be stored at room temperature 24 hours or more it is spare；
Step 3), vulcanization test: vulcanized and foamed test using no rotor foaming fluidisation instrument, it is consistent to filter out conditions of vulcanization
Material piece, so as to integrated molding of the multilayer material under the same conditions of vulcanization；The conditions of vulcanization of screening are as follows: curing temperature
It is 160 DEG C~180 DEG C, vulcanization time is 6min~12min；Sample progress density measurement obtained, sieve after vulcameter is tested
Density difference is selected in 0.2g/cm3~0.3g/cm3In the range of material piece, as mold pressing procedure select different densities layer, system
The reference frame of standby density gradient material；
Step 4), plasma treatment: the material piece of the different densities of screening is cut into, difference consistent with mold shape and size
Material piece surface handle with argon plasma and exposes a period of time in air, to be formed on material piece surface
Oxide and hydrogen peroxide, supply frequency are 40kHz~50kHz, and power is 30W~40W, and argon pressure is 6Pa~8Pa；
Step 5), moulded from foam: density is successively increased into 0.03g/cm3~0.04g/cm3Multiple molded tablets be added to same mould
In tool, thus the assembly that composition density gradually changes；Then it is forced into 8Mpa~10Mpa, molding temperature is 160 DEG C~180
DEG C, clamp time is 6min~12min, after compression molding with after constant temperature flowing water linear shrinkage cooling and shaping up to the low of dimensionally stable
Compressive deformation sheet material.
2. sole according to claim 1 low compression deformation sheet material, which is characterized in that the VA content in the EVA exists
Between 26%~40%.
3. the sole according to claim 1 preparation process of low compression deformation sheet material, which is characterized in that the ternary second
The hardness range of third glue is 60A~70A.
4. a kind of sole according to claim 1 sole made from the preparation process of low compression deformation sheet material is contracted with low pressure
Sheet material is deformed, there is in the low compression deformation sheet material density gradient and is combined closely in uniform in sizing material matrix and in layered laminate
The graphene two-dimensional slice structure of distribution.
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