CN107674292A - A kind of preparation method of the expanded material of doped graphene - Google Patents

A kind of preparation method of the expanded material of doped graphene Download PDF

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Publication number
CN107674292A
CN107674292A CN201610619593.9A CN201610619593A CN107674292A CN 107674292 A CN107674292 A CN 107674292A CN 201610619593 A CN201610619593 A CN 201610619593A CN 107674292 A CN107674292 A CN 107674292A
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parts
expanded material
mixing
preparation
effective doping
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杨与畅
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Fujian Xinfeng Two Mstar Technology Ltd
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Fujian Xinfeng Two Mstar Technology Ltd
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Priority to CN201610619593.9A priority Critical patent/CN107674292A/en
Priority to PCT/CN2017/095422 priority patent/WO2018024191A1/en
Publication of CN107674292A publication Critical patent/CN107674292A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • 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
    • 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
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/50—Footwear, e.g. shoes or parts thereof
    • B29L2031/504—Soles
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • 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
    • C08J2323/06—Polyethene
    • 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
    • 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
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

The invention discloses a kind of preparation method of the expanded material of doped graphene, wherein methods described includes：(1) it is granulated：Parts by weight are stirred to obtain compound for 100 parts of material of main part, 0.5 10 parts of graphene oxide, 14 parts of dispersion enhancing agents, 0.5 5 parts of lubricant；The compound melting mixing that will be obtained, then after supercooling, pelletizing is carried out by pelleter, obtains the pellet containing graphene；(2) banburying：Banbury is put into together with 100 parts by weight AC foaming agents, 14 parts of vulcanizing agent zinc oxide, 15 parts of stearic acid, 15 45 parts of inserts calcium powder or the talcum powder, 14 parts of DCP crosslinking agents and 0.5 3 parts of TAIC crosslinking coagents with 4 15 parts of the pellet that step (1) is obtained and carries out banburying；(3) mill：In blocks, the sheet material for pulling out and being cut into from rubber mixing machine by the adjustment of batch mixing glue；(4) hot-pressing and foaming：Sheet material is loaded in hot press and foamed, water flowing afterwards cools down mould to room temperature, the foamed shoe sole being molded.

Description

A kind of preparation method of the expanded material of doped graphene
Technical field
The present invention relates to polymeric material field, more particularly to a kind of preparation method of the expanded material of doped graphene.
Background technology
Expanded material possesses the functions such as buffering, sound-absorbing, shock-absorbing, insulation, filtering because light weight, pliability are good, extensively should Manufacture for sports equipment, seat cushion, children floor, sport footwear etc..Wherein, the application in the foamed shoe sole of different materials is deposited In following problem：PE foamed shoe sole poor flexibilities, non-skid property is poor, wear for a long time after it is yielding the shortcomings of；EVA foamed shoe soles Mechanical strength, tear resistance and stripper-resistance are not good enough；Therefore expanded material is somewhat limited in the application of sole.
Graphene has unique two-dimension periodic honeycomb lattice structure, and the carbon hexatomic ring stablized in its construction unit is deposited Assigning its excellent hot property, mechanical property and electric conductivity.Therefore graphene is added in expanded material, can effectively carried The mechanical properties such as tear-proof, the antistripping of foamed shoe sole are risen, so as to widen the application of sole.However, graphene compares surface Intrinsic Van der Waals force be present between the huge and lamella of product, thus graphene is easily reunited；Polyethylene etc. is nonpolar poly- simultaneously Compound, with graphene poor compatibility, it is difficult to be peeled off in polyethylene to cause graphene, therefore, is purely added in expanded material Graphene, to the performance improvement DeGrain of expanded material.
The content of the invention
It is an object of the invention to solve the problems, such as that existing expanded material doped graphene is present, there is provided one kind doping stone The preparation method of the expanded material of black alkene, by the way that graphene is effectively evenly spread in expanded material, avoid graphene itself Reunite, so as to lift the mechanical property of expanded material.
To achieve the above object, the invention provides following technical scheme：A kind of foaming material of Effective Doping graphene The preparation method of material, the described method comprises the following steps：(1) it is granulated：By material of main part of the parts by weight for 100 parts, 0.5-10 parts Graphene oxide, 1-4 parts dispersion enhancing agents, the lubricant of 0.5-5 parts be stirred to obtain compound；The compound that will be obtained Melting mixing, then after supercooling, pelletizing is carried out by pelleter, obtains the pellet containing graphene；(2) banburying：By step (1) 100 parts by weight of the pellet obtained and the AC foaming agents of 4-15 parts, the vulcanizing agent zinc oxide of 1-4 parts, the tristearin of 1-5 parts The TAIC crosslinking coagents of acid, the inserts calcium powder of 15-45 parts or talcum powder, the DCP crosslinking agents of 1-4 parts and 0.5-3 parts are put together Enter banbury and carry out banburying；(3) mill：The mixture that step (2) obtains is put into rubber mixing machine together and carries out secondary mixing, allows material Material is sufficiently mixed, and obtains well mixed batch mixing glue；Batch mixing glue is then adjusted in blocks, the piece for pulling out and being cut into from rubber mixing machine Shape expanded material；(4) hot-pressing and foaming：Sheet expanded material is loaded in hot press and foamed, the cooling mould of water flowing afterwards to room temperature, The foamed shoe sole that must be molded.
Preferably, the material of main part of the step (1) is in ethylene-vinyl acetate copolymer, polyethylene or reworked material It is at least one.
Preferably, the dispersion enhancing agents of the step (1) be MAH-g-PE, MAH-g-EVA, MAH-g-HDPE, At least one of MAH-g-SEBS, MAH-g-LLPDE.
Preferably, the compound that is stirred to obtain of the step (1) carries out mixing 5- specifically by homogenizer 30min。
Preferably, the compound melting mixing that obtains a of the step (1) is specially that a is obtained into compound to add double spiral shells Type melting mixing in bar extruder, wherein screw speed are 20-200rmp, and temperature is 130-200 DEG C, mixing time 5- 20min；The compound that is cooled to after twin-screw extrusion through tank by cooling down.
Preferably, the temperature of banburying is 120-130 DEG C in the step (2), mixing time 2-5min.
Preferably, the temperature that secondary mixing is carried out in the step (3) is 110-140 DEG C.
Preferably, batch mixing glue is then adjusted in blocks, the sheet material for pulling out and being cut into from rubber mixing machine in the step (3) Batch mixing glue is specially adjusted to the thick pieces of 1-1.5mm, is pulled out from rubber mixing machine and is cut into 40cm*80cm sheet foaming material Material.
Preferably, sheet expanded material is loaded in hot press in the step (4) and foamed, the cooling of water flowing afterwards mould is extremely Room temperature, the foamed shoe sole for obtaining shaping are specially that sheet material loading temperature foams 10- in 165-190 DEG C of hot press 20min, then water flowing cool down mould to room temperature, obtain the foamed shoe sole of shaping.
Beneficial effects of the present invention：By adding dispersion enhancing agents while expanded material adds graphene, both drew Enter highly polar reactive group, added compatibility, improve the dispersiveness of graphene in the polymer again；So that graphite Alkene Effective Doping in expanded material, so as to lift the tear-proof of foamed shoe sole, antistripping ability.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
The invention discloses a kind of preparation method of the expanded material of Effective Doping graphene, methods described includes following step Suddenly：(1) it is granulated：By material of main part that parts by weight are 100 parts, the graphene oxide of 0.5-10 parts, 1-4 parts dispersion enhancing agents, The lubricant of 0.5-5 parts is stirred to obtain compound；The compound melting mixing that will be obtained, then after supercooling, by cutting Grain machine carries out pelletizing, obtains the pellet containing graphene；
(2) banburying：100 parts by weight of the pellet that step (1) is obtained and the AC foaming agents of 4-15 parts, the sulphur of 1-4 parts Agent zinc oxide, the stearic acid of 1-5 parts, the inserts calcium powder of 15-45 parts or talcum powder, the DCP crosslinking agents and 0.5-3 of 1-4 parts The TAIC crosslinking coagents of part are put into banbury and carry out banburying together；
(3) mill：The mixture that step (2) obtains is put into rubber mixing machine together and carries out secondary mixing, makes material fully mixed Close, obtain well mixed batch mixing glue；Batch mixing glue is then adjusted in blocks, the sheet foaming material for pulling out and being cut into from rubber mixing machine Material；
(4) hot-pressing and foaming：Sheet expanded material is loaded in hot press and foamed, water flowing afterwards cools down mould to room temperature, obtains The sole of shaping.
Wherein, step (1) described material of main part be ethylene-vinyl acetate copolymer, polyethylene or reworked material at least It is a kind of；The dispersion enhancing agents are maleic anhydride grafted polyethylene (MAH-g-PE), maleic anhydride grafted ethene-vinyl acetate is common Polymers (MAH-g-EVA), maleic anhydride grafting ethylene propylene diene rubber (MAH-g-HDPE), maleic anhydride graft phenylethene-ethene- Butadiene-styrene triblock copolymer (MAH-g-SEBS), maleic anhydride grafted linear low density polyethylene (LDPE) (MAH-g- At least one of LLPDE).
Maleic anhydride is grafted compatilizer by introducing highly polar reaction, material is had high polarity and reactivity, increases Compatibility between material, at the same maleic anhydride grafting compatilizer be a kind of unsaturated organic acid acid anhydride base stock, can and oxygen The bonding of the functional groups such as the hydroxyl on graphite alkene surface, carboxyl, can effectively avoid graphene itself from reuniting, beneficial to it in the polymer It is scattered, so as to carry out effective graphene doping to expanded material.
The specific present invention can be carried out as follows specific implementation：
Embodiment 1
First by EVA (ethylene-vinyl acetate copolymer) that parts by weight are 100 parts, 2 parts of graphene oxide, 3 parts MAH-g-EVA (maleic anhydride grafted ethene-acetate ethylene copolymer), 2 parts of lubricant, put homogenizer into and are mixed 10min；Then well mixed compound is added into melting mixing in double screw extruder, screw speed 120rmp, 150 10min is kneaded at DEG C；Then by after tank cools down, carrying out pelletizing operation after twin-screw extrusion by pelleter, being contained The pellet of graphene；
Then by 100 parts of pellet and 8 parts of AC foaming agents, 2 parts of zinc oxide, 1 part of stearic acid, 25 parts of calcium powder, 1 The DCP crosslinking agents and 0.5 part of TAIC crosslinking coagents of part are put into banbury and carry out banburying together, 120 DEG C of temperature, continue 3min； Then the mixture after banburying is put into rubber mixing machine together and carries out secondary mixing, allowed material to be sufficiently mixed, obtain well mixed Batch mixing glue；Mixing temperature is controlled at 125 DEG C；Then it will expect to be adjusted to the thick pieces of 1mm, pulled out from rubber mixing machine and be cut into 40cm* 80cm sheet expanded material；
Finally sheet expanded material loading temperature is foamed 15min in 180 DEG C of hot press, the cooling mould of water flowing afterwards To room temperature, sole formed is obtained.
Embodiment 2
First by EVA (ethylene-vinyl acetate copolymer) that parts by weight are 100 parts, 5 parts of graphene oxide, 3 parts MAH-g-PE (maleic anhydride grafted polyethylene), 1 part of lubricant, put homogenizer into and carry out mixing 10min；Then will be mixed Close uniform compound and add melting mixing in double screw extruder, screw speed 120rmp, 10min is kneaded at 150 DEG C； Then by after tank cools down, carrying out pelletizing operation after twin-screw extrusion by pelleter, obtaining the pellet containing graphene；
Then by 100 parts of pellet and 10 parts of AC foaming agents, 2 parts of zinc oxide, 1 part of stearic acid, 20 parts of calcium powder, 2 parts of DCP crosslinking agents and 1 part of TAIC crosslinking coagents are put into banbury and carry out banburying together, 120 DEG C of temperature, continue 5min；So The mixture after banburying is put into rubber mixing machine together afterwards and carries out secondary mixing, allows material to be sufficiently mixed, obtains well mixed mix Expect glue；Mixing temperature is controlled at 125 DEG C；Then it will expect to be adjusted to the thick pieces of 1mm, pulled out from rubber mixing machine and be cut into 40cm* 80cm sheet expanded material；
Finally sheet expanded material loading temperature is foamed 15min in 180 DEG C of hot press, the cooling mould of water flowing afterwards To room temperature, the sole of shaping is obtained.
Embodiment 3
By 100 parts of PE (polyethylene), 8 parts of graphene oxide, 3 parts of MAH-g-LLPDE, (maleic anhydride is grafted first Linear low density of polyethylene), 2 parts of lubricant, put homogenizer into and carry out mixing 20min；Then well mixed is mixed Close material and add melting mixing in double screw extruder, screw speed 100rmp, 20min is kneaded at 150 DEG C；Then by double spiral shells After bar extrusion after tank cools down, pelletizing operation is carried out by pelleter, obtains the pellet containing graphene；
Then by 100 parts of pellet and 9 parts of AC foaming agents, 3 parts of zinc oxide, 2 parts of stearic acid, 25 parts of calcium powder, 1.5 parts of DCP crosslinking agents and 1 part of TAIC crosslinking coagents are put into banbury and carry out banburying together, 120 DEG C of temperature, continue 3min； Then the mixture after banburying is put into rubber mixing machine together and carries out secondary mixing, allowed material to be sufficiently mixed, obtain well mixed Batch mixing glue；Mixing temperature is controlled at 128 DEG C；Then it will expect to be adjusted to the thick pieces of 1mm, pulled out from rubber mixing machine and be cut into 40cm* 80cm sheet expanded material；
Finally piece foaming material shape material loading temperature is foamed 20min in 175 DEG C of hot press, the cooling mould of water flowing afterwards To room temperature, the sole of shaping is obtained.
Comparative example 1
First by 100 parts of EVA (ethylene-vinyl acetate copolymer), 2 parts of graphene oxide, 2 parts of lubricant, put Enter homogenizer and carry out mixing 10min；Then well mixed compound is added into melting mixing in double screw extruder, Screw speed is 120rmp, and 10min is kneaded at 150 DEG C；Then by after tank cools down, passing through pelleter after twin-screw extrusion Pelletizing operation is carried out, obtains the pellet containing graphene；
Then by 100 parts of pellet and 8 parts of AC foaming agents, 2 parts of zinc oxide, 1 part of stearic acid, 25 parts of calcium powder, 1 The DCP crosslinking agents and 0.5 part of TAIC crosslinking coagents of part are put into banbury and carry out banburying together, 120 DEG C of temperature, continue 3min； Then the mixture after banburying is put into rubber mixing machine together and carries out secondary mixing, allowed material to be sufficiently mixed, obtain well mixed Batch mixing glue；Mixing temperature is controlled at 125 DEG C；Then it will expect to be adjusted to the thick pieces of 1mm, pulled out from rubber mixing machine and be cut into 40cm* 80cm sheet expanded material；
Finally sheet expanded material loading temperature is foamed 15min in 180 DEG C of hot press, the cooling mould of water flowing afterwards To room temperature, the sole of shaping is obtained.
The performance test correction data of above-described embodiment 1,2,3 and comparative example 1 is as shown in table 1.As it can be seen from table 1 this Foamed shoe sole tear resistance relative with foamed shoe sole prepared by comparative example prepared by inventive embodiments lifts tens times, sole It can be obviously improved, and reduce sole density, sole is lighter.
Table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (9)

1. a kind of preparation method of the expanded material of Effective Doping graphene, it is characterised in that the described method comprises the following steps：
(1) it is granulated：By material of main part that parts by weight are 100 parts, the graphene oxide of 0.5-10 parts, 1-4 parts dispersion enhancing agents, The lubricant of 0.5-5 parts is stirred to obtain compound；The compound melting mixing that will be obtained, then after supercooling, by cutting Grain machine carries out pelletizing, obtains the pellet containing graphene；
(2) banburying：100 parts by weight of the pellet that step (1) is obtained and the AC foaming agents of 4-15 parts, the vulcanizing agent of 1-4 parts Zinc oxide, the stearic acid of 1-5 parts, the inserts calcium powder of 15-45 parts or talcum powder, the DCP crosslinking agents of 1-4 parts and 0.5-3 parts TAIC crosslinking coagents are put into banbury and carry out banburying together；
(3) mill：The mixture that step (2) obtains is put into rubber mixing machine together and carries out secondary mixing, allows material to be sufficiently mixed, obtains To well mixed batch mixing glue；Batch mixing glue is then adjusted in blocks, the sheet material for pulling out and being cut into from rubber mixing machine；
(4) hot-pressing and foaming：Sheet material is loaded in hot press and foamed, water flowing afterwards cools down mould to room temperature, obtains the foaming of shaping Sole.
2. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the material of main part of (1) is at least one of ethylene-vinyl acetate copolymer, polyethylene or reworked material.
3. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the dispersion enhancing agents of (1) are in MAH-g-PE, MAH-g-EVA, MAH-g-HDPE, MAH-g-SEBS, MAH-g-LLPDE At least one.
4. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the compound that is stirred to obtain of (1) carries out mixing 5-30min specifically by homogenizer.
5. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the compound melting mixing that a is obtained of (1) is specially that a is obtained into type melting in compound addition double screw extruder to mix Close, wherein screw speed is 20-200rmp, and temperature is 130-200 DEG C, mixing time 5-20min；It is described to be cooled to compound By being cooled down after twin-screw extrusion through tank.
6. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the temperature of banburying is 120-130 DEG C in (2), mixing time 2-5min.
7. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly the temperature that secondary mixing is carried out in (3) is 110-140 DEG C.
8. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly then batch mixing glue is adjusted in flakes in (3), the sheet material for pulling out and being cut into from rubber mixing machine is specially to be adjusted to batch mixing glue Piece thick 1-1.5mm, pulls out from rubber mixing machine and is cut into 40cm*80cm sheet expanded material.
9. the preparation method of the expanded material of Effective Doping graphene according to claim 1, it is characterised in that：The step Suddenly sheet expanded material is loaded in hot press in (4) and foamed, water flowing afterwards cools down mould to room temperature, obtains the expanded material of shaping Specially sheet material loading temperature is foamed 10-20min in 165-190 DEG C of hot press, then water flowing cools down mould to room Temperature, obtain the foamed shoe sole of shaping.
CN201610619593.9A 2016-08-01 2016-08-01 A kind of preparation method of the expanded material of doped graphene Pending CN107674292A (en)

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PCT/CN2017/095422 WO2018024191A1 (en) 2016-08-01 2017-08-01 Method for preparing foam material doped with graphene

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161072A (en) * 2018-06-30 2019-01-08 杭州高烯科技有限公司 A kind of graphene-polyethylene foamed composite material and preparation method
CN109161085A (en) * 2018-06-30 2019-01-08 杭州高烯科技有限公司 A kind of graphene-foaming EVA composite material and preparation method
CN110016181A (en) * 2019-05-08 2019-07-16 福建五持恒科技发展有限公司 Graphene regeneration rubber-plastic foamed shoe-pad and preparation method thereof
CN110054831A (en) * 2019-05-08 2019-07-26 福建五持恒科技发展有限公司 A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof
CN110144075A (en) * 2019-06-05 2019-08-20 福建五持恒科技发展有限公司 A kind of graphene reclaimed rubber foamed shoe sole micelle and preparation method thereof
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
CN110885486A (en) * 2019-10-28 2020-03-17 茂泰(福建)鞋材有限公司 Method for manufacturing foamed 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
CN110938250A (en) * 2019-11-14 2020-03-31 浙江恒诚鞋业有限公司 Foamed sole and preparation method thereof
CN110982132A (en) * 2019-11-14 2020-04-10 浙江恒诚鞋业有限公司 Ozone-resistant rubber sole and preparation method thereof
CN112029248A (en) * 2020-09-08 2020-12-04 吴乙胜 High-elasticity environment-friendly plastic plate and preparation process thereof
CN115071159A (en) * 2022-08-23 2022-09-20 张家港梦康生活家居科技有限公司 Graphene ground mat production line based on self-temperature-control foaming channel

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CN109161072A (en) * 2018-06-30 2019-01-08 杭州高烯科技有限公司 A kind of graphene-polyethylene foamed composite material and preparation method
CN109161085A (en) * 2018-06-30 2019-01-08 杭州高烯科技有限公司 A kind of graphene-foaming EVA composite material and preparation method
CN110016181A (en) * 2019-05-08 2019-07-16 福建五持恒科技发展有限公司 Graphene regeneration rubber-plastic foamed shoe-pad and preparation method thereof
CN110054831A (en) * 2019-05-08 2019-07-26 福建五持恒科技发展有限公司 A kind of graphene regeneration EVA foamed shoe sole micelle and preparation method thereof
CN110144075A (en) * 2019-06-05 2019-08-20 福建五持恒科技发展有限公司 A kind of graphene reclaimed rubber foamed shoe sole micelle and preparation method thereof
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
CN110885486A (en) * 2019-10-28 2020-03-17 茂泰(福建)鞋材有限公司 Method for manufacturing foamed 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
CN110938250A (en) * 2019-11-14 2020-03-31 浙江恒诚鞋业有限公司 Foamed sole and preparation method thereof
CN110982132A (en) * 2019-11-14 2020-04-10 浙江恒诚鞋业有限公司 Ozone-resistant rubber sole and preparation method thereof
CN112029248A (en) * 2020-09-08 2020-12-04 吴乙胜 High-elasticity environment-friendly plastic plate and preparation process thereof
CN115071159A (en) * 2022-08-23 2022-09-20 张家港梦康生活家居科技有限公司 Graphene ground mat production line based on self-temperature-control foaming channel
CN115071159B (en) * 2022-08-23 2022-12-02 张家港梦康生活家居科技有限公司 Graphene ground mat production line based on self-temperature-control foaming channel

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