WO2018024191A1 - 一种掺杂石墨烯的发泡材料的制备方法 - Google Patents

一种掺杂石墨烯的发泡材料的制备方法 Download PDF

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WO2018024191A1
WO2018024191A1 PCT/CN2017/095422 CN2017095422W WO2018024191A1 WO 2018024191 A1 WO2018024191 A1 WO 2018024191A1 CN 2017095422 W CN2017095422 W CN 2017095422W WO 2018024191 A1 WO2018024191 A1 WO 2018024191A1
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parts
mixture
graphene
foamed
rubber
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French (fr)
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杨与畅
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Xifeng 2d (fujian) Material Technology Co Ltd
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Xifeng 2d (fujian) Material Technology Co Ltd
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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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethylene vinyl acetate copolymers
    • 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—Polyethylene
    • 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

Definitions

  • the invention relates to the field of polymer materials, in particular to a method for preparing a foamed material doped with graphene.
  • the foaming material is widely used in the manufacture of sports equipment, seat cushions, children's floors, sports shoes, etc. due to its light weight, good softness, cushioning, sound absorption, shock absorption, heat preservation and filtration.
  • the application in the foam sole of different materials has the following problems: PE foam sole has poor elasticity, poor anti-slip performance, easy deformation after wearing for a long time; EVA foam sole mechanical strength, tear resistance and resistance The peelability is not good enough; therefore, the application of the foamed material to the sole is limited to some extent.
  • Graphene has a unique two-dimensional periodic honeycomb lattice structure, and the existence of a stable carbon six-membered ring in its structural unit gives it excellent thermal properties, mechanical properties and electrical conductivity. Therefore, the addition of graphene to the foaming material can effectively improve the mechanical properties such as tear resistance and peeling resistance of the foamed sole, thereby widening the application range of the sole.
  • the specific surface area of graphene is huge and there is an inherent van der Waals force between the sheets, so graphene is extremely easy to agglomerate; at the same time, polyethylene and the like are non-polar polymers, and the compatibility with graphene is poor, which makes it difficult for graphene to be in polyethylene.
  • the graphene is added purely to the foamed material, and the performance improvement effect on the foamed material is not remarkable.
  • the object of the present invention is to solve the problem that the existing foaming material is doped with graphene, and to provide a method for preparing a foaming material doped with graphene, which can avoid graphite by effectively and uniformly dispersing graphene into the foaming material.
  • the olefin itself agglomerates to enhance the mechanical properties of the foamed material.
  • the present invention provides the following technical solution: a method for preparing a foamed material which is effectively doped with graphene, the method comprising the following steps: (1) granulation: 100 parts by weight The main material, 0.5-10 parts of graphene oxide, 1-4 parts of dispersion accelerator, 0.5-5 parts of lubricant are stirred and mixed to obtain a mixture; the obtained mixture is melt-mixed, and after cooling, pass through the pelletizing The machine performs pelletizing to obtain pellets containing graphene; (2) mixing: the pellet obtained in the step (1) is 100 parts by weight with 4-15 parts of the AC foaming agent, and 1-4 parts of the sulfide Zinc oxide, 1-5 parts of stearic acid, 15-45 parts of filler calcium powder or talc, 1-4 parts of DCP crosslinker and 0.5-3 parts of TAIC crosslinking aid together The refining machine performs the refining; (3) the opening: the mixture obtained in the step (2) is put into the rubber mixing machine for secondary mixing
  • the sheet-like foam material pulled out from the rubber mixer and cut into pieces; (4) hot-press foaming: the sheet-like foaming material is foamed in a hot press, and then the mold is cooled by water to At room temperature, a molded foam sole is obtained.
  • the host material of the step (1) is at least one of ethylene-vinyl acetate copolymer, polyethylene or recycled material.
  • the dispersion promoter of the step (1) is at least one of MAH-g-PE, MAH-g-EVA, MAH-g-HDPE, MAH-g-SEBS, and MAH-g-LLPDE. .
  • the agitation mixing of the step (1) to obtain a mixture is specifically carried out by a high speed mixer for 5-30 min.
  • step (1) the mixture obtained by a is melt-mixed, specifically, the mixture obtained by adding a to the twin-screw extruder is melt-mixed, wherein the screw speed is 20-200 rpm and the temperature is 130-200 ° C.
  • the mixing time is 5-20 min; the cooling is that the mixture is extruded by twin-screw and then cooled by a water tank.
  • the temperature of the mixing in the step (2) is 120-130 ° C, and the mixing time is 2-5 min.
  • the temperature for performing the second mixing in the step (3) is 110-140 ° C.
  • the rubber compound is subsequently adjusted into a sheet, and the sheet material which is pulled out from the rubber mixer and cut into pieces is specifically adjusted to adjust the mixture rubber to a sheet of 1-1.5 mm thickness.
  • the rubber mixer was pulled out and cut into a sheet-shaped foamed material of 40 cm * 80 cm.
  • the sheet-like foaming material is foamed in a hot press, and then the mold is cooled by water to room temperature, and the formed foamed sole is specifically filled with a sheet-like material at a temperature of 165. -190 ° C heat
  • the machine is foamed for 10-20 min, and then the mold is cooled by water to room temperature to obtain a molded foam sole.
  • the invention has the beneficial effects that by adding a dispersing accelerator while adding the graphene to the foaming material, the strong polar reactive group is introduced, the compatibility is increased, and the dispersion of the graphene in the polymer is improved. Therefore, the graphene is effectively doped in the foamed material, thereby improving the tear resistance and peeling resistance of the foamed sole.
  • the invention discloses a preparation method of a foaming material which is effectively doped with graphene, and the method comprises the following steps: (1) granulation: 100 parts by weight of the host material, 0.5-10 parts of graphene oxide 1-4 parts of a dispersion accelerator, 0.5-5 parts of a lubricant are stirred and mixed to obtain a mixture; the obtained mixture is melt-mixed, and after cooling, it is diced by a pelletizer to obtain a pellet containing graphene. ;
  • the pellet obtained in the step (1) is 100 parts by weight with 4-15 parts of the AC foaming agent, 1-4 parts of the vulcanizing agent zinc oxide, 1-5 parts of stearic acid, 15-45 parts of filler calcium powder or talc, 1-4 parts of DCP cross-linking agent and 0.5-3 parts of TAIC cross-linking aid are placed in an internal mixer for mixing;
  • Hot-press foaming The sheet-like foaming material is foamed in a hot press, and then the mold is cooled by water to room temperature to obtain a molded sole.
  • the main material of the step (1) is at least one of ethylene-vinyl acetate copolymer, polyethylene or recycled material;
  • the dispersion promoter is maleic anhydride grafted polyethylene (MAH-g-PE), Maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA), maleic anhydride grafted ethylene propylene diene monomer (MAH-g-HDPE), maleic anhydride grafted styrene-ethylene-butadiene -styrene triblock copolymer (MAH-g-SEBS), at least one of maleic anhydride grafted linear low density polyethylene (MAH-g-LLPDE).
  • MAH-g-PE Maleic anhydride grafted polyethylene
  • MAH-g-EVA Maleic anhydride grafted ethylene-vinyl acetate copolymer
  • MAH-g-HDPE maleic anhydride grafted ethylene propy
  • Maleic anhydride grafting compatibilizers provide high polarity and reactivity by introducing strong polar reactions, increasing the compatibility between materials, while maleic anhydride grafting compatibilizer is an unsaturated organic
  • the basic material of the acid anhydride can be bonded to a functional group such as a hydroxyl group or a carboxyl group on the surface of the graphene oxide, which can effectively avoid the agglomeration of the graphene itself, and facilitate the dispersion in the polymer, thereby performing effective graphene doping on the foamed material.
  • EVA ethylene-vinyl acetate copolymer
  • graphene oxide 2 parts of graphene oxide
  • MAH-g-EVA maleic anhydride grafted ethylene-vinyl acetate copolymer
  • the lubricant is placed in a high-speed mixer for mixing for 10 min; then the mixed mixture is added to a twin-screw extruder for melt mixing, the screw speed is 120 rpm, and the mixture is kneaded at 150 ° C for 10 min; After cooling, the pelletizing operation is performed by a pelletizer to obtain pellets containing graphene;
  • pellets were crosslinked with 8 parts of AC foaming agent, 2 parts of zinc oxide, 1 part of stearic acid, 25 parts of calcium powder, 1 part of DCP crosslinking agent and 0.5 part of TAIC.
  • the agent is placed in an internal mixer for mixing, and the temperature is 120 ° C for 3 minutes; then the mixed mixture is put into a rubber mixing machine for secondary mixing, and the materials are thoroughly mixed to obtain a uniformly mixed rubber;
  • the opening temperature was controlled at 125 ° C; then the material was adjusted to a 1 mm thick piece, which was pulled out from the rubber mixer and cut into a 40 cm * 80 cm sheet-like foam material;
  • the sheet-like foaming material was foamed in a hot press at 180 ° C for 15 min, and then the mold was cooled by water to room temperature to obtain a molded sole.
  • EVA ethylene-vinyl acetate copolymer
  • graphene oxide 5 parts
  • MAH-g-PE maleic anhydride grafted polyethylene
  • lubricant 1 part of lubricant
  • the mixture was mixed in a high-speed mixer for 10 minutes; then the mixed mixture was added to a twin-screw extruder for melt mixing, the screw rotation speed was 120 rpm, and the mixture was kneaded at 150 ° C for 10 minutes; then, after being extruded by twin-screw, cooled by a water tank, The pelletizing operation is performed by a pelletizer to obtain pellets containing graphene;
  • the pellets were crosslinked with 10 parts of AC foaming agent, 2 parts of zinc oxide, 1 part of stearic acid, 20 parts of calcium powder, 2 parts of DCP crosslinking agent and 1 part of TAIC.
  • the agent is placed together in an internal mixer for mixing, and the temperature is 120 ° C for 5 minutes; then the mixed mixture is put into a rubber mixing machine for secondary mixing, and the materials are thoroughly mixed to obtain a uniformly mixed rubber;
  • the opening temperature was controlled at 125 ° C; then the material was adjusted to a 1 mm thick piece, which was pulled out from the rubber mixer and cut into a 40 cm * 80 cm sheet-like foam material;
  • the sheet-like foaming material was foamed in a hot press at 180 ° C for 15 min, and then the mold was cooled to room temperature by water to obtain a molded sole.
  • PE polyethylene
  • MAH-g-LLPDE maleic anhydride grafted linear low density polyethylene
  • lubricant 100 parts of PE (polyethylene), 8 parts of graphene oxide, 3 parts of MAH-g-LLPDE (maleic anhydride grafted linear low density polyethylene), and 2 parts of lubricant are placed in a high speed mixer. Mixing for 20 min; then mixing the uniformly mixed mixture into a twin-screw extruder for melt mixing, screw rotation speed of 100 rpm, and kneading at 150 ° C for 20 min; followed by extrusion by twin-screw, cooling through a water tank, and then passing through a pelletizer a pelletizing operation to obtain a pellet containing graphene;
  • pellets were crosslinked with 9 parts of AC foaming agent, 3 parts of zinc oxide, 2 parts of stearic acid, 25 parts of calcium powder, 1.5 parts of DCP crosslinking agent and 1 part of TAIC.
  • the agent is placed in an internal mixer for mixing, and the temperature is 120 ° C for 3 minutes; then the mixed mixture is put into a rubber mixing machine for secondary mixing, and the materials are thoroughly mixed to obtain a uniformly mixed rubber;
  • the opening temperature was controlled at 128 ° C; then the material was adjusted to a 1 mm thick piece, pulled out from the rubber mixer and cut into 40 cm * 80 cm sheet foam material;
  • the sheet foam material was foamed in a hot press at 175 ° C for 20 min, and then the mold was cooled to room temperature by water to obtain a molded sole.
  • pellets were crosslinked with 8 parts of AC foaming agent, 2 parts of zinc oxide, 1 part of stearic acid, 25 parts of calcium powder, 1 part of DCP crosslinking agent and 0.5 part of TAIC.
  • the agent is placed in an internal mixer for mixing, and the temperature is 120 ° C for 3 minutes; then the mixed mixture is put into a rubber mixing machine for secondary mixing, and the materials are thoroughly mixed to obtain a uniformly mixed rubber;
  • the opening temperature was controlled at 125 ° C; then the material was adjusted to a 1 mm thick piece, which was pulled out from the rubber mixer and cut into a 40 cm * 80 cm sheet-like foam material;
  • the sheet-like foaming material was foamed in a hot press at 180 ° C for 15 min, and then the mold was cooled to room temperature by water to obtain a molded sole.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

一种掺杂石墨烯的发泡材料的制备方法，其中所述方法包括：(1)造粒：将重量份为100份的主体材料、0.5-10份的氧化石墨烯、1-4份分散促进剂、0.5-5份的润滑剂搅拌混合得到混合料；将得到的混合料熔融混合，再经过冷却后，通过切粒机进行切粒，得到含有石墨烯的粒料；(2)密炼：将步骤(1)得到的粒料按重量份100份与4-15份的AC发泡剂、1-4份的硫化剂氧化锌、1-5份的硬脂酸、15-45份的填充料钙粉或滑石粉、1-4份的DCP交联剂及0.5-3份的TAIC交联助剂一起放入密炼机进行密炼；(3)开炼：将混料胶调整成片，从炼胶机中拉出并截成的片状料；(4)热压发泡：将片状料装入热压机内发泡，之后通水冷却模具至室温，得到成型的发泡鞋底。该方法能避免石墨烯自身团聚，从而提升发泡材料的力学性能。

Description

一种掺杂石墨烯的发泡材料的制备方法 技术领域
本发明涉及高分子材料领域，尤其涉及一种掺杂石墨烯的发泡材料的制备方法。
背景技术
发泡材料由于质量轻、柔软度好，具备缓冲、吸音、吸震、保温、过滤等功能，广泛应用于运动器材、座垫、儿童地板、运动鞋等的制造。其中，在不同材料的发泡鞋底中的应用存在如下问题：PE发泡鞋底弹性差，防滑性能较差、长时间穿着后易变形等缺点；EVA发泡鞋底机械强度、抗撕裂性及抗剥离性不够好；因此发泡材料在鞋底的应用受到一定程度的限制。
石墨烯具有独特的二维周期蜂窝状点阵结构，其结构单元中稳定的碳六元环的存在，赋予其优异的热性能、力学性能及导电性能。因此在发泡材料中添加石墨烯，能有效提升发泡鞋底的抗撕裂、抗剥离等力学性能，从而拓宽鞋底的应用范围。然而，石墨烯比表面积巨大且片层之间存在固有的范德华力，因而石墨烯极易团聚；同时聚乙烯等是非极性聚合物，与石墨烯相容性差，造成石墨烯很难在聚乙烯中剥离，因此，纯粹在发泡材料中添加石墨烯，对发泡材料的性能改善效果不明显。
发明内容
本发明的目的在于解决现有发泡材料掺杂石墨烯存在的问题，提供了一种掺杂石墨烯的发泡材料的制备方法，通过将石墨烯有效均匀分散到发泡材料中，避免石墨烯自身团聚，从而提升发泡材料的力学性能。
为实现上述目的，本发明提供了如下的技术方案：一种有效掺杂石墨烯的发泡材料的制备方法，所述方法包括以下步骤：(1)造粒：将重量份为100份 的主体材料、0.5-10份的氧化石墨烯、1-4份分散促进剂、0.5-5份的润滑剂搅拌混合得到混合料；将得到的混合料熔融混合，再经过冷却后，通过切粒机进行切粒，得到含有石墨烯的粒料；(2)密炼：将步骤(1)得到的粒料按重量份100份与4-15份的AC发泡剂、1-4份的硫化剂氧化锌、1-5份的硬脂酸、15-45份的填充料钙粉或滑石粉、1-4份的DCP交联剂及0.5-3份的TAIC交联助剂一起放入密炼机进行密炼；(3)开炼：将步骤(2)得到的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；接着将混料胶调整成片，从炼胶机中拉出并截成的片状发泡材料；(4)热压发泡：将片状发泡材料装入热压机内发泡，之后通水冷却模具至室温，得成型的发泡鞋底。
优选的，所述步骤(1)的主体材料为乙烯-醋酸乙烯共聚物、聚乙烯或再生料中的至少一种。
优选的，所述步骤(1)的所述分散促进剂为MAH-g-PE、MAH-g-EVA、MAH-g-HDPE、MAH-g-SEBS、MAH-g-LLPDE中的至少一种。
优选的，所述步骤(1)的搅拌混合得到混合料具体为通过高速搅拌机进行混合5-30min。
优选的，所述步骤(1)的将a得到混合料熔融混合具体为将a得到混合料加入双螺杆挤出机中机型熔融混合，其中螺杆转速为20-200rmp，温度为130-200℃，混炼时间为5-20min；所述冷却为混合料由双螺杆挤出后经水槽冷却。
优选的，所述步骤(2)中密炼的温度为120-130℃，密炼时间为2-5min。
优选的，所述步骤(3)中进行二次混炼的温度为110-140℃。
优选的，所述步骤(3)中接着将混料胶调整成片，从炼胶机中拉出并截成的片状料具体为将混料胶调整成1-1.5mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料。
优选的，所述步骤(4)中将片状发泡材料装入热压机内发泡，之后通水冷却模具至室温，得成型的发泡鞋底具体为将片状料装入温度在165-190℃的热 压机内发泡10-20min，然后通水冷却模具至室温，得成型的发泡鞋底。
本发明的有益效果：通过在发泡材料加入石墨烯的同时加入了分散促进剂，既引入了强极性反应性基团，增加了相容性，又提升了石墨烯在聚合物中的分散性；从而使石墨烯在发泡材料中有效掺杂，从而提升发泡鞋底的抗撕裂、抗剥离能力。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明公开了一种有效掺杂石墨烯的发泡材料的制备方法，所述方法包括以下步骤：(1)造粒：将重量份为100份的主体材料、0.5-10份的氧化石墨烯、1-4份分散促进剂、0.5-5份的润滑剂搅拌混合得到混合料；将得到的混合料熔融混合，再经过冷却后，通过切粒机进行切粒，得到含有石墨烯的粒料；
(2)密炼：将步骤(1)得到的粒料按重量份100份与4-15份的AC发泡剂、1-4份的硫化剂氧化锌、1-5份的硬脂酸、15-45份的填充料钙粉或滑石粉、1-4份的DCP交联剂及0.5-3份的TAIC交联助剂一起放入密炼机进行密炼；
(3)开炼：将步骤(2)得到的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；接着将混料胶调整成片，从炼胶机中拉出并截成的片状发泡材料；
(4)热压发泡：将片状发泡材料装入热压机内发泡，之后通水冷却模具至室温，得成型的鞋底。
其中，步骤(1)所述主体材料为乙烯-醋酸乙烯共聚物、聚乙烯或再生料中的至少一种；所述分散促进剂为马来酸酐接枝聚乙烯(MAH-g-PE)、马来酸酐接枝乙烯-醋酸乙烯共聚物(MAH-g-EVA)、马来酸酐接枝三元乙丙橡胶(MAH-g-HDPE)、马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯三嵌段共聚物 (MAH-g-SEBS)、马来酸酐接枝线形低密度聚乙烯(MAH-g-LLPDE)中的至少一种。
马来酸酐接枝相容剂通过引入强极性反应，使材料具有高的极性和反应性，增加材料之间的相容性，同时马来酸酐接枝相容剂是一种不饱和有机酸酐基本原料，可以和氧化石墨烯表面的羟基、羧基等官能团键合，能有效避免石墨烯自身团聚，利于其在聚合物中的分散，从而对发泡材料进行有效的石墨烯掺杂。
具体的本发明可以如下进行具体实施：
实施例1
首先将重量份为100份的EVA(乙烯-醋酸乙烯共聚物)、2份的氧化石墨烯、3份的MAH-g-EVA(马来酸酐接枝乙烯-醋酸乙烯共聚物)、2份的润滑剂，放进高速搅拌机进行混合10min；然后将混合均匀的混合料加入双螺杆挤出机中熔融混合，螺杆转速为120rmp，在150℃下混炼10min；接着由双螺杆挤出后经水槽冷却后，通过切粒机进行切粒操作，得到含有石墨烯的粒料；
接着将100份的粒料与8份的AC发泡剂、2份的氧化锌、1份的硬脂酸、25份的钙粉、1份的DCP交联剂及0.5份的TAIC交联助剂一起放入密炼机进行密炼，温度120℃，持续3min；然后将密炼后的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；开炼温度控制在125℃；接着将料调整成1mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料；
最后将片状发泡材料装入温度在180℃的热压机内发泡15min，之后通水冷却模具至室温，得成型鞋底。
实施例2
首先将重量份为100份的EVA(乙烯-醋酸乙烯共聚物)、5份的氧化石墨烯、3份的MAH-g-PE(马来酸酐接枝聚乙烯)、1份的润滑剂，放进高速搅拌机进行混合10min；然后将混合均匀的混合料加入双螺杆挤出机中熔融混合，螺杆转速为120rmp，在150℃下混炼10min；接着由双螺杆挤出后经水槽冷却后， 通过切粒机进行切粒操作，得到含有石墨烯的粒料；
接着将100份的粒料与10份的AC发泡剂、2份的氧化锌、1份的硬脂酸、20份的钙粉、2份的DCP交联剂及1份的TAIC交联助剂一起放入密炼机进行密炼，温度120℃，持续5min；然后将密炼后的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；开炼温度控制在125℃；接着将料调整成1mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料；
最后将片状发泡材料装入温度在180℃的热压机内发泡15min，之后通水冷却模具至室温，得成型的鞋底。
实施例3
首先将100份的PE(聚乙烯)、8份的氧化石墨烯、3份的MAH-g-LLPDE(马来酸酐接枝线形低密度聚乙烯)、2份的润滑剂，放进高速搅拌机进行混合20min；然后将混合均匀的混合料加入双螺杆挤出机中熔融混合，螺杆转速为100rmp，在150℃下混炼20min；接着由双螺杆挤出后经水槽冷却后，通过切粒机进行切粒操作，得到含有石墨烯的粒料；
接着将100份的粒料与9份的AC发泡剂、3份的氧化锌、2份的硬脂酸、25份的钙粉、1.5份的DCP交联剂及1份的TAIC交联助剂一起放入密炼机进行密炼，温度120℃，持续3min；然后将密炼后的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；开炼温度控制在128℃；接着将料调整成1mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料；
最后将片发泡材状料装入温度在175℃的热压机内发泡20min，之后通水冷却模具至室温，得成型的鞋底。
对比例1
首先将100份的EVA(乙烯-醋酸乙烯共聚物)、2份的氧化石墨烯、2份的润滑剂，放进高速搅拌机进行混合10min；然后将混合均匀的混合料加入双螺 杆挤出机中熔融混合，螺杆转速为120rmp，在150℃下混炼10min；接着由双螺杆挤出后经水槽冷却后，通过切粒机进行切粒操作，得到含有石墨烯的粒料；
接着将100份的粒料与8份的AC发泡剂、2份的氧化锌、1份的硬脂酸、25份的钙粉、1份的DCP交联剂及0.5份的TAIC交联助剂一起放入密炼机进行密炼，温度120℃，持续3min；然后将密炼后的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；开炼温度控制在125℃；接着将料调整成1mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料；
最后将片状发泡材料装入温度在180℃的热压机内发泡15min，之后通水冷却模具至室温，得成型的鞋底。
上述实施例1、2、3和对比例1的性能测试对比数据如表1所示。从表1可以看出，本发明实施例制备的发泡鞋底与对比例制备的发泡鞋底相对抗撕裂性能提升几十倍，鞋底性能可以得到了明显的提升，并降低鞋底密度，鞋底更轻。
表1
Figure PCTCN2017095422-appb-000001
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种有效掺杂石墨烯的发泡材料的制备方法，其特征在于，所述方法包括以下步骤：
    (1)造粒：将重量份为100份的主体材料、0.5-10份的氧化石墨烯、1-4份分散促进剂、0.5-5份的润滑剂搅拌混合得到混合料；将得到的混合料熔融混合，再经过冷却后，通过切粒机进行切粒，得到含有石墨烯的粒料；
    (2)密炼：将步骤(1)得到的粒料按重量份100份与4-15份的AC发泡剂、1-4份的硫化剂氧化锌、1-5份的硬脂酸、15-45份的填充料钙粉或滑石粉、1-4份的DCP交联剂及0.5-3份的TAIC交联助剂一起放入密炼机进行密炼；
    (3)开炼：将步骤(2)得到的混合物一起放入炼胶机进行二次混炼，让材料充分混合，得到混合均匀的混料胶；接着将混料胶调整成片，从炼胶机中拉出并截成的片状料；
    (4)热压发泡：将片状料装入热压机内发泡，之后通水冷却模具至室温，得成型的发泡鞋底。
  2. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(1)的主体材料为乙烯-醋酸乙烯共聚物、聚乙烯或再生料中的至少一种。
  3. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(1)的所述分散促进剂为MAH-g-PE、MAH-g-EVA、MAH-g-HDPE、MAH-g-SEBS、MAH-g-LLPDE中的至少一种。
  4. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(1)的搅拌混合得到混合料具体为通过高速搅拌机进行混合5-30min。
  5. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(1)的将a得到混合料熔融混合具体为将a得到混合料加入双螺杆挤出机中机型熔融混合，其中螺杆转速为20-200rmp，温度为130-200℃， 混炼时间为5-20min；所述冷却为混合料由双螺杆挤出后经水槽冷却。
  6. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(2)中密炼的温度为120-130℃，密炼时间为2-5min。
  7. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(3)中进行二次混炼的温度为110-140℃。
  8. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(3)中接着将混料胶调整成片，从炼胶机中拉出并截成的片状料具体为将混料胶调整成1-1.5mm厚的片，从炼胶机中拉出并截成40cm*80cm的片状发泡材料。
  9. 根据权利要求1所述的有效掺杂石墨烯的发泡材料的制备方法，其特征在于：所述步骤(4)中将片状发泡材料装入热压机内发泡，之后通水冷却模具至室温，得成型的发泡材料具体为将片状料装入温度在165-190℃的热压机内发泡10-20min，然后通水冷却模具至室温，得成型的发泡鞋底。
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CN110938250A (zh) * 2019-11-14 2020-03-31 浙江恒诚鞋业有限公司 发泡鞋底及其制备方法
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