WO2020143162A1 - 鞋底用超轻石墨烯橡胶发泡胶粒及其制备方法 - Google Patents

鞋底用超轻石墨烯橡胶发泡胶粒及其制备方法 Download PDF

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WO2020143162A1
WO2020143162A1 PCT/CN2019/091164 CN2019091164W WO2020143162A1 WO 2020143162 A1 WO2020143162 A1 WO 2020143162A1 CN 2019091164 W CN2019091164 W CN 2019091164W WO 2020143162 A1 WO2020143162 A1 WO 2020143162A1
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parts
rubber
graphene
mixing
ultra
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PCT/CN2019/091164
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English (en)
French (fr)
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丁天宁
丁德材
丁幼丝
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福建五持恒科技发展有限公司
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Priority to US16/617,501 priority Critical patent/US11702524B2/en
Priority to JP2019556672A priority patent/JP7017009B2/ja
Publication of WO2020143162A1 publication Critical patent/WO2020143162A1/zh

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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • A43B13/026—Composites, e.g. carbon fibre or aramid fibre; the sole, one or more sole layers or sole part being made of a composite
    • 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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    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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    • 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
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
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Definitions

  • the present invention relates to the technical field of rubber products, in particular to an ultra-light graphene rubber foam rubber for shoe soles and a preparation method thereof.
  • Natural rubber is the rubber material with the best coordination between physical and mechanical properties and processability, and has been widely used in daily life, medical and health care, transportation, agriculture, scientific experiments, national defense and other fields. With the development of society, people have put forward higher requirements on the performance of products, especially rubber foam soles. Traditional rubber foam soles are heavy, wear resistance does not meet the requirements, and have poor thermal shrinkage. It is modified.
  • the object of the present invention is to provide an ultra-light graphene rubber foam rubber particles for shoe soles and a preparation method thereof, to reduce weight, enhance wear resistance, and improve heat shrinkage resistance.
  • Ultralight graphene rubber foam particles for soles consisting of the following parts by weight: natural rubber 60-6 5 parts; isoprene rubber 8-12 parts; butadiene rubber 8-12 parts; butadiene 6-8 parts of styrene rubber; 0.8-1.0 parts of modified graphene; 0.08-0.12 parts of poly-N-vinylacetamide; 0.8-1.0 parts of silicone oil; 3.0-3.5 parts of inorganic nanoparticles; 1.2-1.5 parts of zinc oxide; 0.8-1.0 parts of zinc stearate; 1.0-1.2 parts of stearic acid; 0.8-1.0 parts of crosslinking agent; 2.0-3.0 parts of flow aid; 1.5-1.8 parts of foaming agent.
  • the inorganic nano particles are at least one of nano calcium, kaolin or nano montmorillonite.
  • the cross-linking agent is insoluble sulfur.
  • the flow aid is paraffin.
  • the blowing agent is azodicarbonamide.
  • the modified graphene is a layered functional graphene.
  • the present invention further provides a method for preparing ultra-light graphene rubber foam particles for soles, specifically including the following steps:
  • the heating rate in the third step is controlled as follows: rapid temperature rise to 95°C ⁇ 100°C and heat preservation at low speed for 7min ⁇ 8min, then gradually increase the temperature by 1.0°C/min ⁇ 1.2°C/min To 110°C ⁇ 112°C, discharge.
  • rapid temperature rise to 95°C ⁇ 100°C and heat preservation at low speed for 7min ⁇ 8min then gradually increase the temperature by 1.0°C/min ⁇ 1.2°C/min To 110°C ⁇ 112°C, discharge.
  • the beneficial effects of the present invention uses natural rubber as the main rubber, and isoprene rubber, butadiene rubber and styrene butadiene rubber and modified graphene to modify it, and supplemented with amphiphilic spiral Non-ionic dispersant, inorganic nanoparticles, cinnamone oil and other components, so that the modified graphite is dispersed uniformly in each rubber compound,
  • the rubber foamed rubber particles of the present invention are provided with excellent thermal stability, abrasion resistance, tensile strength, improved permanent compression deformation performance and heat shrinkage resistance, and can reduce weight by more than 50%; and, the present invention uses insoluble sulfur, It can ensure the uniformity of vulcanization, greatly shorten the vulcanization time, and help to improve the aging resistance of foamed rubber particles.
  • This embodiment provides an ultralight graphene rubber foam rubber for soles, which is composed of the following parts by weight: 60 parts of natural rubber; 10 parts of isoprene rubber; 9 parts of butadiene rubber; Styrene 8 parts of rubber; 0.85 parts of layered functionalized graphene; 0.08 parts of poly-N-vinylacetamide; 1.0 parts of silicone oil; 3.0 parts of nano-calcium; 1.5 parts of active zinc oxide; 1.0 parts of zinc stearate; stearic acid 1.2 parts; 0.8 parts of insoluble sulfur; 2.0 parts of paraffin; 1.5 parts of azodicarbonamide.
  • This embodiment provides an ultra-light graphene rubber foam rubber for soles, consisting of the following parts by weight: 65 parts of natural rubber; 8 parts of isoprene rubber; 10 parts of butadiene rubber; Styrene 6 parts of rubber; 1.0 parts of layered functionalized graphene; 0.12 parts of poly-N-vinylacetamide; 1.0 parts of silicone oil; 3.2 parts of nano-calcium; 1.5 parts of active zinc oxide; 0.8 parts of zinc stearate; stearic acid 1.2 parts; insoluble sulfur 1.0 parts; paraffin wax 3.0 parts; azodicarbonamide 1.6 parts.
  • This embodiment provides an ultralight graphene rubber foam rubber for soles, which is composed of the following parts by weight: 62 parts of natural rubber; 12 parts of isoprene rubber; 8 parts of butadiene rubber; Styrene 8 parts of rubber; 1.0 parts of layered functionalized graphene; 0.1 parts of poly-N-vinylacetamide; 0.8 parts of silicone oil; 3.5 parts of nano-calcium; active oxygen 1.2 parts of zincide; 1.0 part of zinc stearate; 1.0 part of stearic acid; 1.0 part of insoluble sulfur; 2.5 parts of paraffin; 1.8 parts of azodicarbonamide.
  • This embodiment provides an ultralight graphene rubber foam rubber for soles, which is composed of the following parts by weight: 60 parts of natural rubber; 12 parts of isoprene rubber; 8 parts of butadiene rubber; Styrene 6 parts of rubber; 0.8 parts of layered functionalized graphene; 0.1 parts of poly-N-vinylacetamide; 0.8 parts of silicone oil; 3.0 parts of kaolin; 1.5 parts of active zinc oxide; 0.8 parts of zinc stearate; 1.2 parts of stearic acid Parts; 1.0 parts of insoluble sulfur; 2.5 parts of paraffin; 1.5 parts of azodicarbonamide.
  • This embodiment provides an ultralight graphene rubber foam rubber for soles, which is composed of the following parts by weight: 62 parts of natural rubber; 8 parts of isoprene rubber; 10 parts of butadiene rubber; Styrene 7 parts of rubber; 1.0 parts of layered functionalized graphene; 0.12 parts of poly-N-vinylacetamide; 1.0 parts of silicone oil; 3.5 parts of nano-montmorillonite; 1.2 parts of active zinc oxide; 1.0 parts of zinc stearate; hard Fatty acid 1.0 parts; insoluble sulfur 0.8 parts; paraffin wax 3.0 parts; azodicarbonamide 1.5 parts.
  • the Comparative Example 1 provides an ultralight graphene rubber foam rubber for soles, which is composed of the following parts by weight: 60 parts of natural rubber; 10 parts of isoprene rubber; 9 parts of butadiene rubber; D 8 parts of styrene rubber; 0.85 parts of layered functionalized graphene; 0.08 parts of poly-N-vinylacetamide; 1.0 parts of silicone oil; 3.0 parts of nano calcium; 1.5 parts of active zinc oxide; 1.0 parts of zinc stearate; stearin 1.2 parts of acid; 0.8 parts of ordinary sulfur; 2.0 parts of paraffin; 1.5 parts of azodicarbonamide.
  • the preparation method refers to the preparation method of Example 1, but the low-speed mixing time in step 3 is more than 10 min.
  • the colloidal particle formulation of Comparative Example 3 is the same as that of Example 1 above, and the only difference in the preparation method is that the mixed rubber obtained in Step 2 is directly involved in the mixing process of Step 3 within 2 hours of smelting.
  • the colloidal particle formulation of Comparative Example 4 is the same as that of Example 1 above, and the difference in the preparation method is only that the temperature rising rate of the third mixing step reaches 1.5°C/min and the discharge temperature reaches 115°C.
  • Examples 1-5 and Comparative Examples 1-3 were made into samples and tested for physical properties. The test results are shown in Table 1.

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

Abstract

本发明涉及鞋底用超轻石墨烯橡胶发泡胶粒，由如下重量份数的组分组成：天然橡胶60-65份；异戊橡胶8-12份；顺丁橡胶8-12份；丁苯橡胶6-8份；改性石墨烯0.8-1.0份；聚N-乙烯基乙酰胺0.08-0.12份；硅酮油0.8-1.0份；无机纳米粒子3.0-3.5份；活性氧化锌1.2-1.5份；硬脂酸锌0.8-1.0份；硬脂酸1.0-1.2份；交联剂0.8-1.0份；流动助剂2.0-3.0份；发泡剂1.5-1.8份。采用本发明，使改性石墨烯均匀分散于各橡胶料中，同时赋予本发明橡胶发泡胶粒优良的热稳定性、耐磨性、拉伸强度，改善永久压缩变形性能及抗热收缩性能，并可减轻50%以上重量。

Description

发明名称；:鞋底用超轻石墨烯橡胶发泡胶粒及其制备方法 技术领域
[0001] 本发明涉及橡胶制品技术领域， 特别是涉及一种鞋底用超轻石墨烯橡胶发泡胶 粒及其制备方法。
背景技术
[0002] 天然橡胶是橡胶材料中物理力学性能与工艺加工性能协调性最好的品种， 目前 已被广泛应用于日常生活、 医疗卫生、 交通运输、 农业、 科学试验、 国防等领 域。 随着社会的发展， 人们对产品的性能提出了更高的要求， 尤其是橡胶发泡 鞋底， 传统橡胶发泡鞋底重量大、 耐磨性能达不到要求， 并且抗热收缩差， 往 往需要对其进行改性。
[0003] 近年来有不少利用石墨烯对橡胶材料进行改性的研究， 但在石墨烯的应用过程 中发现， 石墨烯片层结构存在较强的范德华力或者氢键灯相互作用， 使其极易 发生团聚而不能均匀稳定的分散。 通常， 人们通过化学接枝将羧基、 羟基、 氨 基等一些有机官能团街道石墨烯表面对其进行改性， 从而提高石墨烯在高分子 聚合物中的分散性。 但这种方法破坏了石墨烯的晶体结构， 极大地影响了石墨 烯本身的性能。
发明概述
技术问题
[0004] 本发明目的在于提供一种鞋底用超轻石墨烯橡胶发泡胶粒及其制备方法， 减轻 重量， 增强耐磨性， 改善抗热收缩性能。
问题的解决方案
技术解决方案
[0005] 本发明采用的技术解决方案是：
[0006] 鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组成： 天然橡胶 60-6 5份； 异戊橡胶 8-12份； 顺丁橡胶 8-12份； 丁苯橡胶 6-8份； 改性石墨烯 0.8-1.0份 ； 聚 N-乙烯基乙酰胺 0.08-0.12份； 硅酮油 0.8-1.0份； 无机纳米粒子 3.0-3.5份； 活 性氧化锌 1.2-1.5份； 硬脂酸锌 0.8-1.0份； 硬脂酸 1.0-1.2份； 交联剂 0.8-1.0份； 流 动助剂 2.0-3.0份； 发泡剂 1.5- 1.8份。
[0007] 优选地， 所述无机纳米粒子为纳米钙、 高岭土或纳米蒙脱土中的至少一种。
[0008] 优选地， 所述交联剂为不溶性硫磺。
[0009] 优选地， 所述流动助剂为石蜡。
[0010] 优选地， 所述发泡剂为偶氮二甲酰胺。
[0011] 优选地， 所述改性石墨烯为层叠状功能化石墨烯。
[0012] 本发明还进一步提供一种鞋底用超轻石墨烯橡胶发泡胶粒的制备方法， 具体包 括如下步骤：
[0013] 一、 天然橡胶的素炼： 将所述重量份数的天然橡胶放入密炼机进行素炼 15min 〜 20min， 温度控制在 150°C〜 155°C， 经素炼完毕后的天然橡胶存放 72小时后方 可使用；
[0014] 二、 混炼： 把已素炼好的天然橡胶加上所述重量份数的异戊橡胶、 顺丁橡胶、 丁苯橡胶、 改性石墨稀、 聚 N-乙稀基乙酰胺、 桂酮油、 无机纳米粒子一起放入 密炼机内进行混炼 15min〜 20min， 温度控制在 120°C〜 125°C， 经混炼完毕后的 混炼胶存放 24小时后方可使用；
[0015] 三、 密炼： 把已存放超过 24小时的混炼胶放入密炼机内， 再加入所述重量份数 的活性氧化锌、 硬脂酸锌、 硬脂酸、 交联剂、 流动助剂和发泡剂一起进行密炼 ， 控制升温速率， 待温度达到 110°C〜 112°C停止密炼， 倒出密炼胶；
[0016] 四、 开炼： 把密炼后倒出的密炼胶在开炼机上打薄 2次， 出片；
[0017] 五、 造粒： 把开炼好的开炼胶上造粒机进行造粒。
[0018] 优选地， 所述步骤三中的升温速率控制为： 快速升温至 95°C〜 100°C并保温低 速密炼 7min〜 8min后以 1.0°C/min〜 1.2°C/min逐渐升温至 110°C〜 112°C， 排料。 发明的有益效果
有益效果
[0019] 本发明的有益效果： 本发明以天然橡胶为主胶， 并配合异戊橡胶、 顺丁橡胶和 丁苯橡胶以及改性石墨烯对其改性， 并辅以具有两亲性的螺旋形非离子型分散 剂以及无机纳米粒子、 桂酮油等成分， 使改性石墨稀均匀分散于各橡胶料中， 同时赋予本发明橡胶发泡胶粒优良的热稳定性、 耐磨性、 拉伸强度， 改善永久 压缩变形性能及抗热收缩性能， 并可减轻 50%以上重量； 并且， 本发明采用不溶 性硫磺， 可确保硫化的均匀性， 大大缩短硫化时间， 利于改善发泡胶粒耐老化 性能； 本发明采用层叠状功能化石墨烯形状规整、 结构致密并以层叠状、 稳固 而又均匀分布的特殊结构方式稳固地存在于橡胶基料中， 又由于石墨烯具有独 特的二维片层结构， 由于其极高的径厚比、 表现出柔软的形态， 含有 Si-0-C,C = c,c = 0等活性基团， 其在硫化过程中保持与橡胶基料的良好界面结合力情况下 包覆在发泡微孔表面， 增强发泡微孔的抗热收缩性能及强度， 且外力作用下易 于产生相对滑移， 能够产生能量耗散， 从而起到分散对发泡微孔的破坏冲击影 响。
实施该发明的最佳实施例
本发明的最佳实施方式
[0020] 实施例 1
[0021] 本实施例提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组 成： 天然橡胶 60份； 异戊橡胶 10份； 顺丁橡胶 9份； 丁苯橡胶 8份； 层叠状功能 化石墨烯 0.85份； 聚 N-乙烯基乙酰胺 0.08份； 硅酮油 1.0份； 纳米钙 3.0份； 活性 氧化锌 1.5份； 硬脂酸锌 1.0份； 硬脂酸 1.2份； 不溶性硫磺 0.8份； 石蜡 2.0份； 偶 氮二甲酰胺 1.5份。
[0022] 实施例 2
[0023] 本实施例提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组 成： 天然橡胶 65份； 异戊橡胶 8份； 顺丁橡胶 10份； 丁苯橡胶 6份； 层叠状功能 化石墨烯 1.0份； 聚 N-乙烯基乙酰胺 0.12份； 硅酮油 1.0份； 纳米钙 3.2份； 活性氧 化锌 1.5份； 硬脂酸锌 0.8份； 硬脂酸 1.2份； 不溶性硫磺 1.0份； 石蜡 3.0份； 偶氮 二甲酰胺 1.6份。
[0024] 实施例 3
[0025] 本实施例提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组 成： 天然橡胶 62份； 异戊橡胶 12份； 顺丁橡胶 8份； 丁苯橡胶 8份； 层叠状功能 化石墨烯 1.0份； 聚 N-乙烯基乙酰胺 0.1份； 硅酮油 0.8份； 纳米钙 3.5份； 活性氧 化锌 1.2份； 硬脂酸锌 1.0份； 硬脂酸 1.0份； 不溶性硫磺 1.0份； 石蜡 2.5份； 偶氮 二甲酰胺 1.8份。
[0026] 实施例 4
[0027] 本实施例提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组 成： 天然橡胶 60份； 异戊橡胶 12份； 顺丁橡胶 8份； 丁苯橡胶 6份； 层叠状功能 化石墨烯 0.8份； 聚 N-乙烯基乙酰胺 0.1份； 硅酮油 0.8份； 高岭土 3.0份； 活性氧 化锌 1.5份； 硬脂酸锌 0.8份； 硬脂酸 1.2份； 不溶性硫磺 1.0份； 石蜡 2.5份； 偶氮 二甲酰胺 1.5份。
[0028] 实施例 5
[0029] 本实施例提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分组 成： 天然橡胶 62份； 异戊橡胶 8份； 顺丁橡胶 10份； 丁苯橡胶 7份； 层叠状功能 化石墨烯 1.0份； 聚 N-乙烯基乙酰胺 0.12份； 硅酮油 1.0份； 纳米蒙脱土 3.5份； 活 性氧化锌 1.2份； 硬脂酸锌 1.0份； 硬脂酸 1.0份； 不溶性硫磺 0.8份； 石蜡 3.0份； 偶氮二甲酰胺 1.5份。
[0030] 上述实施例 1-5的鞋底用超轻石墨烯橡胶发泡胶粒的制备方法， 均采用如下方 法， 具体包括如下步骤：
[0031] 一、 天然橡胶的素炼： 将所述重量份数的天然橡胶放入密炼机进行素炼 15min 〜 20min， 温度控制在 150°C〜 155°C， 经素炼完毕后的天然橡胶存放 72小时后方 可使用；
[0032] 二、 混炼： 把已素炼好的天然橡胶加上所述重量份数的异戊橡胶、 顺丁橡胶、 丁苯橡胶、 改性石墨稀、 聚 N-乙稀基乙酰胺、 桂酮油、 无机纳米粒子一起放入 密炼机内进行混炼 15min〜 20min， 温度控制在 120°C〜 125°C， 经混炼完毕后的 混炼胶存放 24小时后方可使用；
[0033] 三、 密炼： 把已存放超过 24小时的混炼胶放入密炼机内， 再加入所述重量份数 的活性氧化锌、 硬脂酸锌、 硬脂酸、 交联剂、 流动助剂和发泡剂一起进行密炼 ， 控制升温速率， 快速升温至 95°C〜 100°C并保温低速密炼 7min〜 8min后以 1.0°C /min〜 1.2°C/min逐渐升温至 110°C〜 112°C, 排料、 倒出密炼胶；
[0034] 四、 开炼： 把密炼后倒出的密炼胶在开炼机上打薄 2次， 出片； [0035] 五、 造粒： 把开炼好的开炼胶上造粒机进行造粒。
[0036] 其中， 本发明的所述层叠状功能化石墨烯 SF-GNRs的制备方法为： 将适量的 G ONRs加入无水乙醇中， GONRs与无水乙醇的比例为 1:500， 超声 1小时形成均匀 分散液， 随后加入一定量 HC1调节体系 pH=3〜 4; 称量适量的 KH-570分散于无水 乙醇中， KH-570与无水乙醇的比例为 3: 100， 超声 30min后加入上述分散液中， 搅拌均匀后，将混合体系升温至 60°C反应 24h; 然后用无水乙醇和去离子水在聚四 氟乙烯滤膜上过滤洗涤多次以除去体系中未反应完全的 KH-570并调节体系至中 性， 在冷干机中干燥得到层叠状功能化石墨烯 F-GONRs ; 将制得的 F-GONRs分 散于去离子水中， 超声 1.5小时形成均匀分散液， 随后加入一定量的氨水调节体 系 PH=9〜 10, 并在一定转速下搅拌均匀。 接着加入水合肼并搅拌 1小时， 搅拌均 勻后,将上述反应体系移至 90°C的油浴锅中反应 12小时； 待反应结束并自然冷却 至室温后， 用无水乙醇和去离子水在聚四氟乙烯滤膜上过滤洗涤多次以充分除 去体系中的微量杂质并调节体系至中性， 在冷干机中干燥得到 SF-GNRs。
[0037] 对比例 1
[0038] 该对比例 1提供一种鞋底用超轻石墨烯橡胶发泡胶粒， 由如下重量份数的组分 组成： 天然橡胶 60份； 异戊橡胶 10份； 顺丁橡胶 9份； 丁苯橡胶 8份； 层叠状功 能化石墨烯 0.85份； 聚 N-乙烯基乙酰胺 0.08份； 硅酮油 1.0份； 纳米钙 3.0份； 活 性氧化锌 1.5份； 硬脂酸锌 1.0份； 硬脂酸 1.2份； 普通硫磺 0.8份； 石蜡 2.0份； 偶 氮二甲酰胺 1.5份。 制备方法参照实施例 1的制备方法， 但步骤三的低速密炼时间 要 10min以上。
[0039] 对比例 2
[0040] 该对比例 3的胶粒配方与上述实施例 1相同， 而制备方法的区别也仅在于步骤二 制得的混炼胶在炼好 2小时内直接参与步骤三的密炼过程。
[0041] 对比例 3
[0042] 该对比例 4的胶粒配方与上述实施例 1相同， 而制备方法的区别也仅在于步骤三 密炼的升温速率达到 1.5°C/min并且排料温度达 115°C。
[0043] 将实施例 1-5和对比例 1-3做出样品， 并进行物性测试， 其测试结果见表 1。
[] 表 1 : 实施例 1 -5和对比例 1 -3制得样品物性测试结果
Figure imgf000008_0001
[0044] 以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点， 本行业 的技术人员应该了解， 本发明不受上述实施例的限制， 上述实施例和说明书中 描述的只是说明本发明的原理， 在不脱离本发明创造精神和范围的前提下， 本 发明还会有各种变化和改进， 这些变化和改进都落入要求保护的本发明范围内 ， 本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims

权利要求书
[权利要求 1] 鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于， 该发泡胶粒由如下重 量份数的组分组成： 天然橡胶 60-65份； 异戊橡胶 8-12份； 顺丁橡胶 8- 12份； 丁苯橡胶 6-8份； 改性石墨稀 0.8-1.0份； 聚 N-乙稀基乙酰胺 0.08 -0.12份； 桂酮油 0.8-1.0份； 无机纳米粒子 3.0-3.5份； 活性氧化锌 1.2-1. 5份； 硬脂酸锌 0.8-1.0份； 硬脂酸 1.0-1.2份； 交联剂 0.8-1.0份； 流动助 齐 1J2.0-3.0份； 发泡齐 ij 1.5- 1.8份。
[权利要求 2] 根据权利要求 1所述的鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于 ， 所述无机纳米粒子为纳米钙、 高岭土或纳米蒙脱土中的至少一种。
[权利要求 3] 根据权利要求 1所述的鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于 ， 所述交联剂为不溶性硫磺。
[权利要求 4] 根据权利要求 1所述的鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于 ， 所述流动助剂为石蜡。
[权利要求 5] 根据权利要求 1所述的鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于 ， 所述发泡剂为偶氮二甲酰胺。
[权利要求 6] 根据权利要求 1所述的鞋底用超轻石墨烯橡胶发泡胶粒， 其特征在于 ， 所述改性石墨稀为层叠状功能化石墨稀。
[权利要求 7] 一种如权利要求 1-6任一项所述的鞋底用超轻石墨烯橡胶发泡胶粒的 制备方法， 其特征在于， 具体包括如下步骤：
一、 天然橡胶的素炼： 将所述重量份数的天然橡胶放入密炼机进行素 炼 15min〜 20min， 温度控制在 150°C〜 155°C， 经素炼完毕后的天然橡 胶存放 72小时后方可使用；
二、 混炼： 把已素炼好的天然橡胶加上所述重量份数的异戊橡胶、 顺 丁橡胶、 丁苯橡胶、 改性石墨稀、 聚 N-乙稀基乙酰胺、 桂酮油、 无机 纳米粒子一起放入密炼机内进行混炼 15min〜 20min， 温度控制在 120 °C〜125°C， 经混炼完毕后的混炼胶存放 24小时后方可使用； 三、 密炼： 把已存放超过 24小时的混炼胶放入密炼机内， 再加入所述 重量份数的活性氧化锌、 硬脂酸锌、 硬脂酸、 交联剂、 流动助剂和发 泡剂一起进行密炼， 控制升温速率， 待温度达到 110°C〜 112°C停止密 炼， 倒出密炼胶；
四、 开炼： 把密炼后倒出的密炼胶在开炼机上打薄 2次， 出片； 五、 造粒： 把开炼好的开炼胶上造粒机进行造粒。
[权利要求 8] 根据权利要求 7所述的鞋底用超轻石墨烯橡胶发泡胶粒的制备方法， 其特征在于， 所述步骤三中的升温速率控制为： 快速升温至 95°C〜 10 0°C并保温低速密炼 7min〜 8min后以 1.0°C/min〜 1.2°C/min逐渐升温至 110°C〜 112°C， 排料。
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