WO2018036430A1 - 一种改性纳米复合橡胶材料及其制备 - Google Patents

一种改性纳米复合橡胶材料及其制备 Download PDF

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WO2018036430A1
WO2018036430A1 PCT/CN2017/098073 CN2017098073W WO2018036430A1 WO 2018036430 A1 WO2018036430 A1 WO 2018036430A1 CN 2017098073 W CN2017098073 W CN 2017098073W WO 2018036430 A1 WO2018036430 A1 WO 2018036430A1
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rubber
modified
graphene
surfactant
quaternary ammonium
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段曦东
赵涛楠
毛志浩
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广东纳路纳米科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

Definitions

  • the invention relates to the technical field of materials, in particular to a modified nano composite rubber material and a preparation thereof.
  • Rubber is a kind of elastic polymer. As an important strategic material, it is widely used in high-tech, national economy and national defense industry. In recent years, the rapid development of the rubber industry has put forward higher requirements for rubber products. Rubber materials must be developed in the direction of refinement, functionalization and diversification. However, traditional rubber products have low weather resistance, low friction resistance, easy cracking and pulling. Defects such as low tensile strength and poor gas barrier properties are no longer sufficient for rapid development. Rubber modification is an effective way to improve material properties, while nanomaterials, graphene oxide, graphene and white graphene, have great potential for enhancing rubber functionalization due to their unique molecular structure and properties. Two key issues in the current development of nanomaterial/rubber composites are the dispersion of nanomaterials and the interaction with the matrix interface.
  • the modified nanocomposite rubber material of the present invention comprises: 100 parts by mass of rubber and 0.1-5 parts of nano material as a filler;
  • the nano material is selected from one of graphene oxide, modified white graphene, and modified graphene, and the number of layers is 5-10 layers.
  • the rubber is at least one selected from the group consisting of natural rubber, ABS rubber, neoprene rubber, urethane rubber, silicone rubber, butadiene rubber, butyl rubber, isoprene rubber, butane rubber, and ethylene propylene rubber.
  • the preparation of the modified nanocomposite rubber material of the present invention comprises:
  • Step 1) Preparation of modified nano material: 5-10 layers of graphene or white graphene are treated with a surfactant to obtain a modified nano material powder;
  • Step 2) The rubber, the graphene oxide or the modified nano material powder obtained in the step 1) is kneaded uniformly in an open mill or an internal mixer to obtain a rubber composite material.
  • the surfactant treatment method of the step 1) is immersed in an aqueous solution of a surfactant having a mass concentration of 0.1% for 24 hours, and vacuum dried at 50 ° C for 48 hours.
  • the step 1) treating the graphene surfactant comprises sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyvinyl alcohol, sodium lignosulfonate, cetyltrimethyl One of ammonium bromide, polyvinylpyrrolidone, and the like;
  • the surfactant for treating the white graphene includes a long-chain Lewis base, a long-chain Lewis acid, a quaternary ammonium compound, a sulfonate, and a nonionic surfactant.
  • the long-chain Lewis base is an amine
  • the long-chain Lewis acid is a borane
  • the quaternary ammonium compound is an alkyltrimethyl quaternary ammonium salt, an alkyldimethylbenzyl quaternary ammonium salt, One of dialkyl dimethyl quaternary ammonium salts
  • the sulfonate is sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium lignosulfonate, sodium glycocholate
  • the nonionic surfactant is one of a polyether, a polyester, a polyvinyl alcohol, and a cellulose derivative.
  • the graphene and white graphene are surface-modified and then added to the rubber as a filler, and the graphene oxide itself is rich in functional groups, thereby ensuring good dispersion of the nano material in the rubber;
  • Modified graphene, graphene oxide or modified white graphene has good performance of isolation gas and high strength, and a small amount of addition can greatly improve the barrier property and mechanical strength of rubber while other properties are not affected;
  • the rubber composite material of the invention has simple preparation process, low production cost, no environmental pollution, and is easy to realize large-scale industrial production.
  • Step 1) Preparation of modified graphene: 5-10 layers of graphene are immersed in a sodium dodecyl sulfate solution having a mass concentration of 0.1% for 24 hours, and vacuum-dried at 50 ° C for 48 hours to obtain modified graphene.
  • Step 2) 100 parts of natural rubber and 0.75 parts of the modified graphene obtained in the step 1) are added to an internal mixer and kneaded uniformly to obtain a composite material of modified graphene and natural rubber.
  • Step 1) Preparation of modified graphene: 5-10 layers of graphene were immersed in a polyvinylpyrrolidone aqueous solution having a mass concentration of 0.1% for 24 hours, and vacuum-dried at 50 ° C for 48 hours to obtain modified graphene.
  • Step 2) 100 parts of fluororubber and 1.5 parts of the modified graphene obtained in the step 1) are added to an internal mixer and kneaded uniformly to obtain a composite material of modified graphene and fluororubber.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene are immersed in a long-chain borane aqueous solution having a mass concentration of 0.1% for 24 hours, and vacuum-dried at 50 ° C for 48 hours to obtain a modified white graphene.
  • Step 2) 100 parts of natural rubber and 0.75 parts of the modified white graphene obtained in the step 1) are added to an internal mixer and kneaded uniformly to obtain a composite material of the modified white graphene and the natural rubber.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene are immersed in an aqueous solution of 0.1% by mass of oleylamine for 24 hours, and dried at 50 ° C for 48 hours to obtain modified white graphene.
  • Step 2) 100 parts of isoprene rubber, 1.5 parts of the modified white graphene obtained in the step 1) are added to an internal mixer and kneaded uniformly to obtain a composite material of modified white graphene and isoprene rubber.
  • Comparative Example 1 is a commercially available natural rubber purchased from Shanghai Yanku Chemical Technology Co., Ltd.
  • Table 1 shows the performance parameters of the commercially available natural rubber of Comparative Example 1 and the rubber composites prepared in Examples 1-6:
  • the preparation method of the present invention can greatly improve the barrier properties and mechanical strength of the nano-modified rubber composite.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种改性纳米复合橡胶材料，包含质量份为100份的橡胶和0.1～5份作为填料的纳米材料；所述纳米材料选自氧化石墨烯、改性白石墨烯、改性石墨烯中的一种，层数为5～10层，具体制备方法为：将氧化石墨烯，或经表面改性后的石墨烯、白石墨烯以填料的方式加入到橡胶中。

Description

一种改性纳米复合橡胶材料及其制备 技术领域
本发明涉及材料技术领域，具体涉及一种改性纳米复合橡胶材料及其制备。
背景技术
橡胶是一种有弹性的聚合物，作为一种重要的战略性物资，广泛应用于高新技术、国民经济和国防军工等领域。近年来橡胶工业的迅速发展对橡胶制品提出了更高的要求，橡胶材料必须向着精细化、功能化和多元化的方向发展，而传统的橡胶制品存在耐候耐摩擦性能低、易龟裂、拉伸强度低、气体阻隔性能差等缺陷，已不能满足迅速发展的需求。橡胶改性是提高材料性能的有效途径，而纳米材料氧化石墨烯、石墨烯和白石墨烯以其独特的分子结构及特性在增强橡胶功能化方面极具应用潜力。目前亟待解决纳米材料/橡胶复合材料的两个关键问题是纳米材料的分散以及与基体界面的相互作用。
发明内容
有鉴于此，有必要针对上述的问题，提供一种以纳米材料为填料，并分散在橡胶中，以增强橡胶的强度、耐磨性及气体阻隔性能的改性纳米复合橡胶材料及其制备。
本发明的改性纳米复合橡胶材料，包括：质量份为100份的橡胶和0.1～5份作为填料的纳米材料；
所述纳米材料选自氧化石墨烯、改性白石墨烯、改性石墨烯中的一种，层数为5～10层。
进一步的，所述橡胶选自天然橡胶、ABS橡胶、氯丁橡胶、聚氨酯橡胶、硅橡胶、顺丁橡胶、丁基橡胶、异戊橡胶、丁戊橡胶、乙丙橡胶中的至少一种。
本发明的改性纳米复合橡胶材料的其制备，包括：
步骤1)改性纳米材料的制备：将5-10层的石墨烯或白石墨烯用表面活性剂处理，得到改性纳米材料粉体；
步骤2)将橡胶、氧化石墨烯或步骤1)得到的改性纳米材料粉体在开炼机或密炼机中进行混炼均匀，得到橡胶复合材料。
进一步的，步骤1)所述表面活性剂处理方式为在质量浓度为0.1％的表面活性剂的水溶液浸泡24h，50℃真空干燥48h。
进一步的，步骤1)处理所述石墨烯的表面活性剂包括十二烷基磺酸钠、十二烷基苯磺酸钠、聚乙烯醇、木质素磺酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮等中的一种；处理所述白石墨烯的表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物、磺酸化物、非离子型表面活性剂中的一种。
进一步的，所述长链路易斯碱为胺类；所述长链路易斯酸为硼烷类；所述季铵化物为烷基三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种；所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸钠、甘胆酸钠中的一种；所述非离子型表面活性剂为聚醚、聚酯、聚乙烯醇、纤维素衍生物中的一种。
本发明的有益效果为：
(1)将石墨烯、白石墨烯经表面改性后以填料的方式加入到橡胶中，而氧化石墨烯本身含有丰富的官能团，保证了纳米材料在橡胶中的良好分散；
(2)改性石墨烯、氧化石墨烯或改性白石墨烯有良好的隔离气体的性能和高的强度，少量添加即能大幅度提高橡胶的阻隔性能和机械强度而其他性能不受影响；
(3)本发明的橡胶复合材料制备工艺简单、生产成本低、无环境污染，易于实现大规模的工业化生产。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
步骤1)改性石墨烯的制备：将5-10层的石墨烯用质量浓度为0.1％的十二烷基磺酸钠溶液浸泡24h，50℃真空干燥48h，得到改性石墨烯。
步骤2)将100份天然橡胶、0.75份步骤1)得到的改性石墨烯加入到密炼机中混炼均匀，得到改性石墨烯和天然橡胶的复合材料。
实施例2
步骤1)改性石墨烯的制备：将5-10层的石墨烯用质量浓度为0.1％的聚乙烯吡咯烷酮水溶液浸泡24h，50℃真空干燥48h，得到改性石墨烯。
步骤2)将100份氟橡胶、1.5份步骤1)得到的改性石墨烯加入密炼机中混炼均匀，得到改性石墨烯和氟橡胶的复合材料。
实施例3
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用质量浓度为0.1％的长链硼烷水溶液浸泡24h，50℃真空干燥48h，得到改性白石墨烯。
步骤2)将100份天然橡胶、0.75份步骤1)得到的改性白石墨烯加入密炼机中混炼均匀，得到改性白石墨烯和天然橡胶的复合材料。
实施例4
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用质量浓度为0.1％的油胺水溶液浸泡24h，50℃真空干燥48h，得到改性白石墨烯。
步骤2)将100份异戊橡胶、1.5份步骤1)得到的改性白石墨烯加入密炼机中混炼均匀，得到改性白石墨烯和异戊橡胶的复合材料。
实施例5：
将100份天然橡胶、0.75份氧化石墨烯加入到密炼机中混炼均匀，得到氧化石墨烯和天然橡胶的复合材料。
实施例6：
将100份丁苯橡胶、1.5份氧化石墨烯加入到密炼机中混炼均匀，得到氧化石墨烯和丁苯橡胶的复合材料。
对比例1为市售天然橡胶，购自上海昱库化工科技有限公司。
表1中为对比例1市售天然橡胶、实施例1-6中所制备得到的橡胶复合材料的性能参数：
表1对比例1市售天然橡胶、实施例1-6所得橡胶复合材料的性能
Figure PCTCN2017098073-appb-000001
从上表可知，本发明的制备方法可以大幅度提高纳米改性橡胶复合材料阻隔性能和机械强度。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和 改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (6)

  1. 一种改性纳米复合橡胶材料，其特征在于，包括：质量份为100份的橡胶和0.1～5份作为填料的纳米材料；
    所述纳米材料选自氧化石墨烯、改性白石墨烯、改性石墨烯中的一种，层数为5～10层。
  2. 根据权利要求1所述的改性纳米复合橡胶材料，其特征在于，所述橡胶选自天然橡胶、ABS橡胶、氯丁橡胶、聚氨酯橡胶、硅橡胶、顺丁橡胶、丁基橡胶、异戊橡胶、丁戊橡胶、乙丙橡胶中的至少一种。
  3. 一种权利要求1所述的改性纳米复合橡胶材料的制备方法，其特征在于，包括：
    步骤1)改性纳米材料的制备：将5-10层的石墨烯或白石墨烯用表面活性剂处理，得到改性纳米材料粉体；
    步骤2)将橡胶、氧化石墨烯或步骤1)得到的改性纳米材料粉体在开炼机或密炼机中进行混炼均匀，得到橡胶复合材料。
  4. 根据权利要求3所述的改性纳米复合橡胶材料的制备方法，其特征在于，,步骤1)所述表面活性剂处理方式为在质量浓度为0.1％的表面活性剂的水溶液浸泡24h，50℃真空干燥48h。
  5. 根据权利要求3所述的改性纳米复合橡胶材料的制备方法，其特征在于，步骤1)处理所述石墨烯的表面活性剂包括十二烷基磺酸钠、十二烷基苯磺酸钠、聚乙烯醇、木质素磺酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮等中的一种；处理所述白石墨烯的表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物、磺酸化物、非离子型表面活性剂中的一种。
  6. 根据权利要求5所述的改性纳米复合橡胶材料的制备方法，其特征在于，所述长链路易斯碱为胺类；所述长链路易斯酸为硼烷类；所述季铵化物为烷基 三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种；所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸钠、甘胆酸钠中的一种；所述非离子型表面活性剂为聚醚、聚酯、聚乙烯醇、纤维素衍生物中的一种。
PCT/CN2017/098073 2016-08-22 2017-08-18 一种改性纳米复合橡胶材料及其制备 WO2018036430A1 (zh)

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CN111749025A (zh) * 2020-07-06 2020-10-09 安徽丰运高分子材料有限公司 一种高分子材料氟橡胶再生的制造方法
CN113321860A (zh) * 2021-06-04 2021-08-31 中交一公局集团有限公司 一种隧道用高效防水材料及其制备方法
CN113321860B (zh) * 2021-06-04 2022-07-15 中交一公局集团有限公司 一种隧道用高效防水材料及其制备方法
CN115386248A (zh) * 2022-08-01 2022-11-25 南京林业大学 一种功能化石墨烯改性的大豆蛋白胶黏剂及其制备方法
CN116444870A (zh) * 2023-03-27 2023-07-18 中北大学 一种高石墨烯含量超细天然橡胶粉末母胶的高效低成本制备方法以及应用

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