WO2022233109A1 - 一种含改性石墨烯的橡胶 - Google Patents

一种含改性石墨烯的橡胶 Download PDF

Info

Publication number
WO2022233109A1
WO2022233109A1 PCT/CN2021/118383 CN2021118383W WO2022233109A1 WO 2022233109 A1 WO2022233109 A1 WO 2022233109A1 CN 2021118383 W CN2021118383 W CN 2021118383W WO 2022233109 A1 WO2022233109 A1 WO 2022233109A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
parts
modified graphene
modifier
piperazine
Prior art date
Application number
PCT/CN2021/118383
Other languages
English (en)
French (fr)
Inventor
吴丹丹
陈登龙
武智鹏
陈晓峰
Original Assignee
福建师范大学泉港石化研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福建师范大学泉港石化研究院 filed Critical 福建师范大学泉港石化研究院
Publication of WO2022233109A1 publication Critical patent/WO2022233109A1/zh

Links

Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the technical field of rubber, and in particular relates to a modified graphene-containing rubber.
  • Rubber also known as elastomer, is a polymer with high elasticity.
  • the rubber industry is one of the important basic industries of the national economy. Necessary materials, in recent years, the development trend of the rubber industry is gratifying. With the continuous expansion of production scale, the rubber industry occupies an important position in my country's industrial economy, but there are also some problems in the rubber itself, such as its The anti-aging effect is not good.
  • anti-aging agent 4020NA anti-aging agent D
  • anti-aging agent RD anti-aging agent RD
  • anti-aging agent 124 anti-aging agent MB
  • anti-aging agent NBC anti-aging agent NBC
  • the purpose of the present invention is to provide a modified graphene-containing rubber, and the rubber obtained by mixing the modified graphene of the present invention with other components of the rubber has the advantage of good anti-aging effect.
  • a kind of rubber containing modified graphene comprising the following parts by weight of raw materials mixed from: 100 parts of rubber, 30-80 parts of carbon black, 1- 8 parts, 0.5-4 parts of stearic acid, 1-5 parts of sulfur, 0.2-4 parts of accelerator, and 1-5 parts of modified graphene;
  • the modified graphene is ball milled by fully mixing graphite and modifier, Then add tert-butyl nitrite and solvent to mix ball milling, fully mix, wash and dry to obtain;
  • the modifiers are aminopropionanilide, 4-aminobenzyl anilide, 2-amino-N-cyclohexyl-N-methyl benzylamine, 4-(4-isopropylpiperazin-1-yl)aniline, (4-aminobenzene)-4-(4-methoxyphenyl)piperazine, (4-(4-amino) One or more of benzyl)piperazin
  • the amino group on the modifier first reacts chemically with tert-butyl nitrite, and then, the modifier reacts with tert-butyl nitrite and the graphene undergoes an addition reaction, so that the modifier reacts with graphene.
  • Modified graphene is formed by connecting with graphene by chemical bonding. After the modified graphene is mixed with other components of the rubber, since the modifier on the modified graphene is not easy to escape from the rubber, The dispersibility of graphene is improved, and the modifier and graphene have a synergistic anti-aging effect, so that the anti-aging effect of the rubber added with modified graphene is better.
  • the modifier is formed by mixing a first substance and a second substance, and the first substance is aminopropionanilide, 4-aminobenzyl anilide, 2-amino-N-cyclohexyl-N- A kind of in methyl benzylamine, described second material is 4-(4-isopropylpiperazine-1-yl) aniline, (4-aminobenzene)-4-(4-methoxyphenyl) ) piperazine, one of (4-(4-aminobenzyl)piperazin-1-yl)ethanone, (4-aminobenzene)-4-(4-methoxyphenyl)piperazine.
  • the modification effect is better compared to the modification by the first substance alone or the use of the second substance alone, so that the first substance is used for modification.
  • the modified graphene obtained by modifying the graphene with the second substance at the same time is added to the rubber, the anti-aging effect of the rubber is better.
  • the mass ratio of graphite: modifier: nitrite is 1:1-50:1-50.
  • the mass ratio of the graphite to the modifier is 1:10.
  • the modified graphene prepared by it has the best modification effect, and the modified graphene formed after such modification is used to make rubber. , can maintain good anti-aging effect on the premise of maintaining other properties of rubber.
  • the solvent is one or more of ethanol, isopropanol, acetone, tetrahydrofuran, ethyl acetate and toluene.
  • the rubber is one or more of natural rubber, styrene-butadiene rubber, butadiene rubber, and butyl rubber.
  • the accelerator is one or more of CZ, DZ, NS, DPG, M, DM, and TMTD.
  • the modifier and graphene are chemically bonded together and mixed with other components of the rubber, the modifier is not easy to escape from the rubber, so that the rubber prepared by using modified graphene has a better anti-aging effect. it is good;
  • the modifier and graphene can interact to produce a synergistic anti-aging effect, so that the rubber prepared by using modified graphene has a better anti-aging effect.
  • a kind of rubber containing modified graphene in parts by weight, first weigh 5 parts of graphite, 50 parts of modifier (25 parts of 2-amino-N-cyclohexyl-N-methylbenzylamine, 25 parts of (4-aminobenzene)-4-(4-methoxyphenyl)piperazine), fully mixed and ball-milled, then added 60 parts of t-butyl nitrite and 200 parts of acetone, mixed and ball-milled, thoroughly mixed and then washed to obtain Modified graphene.
  • modifier 25 parts of 2-amino-N-cyclohexyl-N-methylbenzylamine, 25 parts of (4-aminobenzene)-4-(4-methoxyphenyl)piperazine
  • any values are not limited to the precise ranges or values, which are to be understood to include values near those ranges.
  • the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.
  • Embodiment 1 a kind of rubber containing modified graphene, first take by weighing the mass ratio of 5 parts of graphite, 25 parts of modifier (12.5 parts of aminopropionanilide, 12.5 parts of 1-(4-aminobenzene)-4- (4-methoxyphenyl)piperazine), fully mixed and ball-milled, then added 30 parts of tert-butyl nitrite and 50 parts of toluene, mixed and ball-milled, thoroughly mixed and then washed to obtain modified graphene.
  • modifier 12.5 parts of aminopropionanilide, 12.5 parts of 1-(4-aminobenzene)-4- (4-methoxyphenyl)piperazine
  • Embodiment two a kind of rubber containing modified graphene, in parts by weight, first take by weighing 5 parts of graphite, 50 parts of modifiers (25 parts of 4-aminobenzamide, 25 parts of (4-(4 parts) -aminobenzyl)piperazine-1-yl)ethanone), fully mixed and ball milled, then added 60 parts of t-butyl nitrite and 150 parts of toluene, mixed ball mill, thoroughly mixed and then washed to obtain modified graphene.
  • modifiers 25 parts of 4-aminobenzamide, 25 parts of (4-(4 parts) -aminobenzyl)piperazine-1-yl)ethanone
  • Embodiment 3 a kind of rubber containing modified graphene, in parts by weight, first weigh 5 parts of graphite, 50 parts of modifier (25 parts of 2-amino-N-cyclohexyl-N-methylbenzyl) Amine, 25 parts (4-aminobenzene)-4-(4-methoxyphenyl)piperazine), fully mixed and ball milled, and then added 60 parts of tert-butyl nitrite and 200 parts of acetone, mixed ball mill, and thoroughly mixed After washing, the modified graphene is obtained.
  • modifier 25 parts of 2-amino-N-cyclohexyl-N-methylbenzyl
  • Comparative example one the difference with embodiment one is that the modified graphene prepared according to the present invention is replaced with graphene, aminopropionanilide, 1-(4-aminobenzene)-4-(4-methoxybenzene) base) piperazine mixture.
  • Comparative Example 2 The difference from Example 1 is that the modified graphene prepared according to the present invention is replaced with an anti-aging agent 4020NA.
  • Comparative Example 3 The difference from Example 1 is that the modified graphene prepared according to the present invention is replaced with graphene.
  • Comparative Example 4 The difference with Example 1 is that the modified graphene prepared according to the present invention is replaced by aminopropionanilide and (4-aminobenzene)-4-(4-methoxyphenyl) piperazine. mixture.
  • Comparative Example 5 The difference from Example 1 is that when preparing the modified graphene, all the modifiers were replaced with aminopropionanilide.
  • Comparative Example 6 The difference from Example 1 is that when preparing the modified graphene, all the modifiers were replaced with (4-aminobenzene)-4-(4-methoxyphenyl)piperazine.
  • Comparative example seven the difference with embodiment three is, when preparing modified graphene, its modifier gets 30 parts (15 parts of 2-amino-N-cyclohexyl-N-methylbenzylamine, 15 parts ( 4-aminobenzene)-4-(4-methoxyphenyl)piperazine).
  • Comparative example eight the difference with embodiment three is, when preparing modified graphene, its modifier takes 75 parts (35 parts of 2-amino-N-cyclohexyl-N-methylbenzylamine, 40 parts ( 4-aminobenzene)-4-(4-methoxyphenyl)piperazine).
  • Example 1 The rubber obtained from Example 1 to Example 3 and Comparative Example 1 to Comparative Example 8 was tested for performance, and Table 1 was obtained.
  • the aging coefficient" in Table 1 is the ratio of the product of the tensile strength and the elongation at break of the rubber before and after aging, and it is used to express the retention ability of the rubber properties after aging.
  • the aging coefficients of Examples 1 to 3 are 77.3%, 76.3%, and 76.4%, respectively, and the aging coefficients of Comparative Examples 1 to 3 are 71.5%, 63.1%, and 61.2%.
  • the aging coefficients of Examples 1 to 3 are all greater than those of Comparative Examples 1 to 3, and the anti-aging effect is better, because tert-butyl nitrite chemically reacts with the amino group on the modifier, and then reacts with the amino group on the modifier.
  • Graphene undergoes an addition reaction, so that the modifier is connected with graphene through chemical bonding to form modified graphene. After the modified graphene is mixed with other components of the rubber, due to the modified graphene The modifier is not easy to escape from the rubber, and the dispersibility of graphene is improved, so that the anti-aging effect of the prepared product is better.
  • the aging coefficients of Example 1 and Comparative Example 1 are respectively 77.3% and 71.5%, and the aging coefficients of Comparative Example 3 and Comparative Example 4 are respectively 61.2% and 58.3%.
  • the aging coefficients of Example 1 and Comparative Example 1 are greater than those of Comparative Example 1.
  • the aging coefficient of the third and the comparative example 4 is because the modifier of the present invention and the graphene have a synergistic anti-aging effect, so that the anti-aging effect of the rubber added with the modified graphene is better.
  • the aging coefficient of Comparative Example 4 is 58.3%, and the aging coefficients of Comparative Example 5 and Comparative Example 6 are 54.1% and 53.2%, respectively.
  • the aging coefficient of Comparative Example 4 is greater than that of Comparative Example 5 and Comparative Example 6.
  • the substance interacts with the second substance to synergistically resist aging, so that the rubber prepared by using the modified graphene has a better anti-aging effect.
  • the aging coefficient of Example 3 is 76.4%, and the aging coefficient of Comparative Example 7 is 71.8%.
  • the aging coefficient of Example 3 is greater than that of Comparative Example 7, and its anti-aging effect is better.
  • the aging coefficient of Comparative Example 8 is 79.2 %, although its aging coefficient is 2.8% larger than that of Example 3, other properties begin to decrease significantly, such as elongation at break.
  • the elongation at break has been reduced to 401%, so in order to make the modification effect of modified graphene the best, after using modified graphene to make rubber, it can maintain a better anti-corrosion performance on the premise of maintaining other properties of the rubber.
  • For the aging effect when preparing modified graphene, it is better to set the mass ratio of graphite to modifier to 1:10.

Landscapes

  • 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

一种含改性石墨烯的橡胶，其组分包括橡胶、炭黑、氧化锌、硬脂酸、硫磺、促进剂、防焦剂、改性石墨烯；改性石墨烯是将石墨与改性剂充分混合球磨，然后加入亚硝酸叔丁酯与溶剂混合球磨，充分混合后洗涤干燥得到；改性剂为氨基丙酰苯胺、4-氨基苯甲酰苯胺、2-氨基-N-环己基-N-甲基苯甲胺、4-(4-异丙基哌嗪-1-基)苯胺、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪、(4-(4-氨基苄基)哌嗪-1-基)乙酮中的一种或几种。

Description

一种含改性石墨烯的橡胶 技术领域
本发明属于橡胶技术领域，具体涉及一种含改性石墨烯的橡胶。
 背景技术
橡胶，又称为弹性体，是一种具有高弹性的聚合物，橡胶行业是国民经济的重要基础产业之一，是制造飞机、军舰、汽车、拖拉机、收割机、水利排灌机械、医疗器械等所必需的材料，近年来，橡胶产业的发展态势让人欣喜，随着生产规模的不断扩大，橡胶产业在我国产业经济中占据着重要的地位，但橡胶本身也存在着一些问题，比如它的抗老化效果不好。
目前，提高橡胶抗老化效果的普遍做法是在橡胶组分中添加防老剂4020NA、防老剂D、防老剂RD和防老剂124、防老剂MB、防老剂NBC等物质，但这些物质与橡胶混炼后普遍存在着易迁移、易挥发的特点，时间长了以后，这些防老剂会从橡胶中析出，从而影响橡胶的防老化效果。
另外，也有在橡胶中添加石墨烯的做法，石墨烯具有一定的防老化效果，且相对于普遍的防老剂而言，在橡胶中的稳定性更好，但是石墨烯与橡胶混炼时，极易出现分散不均匀的现象，从而使得石墨烯在橡胶中的防老化效果大打折扣。
 技术问题
如何设计具有抗老化基团的改性剂对石墨烯进行改性，从而发挥石墨烯和改性剂抗老化的协同作用，使橡胶的抗老化效果得到进一步的提升。技术解决方案
本发明的目的在于提供一种含改性石墨烯的橡胶，利用本发明的改性石墨烯与橡胶其它组分混炼得到的橡胶，具有抗老化效果好的优点。
本发明的上述目的是通过以下技术方案得以实现的：一种含改性石墨烯的橡胶，包括以下重量份的原料混炼而成：橡胶100份、炭黑30-80份、氧化锌1-8份、硬脂酸0.5-4份、硫磺1-5份、促进剂0.2-4份、改性石墨烯1-5份；所述改性石墨烯是将石墨与改性剂充分混合球磨，然后加入亚硝酸叔丁酯与溶剂混合球磨，充分混合后洗涤干燥得到；所述改性剂为氨基丙酰苯胺、4-氨基苯甲酰苯胺、2-氨基-N-环己基-N-甲基苯甲胺、4-(4-异丙基哌嗪-1-基)苯胺、 (4-氨基苯)-4-(4-甲氧基苯基)哌嗪、(4-(4-氨基苄基)哌嗪-1-基)乙酮、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪中的一种或几种。
采用上述技术方案，改性剂上的氨基先与亚硝酸叔丁酯发生化学反应，然后，与亚硝酸叔丁酯反应了之后的改性剂与石墨烯发生加成反应，从而使得改性剂通过化学键键合的方式与石墨烯连接在一起形成改性石墨烯，将改性石墨烯与橡胶的其它组分混炼后，由于改性石墨烯上的改性剂不易从橡胶中逸出，石墨烯的分散性得到了改善，而且改性剂与石墨烯具有协同防老化的作用，从而使得加入了改性石墨烯的橡胶的防老化效果更好。
进一步地，所述改性剂由第一物质与第二物质混合而成，所述第一物质为氨基丙酰苯胺、4-氨基苯甲酰苯胺、2-氨基-N-环己基-N-甲基苯甲胺中的一种，所述第二物质为4-(4-异丙基哌嗪-1-基)苯胺、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪、(4-(4-氨基苄基)哌嗪-1-基)乙酮、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪中的一种。
采用上述技术方案，当利用第一物质与第二物质同时进行改性时，相对于单独用第一物质改性或单独使用第二物质而言，其改性效果更好，从而使得利用第一物质与第二物质同时对石墨烯进行改性得到的改性石墨烯添加到橡胶中以后，橡胶的防老化效果更好。
进一步地，所述石墨：改性剂：亚硝酸酯的质量比为1：1-50：1-50。
进一步地，所述石墨与改性剂的质量比为1：10。
采用上述技术方案，其石墨与改性剂的质量比为1：10时，其制备得到的改性石墨烯的改性效果最好，利用这样改性后形成的改性石墨烯制成橡胶后，能够在保持橡胶其它性能的前提下，保持较好的防老化效果。
进一步地，所述溶剂为乙醇、异丙醇、丙酮、四氢呋喃、乙酸乙酯、甲苯中的一种或几种。
进一步地，所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶、丁基橡胶中的一种或多种。
进一步地，所述促进剂为CZ、DZ、NS、DPG、M、DM、TMTD中的一种或多种。
 有益效果
本发明具有以下有益效果：
1、将改性剂与石墨烯通过化学键连在一起并与橡胶其它组分混炼后，改性剂不易从橡胶中逸出，从而使得利用改性石墨烯制得的橡胶其防老化效果更好；
2、改性剂与石墨烯能够相互作用，产生协同抗老化的效果，从而使得利用改性石墨烯制得的橡胶其防老化效果更好。
 本发明的最佳实施方式
一种含改性石墨烯的橡胶，按重量份数计，先称取5份石墨，50份改性剂（25份2-氨基-N-环己基-N-甲基苯甲胺，25份(4-氨基苯)-4-(4-甲氧基苯基)哌嗪），充分混合球磨，然后再加入亚硝酸叔丁酯60份与丙酮200份混合球磨，充分混合后再经过洗涤得到改性石墨烯。称取该改性石墨烯5份，橡胶100份（丁苯橡胶SBR1500为70份，天然橡胶为10份，顺丁橡胶BR9000为20份），炭黑60份，氧化锌2份、硬脂酸1.5份、硫磺2份、促进剂（CZ）1.5份经过混炼制成橡胶。
 本发明的实施方式
以下结合实施例对本发明作进一步详细说明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
实施例一：一种含改性石墨烯的橡胶，先称取质量比为5份石墨，25份改性剂（12.5份氨基丙酰苯胺，12.5份1-(4-氨基苯)-4-(4-甲氧基苯基)哌嗪），充分混合球磨，然后再加入亚硝酸叔丁酯30份与甲苯50份混合球磨，充分混合后再经过洗涤得到改性石墨烯。称取该改性石墨烯5份，橡胶100份（丁苯橡胶SBR1500为70份，天然橡胶为10份，顺丁橡胶BR9000为20份），炭黑60份，氧化锌2份、硬脂酸1.5份、硫磺2份、促进剂（CZ）1.5份经过混炼制成橡胶。
实施例二：一种含改性石墨烯的橡胶，按重量份数计，先称取5份石墨，50份改性剂（25份4-氨基苯甲酰苯胺，25份(4-(4-氨基苄基)哌嗪-1-基)乙酮），充分混合球磨，然后再加入亚硝酸叔丁酯60份与甲苯150份混合球磨，充分混合后再经过洗涤得到改性石墨烯。称取该改性石墨烯5份，橡胶100份（丁苯橡胶SBR1500为70份，天然橡胶为10份，顺丁橡胶BR9000为20份），炭黑60份，氧化锌2份、硬脂酸1.5份、硫磺2份、促进剂（CZ）1.5份经过混炼制成橡胶。
实施例三：一种含改性石墨烯的橡胶，按重量份数计，先称取5份石墨，50份改性剂（25份2-氨基-N-环己基-N-甲基苯甲胺，25份(4-氨基苯)-4-(4-甲氧基苯基)哌嗪），充分混合球磨，然后再加入亚硝酸叔丁酯60份与丙酮200份混合球磨，充分混合后再经过洗涤得到改性石墨烯。称取该改性石墨烯5份，橡胶100份（丁苯橡胶SBR1500为70份，天然橡胶为10份，顺丁橡胶BR9000为20份），炭黑60份，氧化锌2份、硬脂酸1.5份、硫磺2份、促进剂（CZ）1.5份经过混炼制成橡胶。
对比例一：与实施例一的区别在于，将按照本发明制备的改性石墨烯替换为石墨烯，氨基丙酰苯胺，1-(4-氨基苯)-4-(4-甲氧基苯基)哌嗪的混合物。
对比例二：与实施例一的区别在于，将按照本发明制备的改性石墨烯替换为防老剂4020NA。
对比例三：与实施例一的区别在于，将按照本发明制备的改性石墨烯替换为石墨烯。
对比例四：与实施例一的区别在于，将按照本发明制备的改性石墨烯替换为氨基丙酰苯胺和 (4-氨基苯)-4-(4-甲氧基苯基)哌嗪的混合物。
对比例五：与实施例一的区别在于，在制备改性石墨烯时，将改性剂全部替换为氨基丙酰苯胺。
对比例六：与实施例一的区别在于，在制备改性石墨烯时，将改性剂全部替换为(4-氨基苯)-4-(4-甲氧基苯基)哌嗪。
对比例七，与实施例三的区别在于，在制备改性石墨烯时，其改性剂取30份（15份2-氨基-N-环己基-N-甲基苯甲胺，15份(4-氨基苯)-4-(4-甲氧基苯基)哌嗪）。
对比例八，与实施例三的区别在于，在制备改性石墨烯时，其改性剂取75份（35份2-氨基-N-环己基-N-甲基苯甲胺，40份(4-氨基苯)-4-(4-甲氧基苯基)哌嗪）。
对实施例一至实施例三，对比例一至对比例八所得的橡胶进行性能测试，得到表1。
Figure 930599dest_path_image001
上述实施例与对比例的老化实验均依照GB/T 3512-2014执行，其老化温度为100℃，老化时长为48h。其中，表1的“老化系数”为橡胶老化前后橡胶拉伸强度与拉断伸长率乘积的比值，并以此来表达老化后橡胶性能的保持能力。
经检测，由表1的数据对比结果可知，实施例一至实施例三的老化系数分别为77.3%、76.3%、76.4%，对比例一至对比例三的老化系数为71.5%、63.1%、61.2%，其实施例一至实施例三老化系数均大于对比例一至对比例三的老化系数，其抗老化效果更好，这是因为亚硝酸叔丁酯与改性剂上的氨基发生化学反应，然后与石墨烯发生加成反应，从而使得改性剂通过化学键键合的方式与石墨烯连接在一起形成改性石墨烯，该改性石墨烯与橡胶的其它组分混炼后，由于改性石墨烯上的改性剂不易从橡胶中逸出，且石墨烯的分散性得到改善，从而使制得的产品的抗老化效果更好。
实施例一和对比例一的老化系数分别为77.3%、71.5%，对比例三和对比例四的老化系数分别为61.2%、58.3%，其实施例一和对比例一的老化系数大于对比例三和对比例四的老化系数，这是因为本发明的改性剂与石墨烯具有协同防老化的作用，从而使得加入了改性石墨烯的橡胶的防老化效果更好。
对比例四的老化系数为58.3%，对比例五、对比例六的老化系数分别为54.1%、53.2%，对比例四的老化系数大于对比例五和对比例六的老化系数，这说明第一物质与第二物质相互作用，协同抗老化，从而使得利用改性石墨烯制得的橡胶其防老化效果更好。
实施例三的老化系数为76.4%，对比例七的老化系数为71.8%，实施例三的老化系数大于对比例七的老化系数，其抗老化效果更好，对比例八的老化系数虽然是79.2%，其老化系数虽然比实施例三的老化系数大了2.8%，但其它性能开始大幅度降低，比如拉断伸长率，实施例三的拉断伸长率为419%，而对比例八的拉断伸长率降低到了401%，故为了使得改性石墨烯的改性效果最好，利用改性石墨烯制成橡胶后，能够在保持橡胶其它性能的前提下，保持较好的防老化效果，其制备改性石墨烯时，将石墨与改性剂的质量比设置为1：10较好。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (7)

  1. 一种含改性石墨烯的橡胶，其特征在于，包括以下重量份的原料混炼而成：橡胶100份、炭黑30-80份、氧化锌1-8份、硬脂酸0.5-4份、硫磺1-5份、促进剂0.2-4份、改性石墨烯1-5份；所述改性石墨烯是将石墨与改性剂充分混合球磨，然后加入亚硝酸叔丁酯与溶剂混合球磨，充分混合后洗涤干燥得到；所述改性剂为氨基丙酰苯胺、4-氨基苯甲酰苯胺、2-氨基-N-环己基-N-甲基苯甲胺、4-(4-异丙基哌嗪-1-基)苯胺、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪、(4-(4-氨基苄基)哌嗪-1-基)乙酮、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪中的一种或几种。
  2. 根据权利要求1所述的一种含改性石墨烯的橡胶，其特征在于，所述改性剂由第一物质与第二物质混合而成，所述第一物质为氨基丙酰苯胺、4-氨基苯甲酰苯胺、2-氨基-N-环己基-N-甲基苯甲胺中的一种，所述第二物质为4-(4-异丙基哌嗪-1-基)苯胺、 (4-氨基苯)-4-(4-甲氧基苯基)哌嗪、(4-(4-氨基苄基)哌嗪-1-基)乙酮、(4-氨基苯)-4-(4-甲氧基苯基)哌嗪中的一种。
  3. 根据权利要求1所述的一种含改性石墨烯的橡胶，其特征在于，所述石墨：改性剂：亚硝酸酯的质量比为1：1-50：1-50。
  4. 根据权利要求3所述的一种含改性石墨烯的橡胶，其特征在于，所述石墨与改性剂的质量比为1：10。
  5. 根据权利要求1所述的一种含改性石墨烯的橡胶，其特征在于，所述溶剂为乙醇、异丙醇、丙酮、四氢呋喃、乙酸乙酯、甲苯中的一种或几种。
  6. 根据权利要求1所述的一种含改性石墨烯的橡胶，其特征在于，所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶、丁基橡胶中的一种或多种。
  7. 根据权利要求1所述的一种含改性石墨烯的橡胶，其特征在于，所述促进剂为CZ、DZ、NS、DPG、M、DM、TMTD中的一种或多种。
PCT/CN2021/118383 2021-05-06 2021-09-15 一种含改性石墨烯的橡胶 WO2022233109A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110490415.1 2021-05-06
CN202110490415.1A CN113185759B (zh) 2021-05-06 2021-05-06 一种含改性石墨烯的橡胶

Publications (1)

Publication Number Publication Date
WO2022233109A1 true WO2022233109A1 (zh) 2022-11-10

Family

ID=76983728

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/118383 WO2022233109A1 (zh) 2021-05-06 2021-09-15 一种含改性石墨烯的橡胶

Country Status (2)

Country Link
CN (1) CN113185759B (zh)
WO (1) WO2022233109A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185759B (zh) * 2021-05-06 2022-04-01 福建师范大学泉港石化研究院 一种含改性石墨烯的橡胶
CN113999462A (zh) * 2021-12-03 2022-02-01 江苏安路驰科技有限公司 一种耐磨损的摩托车轮胎橡胶材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194096A (zh) * 2014-09-22 2014-12-10 安徽电气集团股份有限公司 一种高强度改性丁腈橡胶及其制备方法
CN107445148A (zh) * 2016-05-25 2017-12-08 中国科学院理化技术研究所 一种球磨制备功能化石墨烯的方法
CN108793138A (zh) * 2017-04-26 2018-11-13 中国科学院理化技术研究所 一种功能化石墨烯浆料的制备方法
CN109346331A (zh) * 2018-09-26 2019-02-15 武汉工程大学 一种双网络复合导电橡胶及其制备方法和应用
CN113185759A (zh) * 2021-05-06 2021-07-30 福建师范大学泉港石化研究院 一种含改性石墨烯的橡胶

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108503888A (zh) * 2018-03-28 2018-09-07 四川大学 一种非迁移性氧化石墨烯接枝防老剂及其制备方法
CN109535770B (zh) * 2018-10-15 2021-03-30 吉林师范大学 一种功能化氧化石墨烯及其制备方法和应用
KR102225469B1 (ko) * 2019-06-19 2021-03-10 한국과학기술연구원 기능화된 산화그래핀 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194096A (zh) * 2014-09-22 2014-12-10 安徽电气集团股份有限公司 一种高强度改性丁腈橡胶及其制备方法
CN107445148A (zh) * 2016-05-25 2017-12-08 中国科学院理化技术研究所 一种球磨制备功能化石墨烯的方法
CN108793138A (zh) * 2017-04-26 2018-11-13 中国科学院理化技术研究所 一种功能化石墨烯浆料的制备方法
CN109346331A (zh) * 2018-09-26 2019-02-15 武汉工程大学 一种双网络复合导电橡胶及其制备方法和应用
CN113185759A (zh) * 2021-05-06 2021-07-30 福建师范大学泉港石化研究院 一种含改性石墨烯的橡胶

Also Published As

Publication number Publication date
CN113185759B (zh) 2022-04-01
CN113185759A (zh) 2021-07-30

Similar Documents

Publication Publication Date Title
WO2022233109A1 (zh) 一种含改性石墨烯的橡胶
Sheikh et al. The potential of kaolin as a reinforcing filler for rubber composites with new sulfur cure systems
CN105924690B (zh) 一种耐老化改性天然橡胶复合材料
CN108192162B (zh) 一种运动鞋底用耐磨橡胶及其制备方法
JP5448803B2 (ja) ゴム組成物
CN105733087A (zh) 橡胶组合物及其制备方法
CN108948725A (zh) 一种耐热耐磨的改性聚氨酯弹性体材料的制备方法
CN102977438A (zh) 一种航空轮胎垫带胶
Abdul Salim et al. The Effect of High Purity Rice Husk Silica Synthesised using Solvent-thermal Extraction Method on the Properties of Natural Rubber Compounds.
CN108276622A (zh) 一种低滚动阻力胎面内衬层橡胶组合物及其应用
CN103254473A (zh) 一种橡胶组合物和硫化橡胶及其制备方法
CN107033405B (zh) 内层胶用橡胶组合物与硫化橡胶及其制备方法和应用
US3364156A (en) Rubber reinforced with carbon black blends
CN109666195A (zh) 一种橡胶复合材料的制备方法
CN107573702B (zh) 炭黑分散剂及其制备方法和应用以及橡胶组合物和硫化橡胶及其制备方法
CN107652479A (zh) 一种β型碳化硅晶须和橡胶并用的网球胶料及其制备方法
CN114672172A (zh) 一种添加铂金硫化剂可长期存放硅橡胶及其制备方法
CN111978602B (zh) 一种高阻尼恒门尼粘度天然橡胶的制备方法及其制得的产品
CN105001454B (zh) 水滑石‑炭黑杂化料的制备方法，水滑石‑炭黑杂化料/橡胶复合材料及其应用
CN112573560A (zh) 一种高分散氧化锌的制备方法
CN113480853A (zh) 一种复合型硫化硅胶垫片及其制备方法
CN106589488B (zh) 一种橡胶组合物和硫化橡胶及其制备方法和应用
CN109504092A (zh) 一种耐磨橡胶
CN113150411B (zh) 耐高温高压橡胶管中胶与内胶综合促进剂及其制备方法
CN103642080A (zh) 高压缩载荷保持率天然橡胶海绵及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21939754

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21939754

Country of ref document: EP

Kind code of ref document: A1