CN111454591A - 一种改性二氧化硅的方法、改性二氧化硅及应用 - Google Patents
一种改性二氧化硅的方法、改性二氧化硅及应用 Download PDFInfo
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
Description
技术领域
本发明涉及无机粉体改性技术领域,进一步地说,是涉及一种改性二氧化硅的方法、改性二氧化硅及应用。
背景技术
近几年,随着石油危机的爆发,以石油为原料制备的炭黑价格越来越高,并且在生产过程中污染程度高、能源消耗大,使其应用范围受到了极大的限制。白炭黑是纳米二氧化硅的俗称,不仅可以保证轮胎的使用寿命与良好的机械性能,还具有优异的抗湿滑性能,低的滚动阻力和良好的耐磨性,即所谓的“绿色轮胎”。但白炭黑表面存在着大量的羟基基团。羟基间的相互吸引导致了二氧化硅粒子间的聚集,这严重影响了白炭黑的应用。因此,白炭黑要想进一步被应用,对其进行表面改性是必要的,目前市场上主要以硅烷偶联剂进行改性,硅烷偶联剂的通式可以表示为R-SiZn,其中Z代表烷氧基,R代表有机基团,在改性白炭黑时,烷氧基可以和表面羟基作用,有机基团可以和橡胶分子链发生反应,以起到偶联桥作用,但是硅烷偶联剂在改性过程中,会产生小分子的乙醇有机物,从而对环境造成污染。
发明内容
为解决现有技术中出现的问题,本发明提供了一种改性二氧化硅的方法、改性二氧化硅及应用。本发明改性白炭黑时产生小分子有机物明显减少,甚至可以做到没有任何VOC排放,有利于环境的保护,并且价格便宜没有毒性。
本发明的目的之一是提供一种改性二氧化硅的方法。
包括:
改性剂与二氧化硅粉末混合研磨加热,得到改性二氧化硅;
所述改性剂为化合物A,或者化合物A和硅烷偶联剂;
所述化合物A的结构式为:
其中,W+X+Y+Z=n,n的值在4-30之间,式中R1为烷基链段结构、直链或支链结构、脂肪酸结构、芳香族结构、或是具有可与橡胶不饱和键反应的基团的杂链结构。
其中,
所述化合物A优选为聚氧乙烯失水山梨醇脂肪酸酯
所述聚氧乙烯失水山梨醇脂肪酸酯优选为聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨糖醇酐单棕榈酸酯、聚氧乙烯山梨醇酐单硬脂酸酯、聚氧乙烯20山梨醇酐单油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯中的一种或组合。
化合物A和硅烷偶联剂的用量比为1:5~5:1,优选为1:2~2:1。
改性剂的用量为白炭黑质量的0.1%~100%;优选为0.1%~50%,更优选为1%~20%。
本发明的目的之二是提供一种由所述方法得到的改性二氧化硅。
本发明的目的之三是提供一种改性二氧化硅在橡胶组合物中的应用。
本申请采用的改性剂化合物A,
其中,W+X+Y+Z=n,n的值在4-30之间,式中R1可为饱和的或非饱和的烷基链段结构、直链或支链结构、脂肪酸结构、芳香族结构、或是具有可以与橡胶不饱和键反应的基团的杂链结构(如-F、-Cl、-Br、-I、HS-、-NH2、HNR'-),支链结构中的醚键可以和白炭黑表面羟基形成氢键,端羟基可以和白炭黑表面的硅羟基发生脱水缩合反应形成Si-O-Si键。其特征在于,式中R1为不饱和烷基链段或不饱和脂肪酸链结构时(链段结构中含有-CH=CH-),在硫化的过程中,白炭黑表面接枝的改性剂会和橡胶的不饱和键在硫化剂的作用下进行共交联,将白炭黑接枝在橡胶的分子链上;R1链段具有可以与橡胶反应的基团(如巯基HS-),可直接将改性后的白炭黑接枝在橡胶分子链上;R1链段中具有不饱和链段和高活性的基团是,该改性剂具有与传统硅烷偶联剂类似的作用机理,都是先接枝在白炭黑表面上进行改性,然后再通过改性剂与橡胶分子链形成化学键将白炭黑接枝在橡胶分子链上,R1为饱和脂肪酸链时,长链结构可以包覆白炭黑表面,遮蔽白炭黑表面的羟基,降低白炭黑的极性,提高与非极性橡胶的相容性,改善白炭黑的分散;主要是起到解决白炭黑分散的问题,R1基团为脂肪酸结构,TWEEN系列化合物就是此结构中的一种。
本发明的改性方法可以采用现有技术中常规的改性白炭黑的方法。
本申请所采用的设备包括不仅限于采用高速搅拌机、粉碎机、分散机、研磨机等设备对白炭黑干粉进行改性,上述设备可单独使用或串联并用,其步骤为将待改性的白炭黑粉末置于上述设备中,将配好的上述改性剂的一种或多种混合喷洒在白炭黑表面,然后通过高速的研磨、剪切,让改性剂充分和白炭黑接触,然后将混合好的白炭黑置于包括不仅限于烘箱、动态硫床、沸腾床等可加热的设备中,进行进一步反应,最终得到改性白炭黑,也称为有机化白炭黑。上述改性剂的用量为白炭黑质量份数的0.1%~100%,优选为0.1%~50%,更优选为1%~20%,上述混合或研磨设备的运转转速应保持在100~100000rpm之间,优选为100~50000rpm,更优选为100~20000rpm,上述加热设备温度应控制在30~400℃,优选为50~200℃,更优选为60~160℃,和改性剂混合好的白炭黑在加热设备中停留的时间应控制在5min~120min,优选为10min~100min,更优选为20min~60min。
也可以采用:
将上述改性剂加入到白炭黑前驱体水玻璃中,在白炭黑粒子形成的同时对其进行表面改性,可以有效的控制白炭黑粒子的大小,并且在白炭黑粒子形成的第一时间对其进行表面处理,降低白炭黑的表面极性,更有效的阻止了生成的白炭黑粒子团聚,最后通过干燥得到改性白炭黑,
步骤为:
1、水玻璃除杂后将水玻璃固体溶解得到原料粗液,然后稀释、沉淀、过滤后得到合格的水玻璃溶液;
2、白炭黑合成及改性,将步骤1得到的水玻璃溶液与浓硫酸、盐酸、碳酸、碳酸氢铵等混合,在硅酸钠反应生成原硅酸及二氧化硅的同时将上述的改性剂加入到反应溶液中对白炭黑进行改性,反应后得到改性白炭黑粗产物,改性剂的用量为白炭黑质量(干物质)的1%~20%,改性剂的加入要和白炭黑粒子的形成匹配,过早的将所有改性剂都加入到反应溶液中会影响白炭黑的合成,加入的过晚,生成的白炭黑粒子又会团聚成聚集体;
3、白炭黑提纯,对步骤2得到的白炭黑粗产物进行压滤、洗涤、打浆,干燥后得到改性白炭黑成品。
二、通过新型改性剂制备改性白炭黑,也可以在二氧化硅粒子形成后未干燥前处于水浆状态时加入上述改性剂进行表面改性,然后再通过喷雾干燥得到改性白炭黑,这种方法的好处在于,操作更简易,并且不会影响白炭黑的合成,改性反应可控性更好,同时,不受酸浓度的影响,改性剂的用量与上述方法的用量相当。该方法关键是白炭黑粒子形成后很快就会团聚为团聚体,所以采用该方法制备改性白炭黑,在改性的同时需要采用胶体磨(或其他具有相同作用的设备)对白炭黑水浆进行研磨设备,特点在于,边将破除白炭黑聚集体,边对白炭黑进行改性。
本发明的改性剂,分子链具有醚键、链端带有醚羟基,且具有长脂肪链的带氧五元杂环结构。该结构的化合物不仅可以单独使用直接对白炭黑改性,还可以与硅烷偶联剂并用,其操作简单,效果显著,两种方法都可以达到对白炭黑的分散,与传统的硅烷偶联剂改性白炭黑方法相比,该方法在降低甚至不使用硅烷偶联剂的情况下,白炭黑的分散没有降低,最重要是降低甚至不产生在改性过程中产生的VOC排放,有利于环境保护,同时TWEEN价格较便宜,且毒性几乎没有。
附图说明
图1是TWEEN-20有机改性白炭黑的热重(TG)图谱;
图1测的是热失重,测试温度范围是40℃-800℃,原理是通过升高温度,化合物里面分解温度低的会先分解,分解温度高的会晚一点分解,因此会出现随着温度的升高,曲线是一直下降的,first region是40℃到120℃,我们把它看做是水的挥发,包括自由水和结合水。second region是从120℃到800℃,可以理解为改性剂接枝改性二氧化硅上,然后升温会分解,纵坐标的重量百分比减小,这里面改性剂就是吐温20。
图1横坐标是温度;纵坐标是重量;
图2是TWEEN-20有机改性白炭黑的红外(FT-IR)图谱;
图3是TWEEN-20有机改性白炭黑的X-射线光电子能谱(XPS)图谱;
图4是不添加改性剂的白炭黑与经TWEEN-20、TWEEN-65、TWEEN-80、TWEEN-85改性后的白炭黑的混炼胶的储能模量(RPA)图;
图5是图4的局部放大图;
图6是TWEEN-20与硅烷偶联剂不同比例改性与单独使用纯的硅烷偶联剂改性白炭黑混炼胶的储能模量(RPA)图。
具体实施方式
下面结合实施例,进一步说明本发明。
实施例中所用原料均为市售。
实施例1
首先对于白炭黑干粉改性,我们采取高速粉碎机,在粉碎之前,我们按照质量比TWEEN-20:白炭黑=1:10,准确称量好,先将白炭黑加入到粉碎机中,然后把TWEEN-20均匀的喷洒在白炭黑表面,关于喷洒可以用喷雾器等设备,然后打开高速粉碎机,设置转速为10000rpm,设置加热温度为150℃,粉碎时间为20分钟,利用粉碎机的高速转动,其拥有的强大的剪切力使白炭黑颗粒剪切的更小,以达到与改性剂接触的更加充分,从而改性的更加的完全,设置高温从动力学角度,可以增加改性剂的活性,使反应进行的更快,选择20分钟,目的是延长一定反应时间,使反应可以更加的彻底。粉碎机粉碎结束后,把反应后的混合物放进150℃烘箱,并把白炭黑铺平,以增加表面积,从而反应可以进行的更加彻底,放进烘箱2小时,最终得到改性白炭黑,也称为有机化白炭黑。
实施例2
对白炭黑改性,我们也可以在白炭黑水浆中对其进行改性具体步骤为:因为白炭黑时水浆溶液,因此我们是按照水浆中白炭黑含量计算成白炭黑干粉量,然后我们按照质量比TWEEN-20:白炭黑干粉=1:10,准确称量好,利用胶体磨进行不停的循环,达到在溶液中对白炭黑进行改性,这种在液体中对白炭黑进行改性的接触表面积更大,因此更加的容易混均匀,并且胶体磨利用不停的磨可以把白炭黑磨的颗粒更加的细小,以至于可以和改性剂达到暂时的稳定,我们选择在5℃进行磨,低温可以降低白炭黑表面羟基的活性,不至于刚刚把白炭黑的颗粒磨小后,又立即进行团聚,因此我们选择5℃进行磨,磨的时间以30分钟,以使白炭黑颗粒更加的细小,同时达到暂时的稳定。然后利用白炭黑和改性剂的混合物进行喷雾,我们选择的喷雾温度是200℃,喷雾的原理在于利用喷雾机器,使白炭黑和改性的混合物以类似雾的状态喷出,在200℃高温下,瞬间干燥变成改性白炭黑,以此达到白炭黑的改性。
实施例3
首先采用直接改性白炭黑,称取TWEEN-20:白炭黑=1:10,用万能高速粉碎机对其混合物进行粉碎,以达到混均匀,然后放到烘箱以150℃进行反应2h。反应结束后,用乙醇进行洗涤并抽滤,把吸附在白炭黑上面而没有起作用的TWEEN-20洗掉,然后放到烘箱以60℃烘干24h,直至恒重。取适量进行热重、红外、X-射线光电子能谱进行测试,发现TWEEN-20是可以接枝到白炭黑上。见图1~图3。
实施例4
同实施例1,区别在于改性剂采用TWEEN-65,TWEEN-65:白炭黑=1:1。
实施例5
同实施例1,区别在于改性剂采用TWEEN-80,TWEEN-80:白炭黑=1:5。
实施例6
同实施例1,区别在于改性剂采用TWEEN-85,TWEEN-85:白炭黑=1:3.
实施例7
同实施例1,区别在于改性剂采用TWEEN-20与Si69并用,Si69:T20=1:1。
实施例8
同实施例7,Si69:T20=2:1。
实施例9
本实验以天然橡胶为例,所用基本配方见下表一。取白炭黑70g,及实施例1,4,5,6,7改性白炭黑,首先在开炼机上进行混炼,先把生胶在开炼机上薄通6遍,将称量好的白炭黑、或者改性白炭黑分三次加入到开炼机上,再加入氧化锌、硬脂酸,混炼均匀后,在密炼机中进行热处理,150℃处理5分钟,最后在开炼机上加促进剂及硫磺。炼完24h后,用RPA对该混炼胶的储能模量(G′)进行应变扫描,结果显示,改性后白炭黑填充的混炼胶,其初始模量值有明显的降低,说明改性后的白炭黑分散得到了极大的改善,并且此方法改性白炭黑没有任何VOC产生。见图4~图5。
表一
实施例10
本实验以天然橡胶为例,所用基本配方见下表二。取白炭黑70g,实施例7,8的改性白炭黑进行实验,意在验证不同比例配合使用是否会有更好的效果。首先在开炼机上进行混炼,先把生胶在开炼机上薄通6遍,将称量好的白炭黑、或改性白炭黑分三次加入到开炼机上,再加入氧化锌、硬脂酸,混炼均匀后,在密炼机中进行热处理,150℃处理5分钟,最后在开炼机上加促进剂及硫磺。炼完24h后,用RPA对该混炼胶的储能模量(G′)进行应变扫描,拉力机进行力学性能测试,结果显示,改性后白炭黑填充的混炼胶,其初始模量值较低,在减弱了硅烷偶联剂的情况下,分散比全部用硅烷偶联的还低,并且力学性能甚至更高,说明填料网络结构变弱,白炭黑分散较好,并且极大的减少了VOC产生。见图6及表三。
表二
表三
样品 | Si69 | Si69:T20=1:1 | Si69:T20=2:1 |
100%定伸应力/Mpa | 2.8 | 2.7 | 2.7 |
300%定伸应力/Mpa | 12.0 | 11.5 | 11.3 |
扯断伸长率/% | 468 | 502 | 466 |
拉伸强度/MPa | 21.2 | 22.7 | 20.7 |
撕裂强度/KN/m | 116 | 126 | 119 |
邵A硬度 | 67 | 69 | 65 |
Claims (10)
2.如权利要求1所述的改性二氧化硅的方法,其特征在于:
所述化合物A为聚氧乙烯失水山梨醇脂肪酸酯。
3.如权利要求2所述的改性二氧化硅的方法,其特征在于:
所述聚氧乙烯失水山梨醇脂肪酸酯为聚氧乙烯山梨醇酐单月桂酸酯、聚氧乙烯山梨糖醇酐单棕榈酸酯、聚氧乙烯山梨醇酐单硬脂酸酯、聚氧乙烯20山梨醇酐单油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯中的一种或组合。
4.如权利要求1所述的改性二氧化硅的方法,其特征在于:
化合物A和硅烷偶联剂的用量比为1:5~5:1。
5.如权利要求4所述的改性二氧化硅的方法,其特征在于:
化合物A和硅烷偶联剂的用量比为1:2~2:1。
6.如权利要求1所述的改性二氧化硅的方法,其特征在于:
改性剂的用量为白炭黑质量的0.1%~100%。
7.如权利要求6所述的改性二氧化硅的方法,其特征在于:
改性剂的用量为白炭黑质量的0.1%~50%。
8.如权利要求7所述的改性二氧化硅的方法,其特征在于:
改性剂的用量为白炭黑质量的1%~20%。
9.如权利要求1~8之一所述的方法得到的改性二氧化硅。
10.如权利要求9所述的改性二氧化硅在橡胶组合物中的应用。
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