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            壽光市恒泰新材料有限公司

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            白炭黑對硅橡膠的結構化和觸變作用有多大?

            添加時間:2019-07-31


               硅橡膠的結構化,是個常見的問題。國外有機硅巨頭產品已經有很好的解決方案,而國內不但缺乏基礎性研究,而且由于國人廠家的理念和人家巨頭不同,總是希望能做個啥“神油”,加入一點點就能簡單、方便和低成本的解決之。
               我自己也曾經這么想過,就是開發出一種有效的助劑,期望解決這個問題,通過銷售助劑順便賺點快錢。因此,2010年我在論壇就發了一個求助帖:如何快速測試混煉膠結構化?得到了不少朋友的熱情幫助。后來發現有不少人都有硅橡膠的結構化快速測試需求。
             
            經過一番努力,至今為止,沒有找到所謂的“神油”。隨后,我將注意力轉移到了白炭黑的處理上。由此,對硅橡膠結構化現象有了更深入的認識。
             
            我認為,白炭黑導致硅橡膠結構化,主要是基于白炭黑與高分子量聚硅氧烷巨量的氫鍵作用,這個結論,早就有人得出了,我只是加了兩個字“巨量”。
             
            而白炭黑對硅橡膠(包括涂料中涂料體系)的觸變性貢獻,主要是基于白炭黑與白炭黑之間的相互作用。
             
            于是,問題得到了簡化:
            結構化:白炭黑------硅生膠之間的相互作用(巨量氫鍵),聚硅氧烷高分子鏈相互糾纏,這兩個效應綜合的結果
            觸變性:白炭黑------白炭黑之間的作用,氫鍵,范德華力綜合所致
             
            1結構化細解
             
            白炭黑表面有三種硅羥基-----這不是我的實驗結果,借人家研究結果而已,導致結構化(氫鍵)作用的,應該是那種孤立、高活性硅羥基。這里的巨量氫鍵,是納米級粉體所致,如果是微米級別的硅微粉,數量太少,幾乎無結構化作用。當白炭黑的這種硅羥基被某種方式封閉或者隔離之后,結構化隨之減少,如果封閉或者隔離足夠充分,結構化也就不會發生。這是我的實驗結果,也是很多人的實驗結果。這個過程,通常就是所謂的白炭黑處理,產品稱為“疏水白炭黑”,盡管商業上,我也使用疏水白炭黑這個說法,但我認為這個稱謂是錯誤的,至少是不科學的。原因在于,疏水白炭黑(確實具有外在的疏水性),同樣一種親水白炭黑為原料,但不同的處理,盡管疏水度可以完全一樣,當加入到硅橡膠后,不一定具有抗結構化效果。也就是說,作為硅橡膠的技術人員,不是說只要選用疏水白炭黑,肯定就可以得到抗結構化的產品。
             
            結構化,可以通過封閉羥基、隔離或加入合適的助劑得到不同成都的控制。以化學反應完全封閉羥基,確實可以消除結構化現象。隔離,比如加入大量白油,也可以消除結構化。助劑,比如低分子的羥基硅油,可以延緩結構化(足夠量的加入,也可以長期不結構化)。這些措施,根據產品要求選擇一種或者幾種的組合。
             
            工業上,煉膠的時候,加入硅氮烷,就是一種有效的封閉硅羥基措施,要達到完全的封閉,需要大量的添加量,成本很高,后處理麻煩,而且對膠的力學性能可能有負面影響。加入大量白油,只適合某些產品。目前比較經濟的是加入低分子量的羥基硅油(為什么是短鏈?一般是5鏈節,這個問題很有趣,自己可以試驗試試),或者烷氧基硅烷的水解物、二苯基二羥基硅烷等。甚至,加入水,醇也具有一定的抗結構化作用。
             
            有一個說法,就是結構化可能含有化學鍵,基于這樣的現象:結構化后的膠,經過返練雖然可以繼續使用,但性能和結構化前比有一定差距。我認為,結構化后,由于白炭黑與聚硅氧烷之間的巨量氫鍵、聚硅氧烷之間的高分子糾纏,返練需要極大的剪切力和一定的溫度,局部巨大的摩擦力(局部高溫)可能導致聚硅氧烷鏈節斷裂、降解,性能有所變化就不奇怪了。結構化雖然在煉膠的時候就不可避免,但我們通常關注的的結構化,指的是在常溫常壓、很溫和的條件下存放幾個月內產生的現象。從生膠的結構看,哪個基團具有在常溫常壓溫和條件下與白炭黑產生化學反應的可能呢?你可以說白炭黑含氯,有酸性,那只要加入極微量的胺,結構化就不應該產生,可到目前為止,沒有任何人通過加入胺或者調整白炭黑為中性的辦法獲得抗結構化產品,因此結構化只能是巨量氫鍵的作用。
             
            低分子聚硅氧烷(這里不是指羥基或者烷氧基封端的那種,而是只對白炭黑惰性的甲基或者乙烯基之類),觀察不到結構化現象,或者程度很輕,很明顯和高分子鏈的糾纏有關。
            因此,我認為結構化首先是白炭黑與生膠的作用,其次是生膠高分子糾纏強化了這種作用。
             
            2觸變性細解
            無論是否經過處理,白炭黑在不少體系中均具有良好的觸變性,當然,同樣需要納米級的才具有很明顯的效果,微米級的硅微粉就差多了。甚至,白炭黑自身就可以觀察到類似觸變性現象(我不敢肯定這算不算是觸變性):將硅烷處理后的白炭黑晃動,白炭黑像水一樣的流動性,當靜置一會以后,白炭黑似乎結成團塊,再晃動,立即又具有水一樣的流動性。這個過程可以反復進行。這里,白炭黑在晃動時,產生高壓靜電,粉體之間因此具有很好的流動性(我認為不是硅烷處理后的摩擦力下降所致,雖然也是一個因素),出現結塊現象的時間取決于靜電導出的時間。當白炭黑以較少的量加入到其它粉體時,可提高流動性,也和白炭黑摩擦產生靜電有關,特別是經過處理以后,疏水性的白炭黑效果更好。
            不具備對硅橡膠產生結構化的,經過處理后的白炭黑,依然具有良好的觸變性,甚至在非極性涂料體系中更好使用。因此,可以預見,導致白炭黑具有產生觸變性的因素應該是范德華力,當然,氫鍵也不會沒作用,因為未處理的親水的白炭黑,在良好分散時,觸變性似乎更強。因此,我認為是綜合結果,但以范德華力為主。我不認為白炭黑的觸變性是超分子性的結果,超分子性的觸變劑,是那種嵌段的,比如聚氨酯類,通常用作增稠劑。白炭黑似乎沒有嵌段性,但技術是發展的,將白炭黑弄成嵌段結構不是沒有可能,但問題是,白炭黑不需要嵌段結構就具有很好的觸變性。
               既然氫鍵強度遠遠超過范德華力------這似乎有個矛盾,那為什么觸變性是以范德華力為主呢?其實可以這么理解,只有幾納米的氣相白炭黑,不會以單獨的方式,而是以團聚的方式存在,或者說,白炭黑自身已經結構化了,也可以理解為,氫鍵構建在團聚的白炭黑內了,當然,只是由于固體局限,團聚只能到一定程度,成微米級別。當煉膠時,團聚的粒子被打散,大量硅羥基暴露,給發生結構化造成了一個極為有利的條件,不過,要說明的是,解開團聚,不僅僅是機械力的作用,硅生膠也有重要的貢獻------對比非硅類聚合物就明白。不過,即使施以最大的剪切力,并借助于硅生膠的親和作用,鑒于納米白炭黑巨大的比表面積,巨量的硅羥基強氫鍵作用,要分散到單顆粒子,幾乎是不可能的。至此,基于對納米粉體團聚認識,再回過頭去看結構化,對下列現象是不是有了新的認識?
            1、結構化隨時間緩慢進行,很可能是團聚的粉體緩慢暴露出更多的硅羥基,給人的感覺似乎是羥基硅油之類的抗結構化劑失去了效果。
            2、雖然暴露出更多的硅羥基,但白炭黑之間的氫鍵作用更強,生膠或者助劑不足以將白炭黑分散的更有效(因此不會結構化后更透明,甚至透明度下降),可以視作是團聚白炭黑表面粒子部分出現一個小小的“轉身”。
            3、接下來得到一個結論,就地處理(通常是加硅氮烷),很難將硅羥基消滅干凈,同樣可以理解,專業的白炭黑處理,也未必就能夠處理的到位,純粹考慮處理劑鍵能,也就顯的不足了。回頭再看觸變性,自然而然就可以理解為白炭黑之間范德華力為主的一種作用,當然不能排除氫鍵的作用,所以,只要不大的外作用力,就可以讓體系流動,幾乎無限可逆,構建也很快,并且在非硅類體系中也有效。
             

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