
硅橡膠是(shi)指(zhi)主鏈由硅(gui)和(he)氧原(yuan)子交替(ti)構(gou)成,硅(gui)原(yuan)子上(shang)通常連有(you)(you)兩個有(you)(you)機基(ji)團的(de)(de)橡(xiang)(xiang)(xiang)膠。普通的(de)(de)硅(gui)橡(xiang)(xiang)(xiang)膠主要由含甲基(ji)和(he)少量乙烯(xi)基(ji)的(de)(de)硅(gui)氧鏈節組成。苯基(ji)的(de)(de)引入可(ke)提高(gao)硅(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)高(gao)、低(di)溫(wen)性(xing)(xing)能(neng)(neng),三氟丙基(ji)及氰基(ji)的(de)(de)引入則(ze)可(ke)提高(gao)硅(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)溫(wen)及耐(nai)(nai)油(you)性(xing)(xing)能(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠耐(nai)(nai)低(di)溫(wen)性(xing)(xing)能(neng)(neng)良好,一(yi)般(ban)在(zai)-55℃下(xia)仍能(neng)(neng)工作(zuo)。引入苯基(ji)后,可(ke)達(da)-73℃。硅(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)熱性(xing)(xing)能(neng)(neng)也很(hen)突出,在(zai)180℃下(xia)可(ke)長(chang)期工作(zuo),稍高(gao)于200℃也能(neng)(neng)承受數周或更長(chang)時間仍有(you)(you)彈性(xing)(xing),瞬(shun)時可(ke)耐(nai)(nai)300℃以上(shang)的(de)(de)高(gao)溫(wen)。硅(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)透氣性(xing)(xing)好,氧氣透過率在(zai)合成聚合物中是(shi)較高(gao)的(de)(de)。此外,硅(gui)橡(xiang)(xiang)(xiang)膠還具有(you)(you)生理惰性(xing)(xing)、不(bu)會(hui)導致凝(ning)血的(de)(de)突出特性(xing)(xing),因此在(zai)醫用(yong)領域(yu)應用(yong)廣泛。
主要品種
硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)分類(lei)的(de)(de)方法(fa)很多,通常按(an)(an)(an)固化(hua)前(qian)的(de)(de)形態(tai)分為固體硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)和(he)液(ye)體硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao);按(an)(an)(an)硫(liu)(liu)化(hua)溫(wen)度分為室溫(wen)硫(liu)(liu)化(hua)硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao),高(gao)溫(wen)硫(liu)(liu)化(hua)硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao);按(an)(an)(an)所用單體的(de)(de)不(bu)同(tong),可(ke)分為甲基乙烯基硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao),甲基苯基乙烯基硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)等(deng)(deng);按(an)(an)(an)性能和(he)用途的(de)(de)不(bu)同(tong)又可(ke)分為通用型(xing)、超(chao)耐低溫(wen)型(xing)、超(chao)耐高(gao)溫(wen)型(xing)、高(gao)強力型(xing)、耐油型(xing)、醫用型(xing)等(deng)(deng)等(deng)(deng)。
發展史
硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)早(zao)期是由美國(guo)(guo)(guo)以三氯(lv)化(hua)鐵為催化(hua)劑合(he)成(cheng)的。1945年(nian)(nian),硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)產(chan)品問(wen)世。1948年(nian)(nian),采(cai)用高(gao)比表面積的氣相法白炭黑補強的硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)研制成(cheng)功,使硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的性能(neng)躍升(sheng)到實(shi)用階段,奠定了現代(dai)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)生產(chan)技(ji)術的基礎。從二甲基二氯(lv)硅(gui)(gui)(gui)(gui)烷合(he)成(cheng)開始生產(chan)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的國(guo)(guo)(guo)家有(you)美國(guo)(guo)(guo)。俄羅斯、德國(guo)(guo)(guo)、日本、韓(han)國(guo)(guo)(guo)和(he)(he)中(zhong)(zhong)國(guo)(guo)(guo)等。中(zhong)(zhong)國(guo)(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的工業化(hua)研究(jiu)始于1957年(nian)(nian),多家研究(jiu)所和(he)(he)企(qi)業陸續開發出各(ge)種(zhong)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)。到2003年(nian)(nian)底,中(zhong)(zhong)國(guo)(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)生產(chan)能(neng)力為135千噸,其中(zhong)(zhong)高(gao)溫膠(jiao)(jiao)(jiao)100千噸。
高溫硫化硅橡膠
高(gao)溫硫(liu)化硅(gui)橡膠(jiao)(jiao)是(shi)指聚硅(gui)氧烷(wan)變成(cheng)彈(dan)性(xing)(xing)體(ti)(ti)的(de)(de)(de)(de)過程是(shi)經過高(gao)溫(110-170℃)硫(liu)化成(cheng)型的(de)(de)(de)(de)。它主(zhu)要以高(gao)分子量的(de)(de)(de)(de)聚甲基(ji)乙烯(xi)基(ji)硅(gui)氧烷(wan)為生膠(jiao)(jiao),混入(ru)補強(qiang)填料、硫(liu)化劑等,在(zai)加熱加壓下硫(liu)化成(cheng)彈(dan)性(xing)(xing)體(ti)(ti)。硅(gui)橡膠(jiao)(jiao)的(de)(de)(de)(de)補強(qiang)主(zhu)要是(shi)各種(zhong)類型的(de)(de)(de)(de)白(bai)炭黑,可(ke)使硫(liu)化膠(jiao)(jiao)的(de)(de)(de)(de)強(qiang)度增加數(shu)十倍。有(you)時(shi)為了降低(di)成(cheng)本或改善膠(jiao)(jiao)料性(xing)(xing)能及賦予硫(liu)化膠(jiao)(jiao)各種(zhong)特殊的(de)(de)(de)(de)性(xing)(xing)能,也加入(ru)相應的(de)(de)(de)(de)各種(zhong)添加劑。硫(liu)化劑是(shi)各種(zhong)有(you)機過氧化物或加成(cheng)反應催化劑。
加(jia)工成(cheng)型(xing)方法如(ru)圖所(suo)示。一次硫化(hua)(hua)(hua)的目的是進行(xing)高分(fen)子(zi)鏈(lian)的交(jiao)(jiao)聯(lian)(lian)反應;二(er)次硫化(hua)(hua)(hua)的目的是進行(xing)補(bu)充交(jiao)(jiao)聯(lian)(lian)、驅除硫化(hua)(hua)(hua)劑分(fen)解(jie)產物和其他(ta)揮發性(xing)化(hua)(hua)(hua)合(he)物以穩(wen)定硫化(hua)(hua)(hua)膠的各項性(xing)能。常用的設備有開放(fang)式煉膠機、捏合(he)機及真空密煉機。
主要性能
(1)高(gao)(gao)(gao)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)顯著的(de)(de)(de)特(te)征是高(gao)(gao)(gao)溫(wen)(wen)(wen)穩定(ding)(ding)性(xing)(xing)(xing)(xing)(xing)(xing),雖(sui)然常溫(wen)(wen)(wen)下(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)強(qiang)度(du)僅是天(tian)然橡(xiang)(xiang)(xiang)膠(jiao)(jiao)或某些(xie)合(he)成橡(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)一半(ban),但在(zai)(zai)200℃以上的(de)(de)(de)高(gao)(gao)(gao)溫(wen)(wen)(wen)環境下(xia),硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)仍能(neng)保持(chi)一定(ding)(ding)的(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)、回彈(dan)性(xing)(xing)(xing)(xing)(xing)(xing)和表面硬(ying)度(du),且力學性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)無明(ming)顯變化(hua)(hua)。(2)低(di)(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)玻璃化(hua)(hua)溫(wen)(wen)(wen)度(du)一般為(wei)-70~-50℃,特(te)殊(shu)配方可(ke)達-100℃,表明(ming)其(qi)(qi)低(di)(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)異。這(zhe)對(dui)航空、宇航工業(ye)的(de)(de)(de)意義重大。(3)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)中(zhong)Si-O-Si鍵對(dui)氧、臭氧及紫(zi)外線等十分穩定(ding)(ding),在(zai)(zai)不加任何添(tian)加劑的(de)(de)(de)情況下(xia),就具有優(you)良(liang)的(de)(de)(de)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)(dian)(dian)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)具有優(you)異的(de)(de)(de)絕(jue)緣性(xing)(xing)(xing)(xing)(xing)(xing)能(neng),耐(nai)電(dian)(dian)(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)電(dian)(dian)(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)也(ye)非常好。(5)物(wu)(wu)理機械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)常溫(wen)(wen)(wen)下(xia)的(de)(de)(de)物(wu)(wu)理機械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)比通(tong)用橡(xiang)(xiang)(xiang)膠(jiao)(jiao)差,但在(zai)(zai)150℃的(de)(de)(de)高(gao)(gao)(gao)溫(wen)(wen)(wen)和-50℃的(de)(de)(de)低(di)(di)溫(wen)(wen)(wen)下(xia),其(qi)(qi)物(wu)(wu)理機械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)于通(tong)用橡(xiang)(xiang)(xiang)膠(jiao)(jiao)。(6)耐(nai)油(you)(you)及化(hua)(hua)學試(shi)劑性(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)具有中(zhong)等的(de)(de)(de)耐(nai)油(you)(you)、耐(nai)溶(rong)劑性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。(7)氣(qi)體(ti)透(tou)(tou)過性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。室溫(wen)(wen)(wen)下(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)對(dui)空氣(qi)、氮、氧、二氧化(hua)(hua)碳(tan)等氣(qi)體(ti)的(de)(de)(de)透(tou)(tou)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)比天(tian)然橡(xiang)(xiang)(xiang)膠(jiao)(jiao)高(gao)(gao)(gao)出(chu)30-50倍。(8)生理惰性(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)無毒,無味(wei),無嗅,與(yu)人體(ti)組(zu)織不粘連(lian),具有抗凝血作用,對(dui)肌體(ti)組(zu)織的(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)非常少。特(te)別適合(he)作為(wei)醫用材料(liao)。
硅橡膠的用量
據中(zhong)國(guo)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工業(ye)(ye)協(xie)會統計,2012年(nian)(nian),汽(qi)(qi)(qi)(qi)(qi)車(che)(che)產銷分別(bie)(bie)達到1927.18萬輛和(he)(he)1930.64萬輛,同比分別(bie)(bie)增(zeng)(zeng)長4.63%和(he)(he)4.33%,汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工業(ye)(ye)硅橡膠(jiao)(jiao)(jiao)的用量約達2.0萬t。根據觀研天下的新研究(jiu),增(zeng)(zeng)加有(you)機硅材料(liao)在汽(qi)(qi)(qi)(qi)(qi)車(che)(che)零部件(jian)(jian)方(fang)面的用量,可以(yi)大(da)幅度(du)提(ti)高汽(qi)(qi)(qi)(qi)(qi)車(che)(che)的安(an)全性(xing)能,因(yin)此,汽(qi)(qi)(qi)(qi)(qi)車(che)(che)產量和(he)(he)單車(che)(che)用量水(shui)平的提(ti)高都將推動汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工業(ye)(ye)對(dui)硅橡膠(jiao)(jiao)(jiao)需求(qiu)的增(zeng)(zeng)加。國(guo)家(jia)鼓勵自(zi)主(zhu)品(pin)牌(pai)的汽(qi)(qi)(qi)(qi)(qi)車(che)(che)發(fa)(fa)展,關(guan)鍵汽(qi)(qi)(qi)(qi)(qi)車(che)(che)零部件(jian)(jian)實現自(zi)主(zhu)化(hua),《2012年(nian)(nian)度(du)黨政(zheng)(zheng)機關(guan)公務(wu)用車(che)(che)選用車(che)(che)型目錄(征求(qiu)意見稿)》為(wei)(wei)自(zi)主(zhu)品(pin)牌(pai)擴(kuo)大(da)在政(zheng)(zheng)府采購的市場份額(e),為(wei)(wei)改變目前國(guo)內政(zheng)(zheng)府采購以(yi)合(he)資(zi)品(pin)牌(pai)產品(pin)為(wei)(wei)主(zhu)的局面提(ti)供了保障(zhang)(zhang)。促進自(zi)主(zhu)品(pin)牌(pai)發(fa)(fa)展,國(guo)產汽(qi)(qi)(qi)(qi)(qi)車(che)(che)業(ye)(ye)的繁榮將為(wei)(wei)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)膠(jiao)(jiao)(jiao)的應(ying)用提(ti)供有(you)力保障(zhang)(zhang)。預測未來(lai)3年(nian)(nian),我(wo)國(guo)室溫硫化(hua)硅橡膠(jiao)(jiao)(jiao)在汽(qi)(qi)(qi)(qi)(qi)車(che)(che)行業(ye)(ye)將以(yi)年(nian)(nian)均20%增(zeng)(zeng)長。
此外(wai),硅(gui)(gui)橡膠(jiao)是(shi)重(zhong)要(yao)的(de)(de)(de)非(fei)(fei)石油(you)基合(he)成橡膠(jiao),約占非(fei)(fei)石油(you)基合(he)成橡膠(jiao)消費量的(de)(de)(de)98%。但因(yin)(yin)為(wei)石油(you)價格的(de)(de)(de)大幅(fu)上(shang)漲,同(tong)時(shi)我國在硅(gui)(gui)橡膠(jiao)的(de)(de)(de)關鍵原料有(you)(you)(you)(you)機(ji)硅(gui)(gui)單(dan)體的(de)(de)(de)生產技(ji)術方面取(qu)得突破(po),有(you)(you)(you)(you)機(ji)硅(gui)(gui)單(dan)體的(de)(de)(de)生產技(ji)術在2005年(nian)(nian)前被幾家跨國公(gong)司壟(long)斷,但目前我國已發(fa)展(zhan)成為(wei)全球有(you)(you)(you)(you)機(ji)硅(gui)(gui)單(dan)體第1大國,這2個方面原因(yin)(yin)使硅(gui)(gui)橡膠(jiao)的(de)(de)(de)價格從2011年(nian)(nian)起開始低于(yu)石油(you)基合(he)成橡膠(jiao),僅(jin)約為(wei)大宗石油(you)基橡膠(jiao)的(de)(de)(de)80%~90%,成為(wei)廉價的(de)(de)(de)合(he)成橡膠(jiao),并開始大規模替(ti)代(dai)石油(you)基合(he)成橡膠(jiao)。這將(jiang)極大拓展(zhan)有(you)(you)(you)(you)機(ji)硅(gui)(gui)產業的(de)(de)(de)市場空間,同(tong)時(shi)將(jiang)帶動硅(gui)(gui)油(you)、硅(gui)(gui)烷偶聯劑和硅(gui)(gui)樹脂等其(qi)他有(you)(you)(you)(you)機(ji)硅(gui)(gui)產品(pin)的(de)(de)(de)消費。