
硅橡膠是指主鏈由硅(gui)(gui)(gui)和氧原(yuan)子交替構成(cheng),硅(gui)(gui)(gui)原(yuan)子上通常連有(you)兩個有(you)機(ji)基(ji)團的(de)橡(xiang)(xiang)膠。普(pu)通的(de)硅(gui)(gui)(gui)橡(xiang)(xiang)膠主要由含甲基(ji)和少量乙烯基(ji)的(de)硅(gui)(gui)(gui)氧鏈節組成(cheng)。苯(ben)基(ji)的(de)引(yin)入可提高(gao)(gao)(gao)(gao)硅(gui)(gui)(gui)橡(xiang)(xiang)膠的(de)耐(nai)高(gao)(gao)(gao)(gao)、低溫(wen)(wen)性(xing)(xing)(xing)(xing)能(neng)(neng),三氟丙(bing)基(ji)及氰(qing)基(ji)的(de)引(yin)入則可提高(gao)(gao)(gao)(gao)硅(gui)(gui)(gui)橡(xiang)(xiang)膠的(de)耐(nai)溫(wen)(wen)及耐(nai)油性(xing)(xing)(xing)(xing)能(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)膠耐(nai)低溫(wen)(wen)性(xing)(xing)(xing)(xing)能(neng)(neng)良好,一般在(zai)-55℃下(xia)仍(reng)能(neng)(neng)工作。引(yin)入苯(ben)基(ji)后,可達(da)-73℃。硅(gui)(gui)(gui)橡(xiang)(xiang)膠的(de)耐(nai)熱性(xing)(xing)(xing)(xing)能(neng)(neng)也很(hen)突(tu)出,在(zai)180℃下(xia)可長期工作,稍高(gao)(gao)(gao)(gao)于200℃也能(neng)(neng)承受數周或更長時間(jian)仍(reng)有(you)彈性(xing)(xing)(xing)(xing),瞬時可耐(nai)300℃以上的(de)高(gao)(gao)(gao)(gao)溫(wen)(wen)。硅(gui)(gui)(gui)橡(xiang)(xiang)膠的(de)透(tou)氣性(xing)(xing)(xing)(xing)好,氧氣透(tou)過率在(zai)合(he)成(cheng)聚合(he)物中是較高(gao)(gao)(gao)(gao)的(de)。此外,硅(gui)(gui)(gui)橡(xiang)(xiang)膠還(huan)具有(you)生理惰(duo)性(xing)(xing)(xing)(xing)、不會導致凝(ning)血的(de)突(tu)出特(te)性(xing)(xing)(xing)(xing),因(yin)此在(zai)醫用領域應(ying)用廣泛。
主要品種
硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)分(fen)類的(de)方法很多,通常(chang)按(an)固(gu)化前的(de)形態分(fen)為(wei)固(gu)體(ti)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)和(he)液體(ti)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao);按(an)硫化溫度(du)分(fen)為(wei)室溫硫化硅(gui)橡(xiang)(xiang)膠(jiao)(jiao),高(gao)(gao)溫硫化硅(gui)橡(xiang)(xiang)膠(jiao)(jiao);按(an)所用(yong)單(dan)體(ti)的(de)不(bu)同,可分(fen)為(wei)甲基(ji)乙(yi)烯基(ji)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao),甲基(ji)苯基(ji)乙(yi)烯基(ji)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)、氟硅(gui),腈硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)等(deng);按(an)性能和(he)用(yong)途的(de)不(bu)同又可分(fen)為(wei)通用(yong)型(xing)(xing)(xing)、超耐低溫型(xing)(xing)(xing)、超耐高(gao)(gao)溫型(xing)(xing)(xing)、高(gao)(gao)強力(li)型(xing)(xing)(xing)、耐油型(xing)(xing)(xing)、醫用(yong)型(xing)(xing)(xing)等(deng)等(deng)。
發展史
硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)早期是(shi)由美國(guo)(guo)以三氯化鐵(tie)為催化劑(ji)合成的(de)。1945年(nian),硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)產品問世。1948年(nian),采用(yong)高(gao)比表面積(ji)的(de)氣相法白(bai)炭黑補強的(de)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)研制成功(gong),使硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)性能躍升到實用(yong)階段,奠定(ding)了現代硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)生產技(ji)術的(de)基礎。從二(er)甲基二(er)氯硅(gui)烷合成開始(shi)生產硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)國(guo)(guo)家有(you)美國(guo)(guo)。俄羅(luo)斯、德國(guo)(guo)、日本、韓國(guo)(guo)和中(zhong)國(guo)(guo)等。中(zhong)國(guo)(guo)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)工業(ye)化研究始(shi)于(yu)1957年(nian),多家研究所和企業(ye)陸續(xu)開發出各種硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)。到2003年(nian)底,中(zhong)國(guo)(guo)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)生產能力為135千(qian)噸(dun),其中(zhong)高(gao)溫膠(jiao)100千(qian)噸(dun)。
高溫硫化硅橡膠
高(gao)溫硫(liu)(liu)(liu)化硅(gui)橡膠(jiao)是(shi)指聚(ju)硅(gui)氧烷變成彈(dan)(dan)性(xing)(xing)(xing)體的(de)過(guo)程(cheng)是(shi)經(jing)過(guo)高(gao)溫(110-170℃)硫(liu)(liu)(liu)化成型的(de)。它主要(yao)以高(gao)分子(zi)量的(de)聚(ju)甲基(ji)乙烯基(ji)硅(gui)氧烷為(wei)生(sheng)膠(jiao),混入補強填料、硫(liu)(liu)(liu)化劑(ji)等,在(zai)加(jia)(jia)熱(re)加(jia)(jia)壓下硫(liu)(liu)(liu)化成彈(dan)(dan)性(xing)(xing)(xing)體。硅(gui)橡膠(jiao)的(de)補強主要(yao)是(shi)各種類(lei)型的(de)白炭黑,可使硫(liu)(liu)(liu)化膠(jiao)的(de)強度增加(jia)(jia)數十(shi)倍(bei)。有時(shi)為(wei)了降低成本(ben)或改善(shan)膠(jiao)料性(xing)(xing)(xing)能(neng)及賦(fu)予硫(liu)(liu)(liu)化膠(jiao)各種特殊的(de)性(xing)(xing)(xing)能(neng),也加(jia)(jia)入相應的(de)各種添加(jia)(jia)劑(ji)。硫(liu)(liu)(liu)化劑(ji)是(shi)各種有機過(guo)氧化物(wu)或加(jia)(jia)成反應催(cui)化劑(ji)。
加(jia)工(gong)成(cheng)型方法如圖所示。一次(ci)硫(liu)化的(de)(de)(de)目的(de)(de)(de)是進行高(gao)分子鏈(lian)的(de)(de)(de)交(jiao)(jiao)聯(lian)(lian)反應;二次(ci)硫(liu)化的(de)(de)(de)目的(de)(de)(de)是進行補(bu)充交(jiao)(jiao)聯(lian)(lian)、驅(qu)除硫(liu)化劑(ji)分解產物和其他揮發性(xing)化合物以(yi)穩定硫(liu)化膠(jiao)的(de)(de)(de)各項性(xing)能。常用的(de)(de)(de)設備有(you)開(kai)放(fang)式煉(lian)膠(jiao)機(ji)(ji)、捏合機(ji)(ji)及真(zhen)空密煉(lian)機(ji)(ji)。
主要性能
(1)高(gao)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)(de)特征是高(gao)溫(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)(ran)常(chang)(chang)溫(wen)(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)強度僅是天(tian)然(ran)(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)或(huo)某些合成(cheng)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)一(yi)半,但(dan)在(zai)200℃以上的(de)(de)高(gao)溫(wen)(wen)環境下(xia)(xia),硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)仍能(neng)保持一(yi)定(ding)的(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)表(biao)面硬度,且力(li)學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)無明(ming)顯(xian)變化(hua)(hua)。(2)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)玻璃化(hua)(hua)溫(wen)(wen)度一(yi)般為(wei)-70~-50℃,特殊配方可達-100℃,表(biao)明(ming)其(qi)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)(you)異(yi)。這對航(hang)(hang)空、宇(yu)航(hang)(hang)工業的(de)(de)意義重大。(3)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對氧、臭氧及(ji)紫外線等十分穩定(ding),在(zai)不加(jia)任何(he)添加(jia)劑(ji)的(de)(de)情況下(xia)(xia),就具(ju)有(you)優(you)(you)良的(de)(de)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有(you)優(you)(you)異(yi)的(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng),耐(nai)(nai)電(dian)暈(yun)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)電(dian)弧(hu)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常(chang)(chang)好(hao)。(5)物(wu)理機械(xie)(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)常(chang)(chang)溫(wen)(wen)下(xia)(xia)的(de)(de)物(wu)理機械(xie)(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)比(bi)通(tong)用(yong)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)差,但(dan)在(zai)150℃的(de)(de)高(gao)溫(wen)(wen)和(he)-50℃的(de)(de)低(di)溫(wen)(wen)下(xia)(xia),其(qi)物(wu)理機械(xie)(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)(you)于通(tong)用(yong)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及(ji)化(hua)(hua)學(xue)試劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有(you)中(zhong)等的(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。(7)氣(qi)體透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。室溫(wen)(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)對空氣(qi)、氮(dan)、氧、二氧化(hua)(hua)碳等氣(qi)體的(de)(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)天(tian)然(ran)(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)高(gao)出30-50倍。(8)生理惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)無毒,無味,無嗅,與人(ren)體組織(zhi)(zhi)不粘連,具(ju)有(you)抗凝血(xue)作用(yong),對肌體組織(zhi)(zhi)的(de)(de)反應(ying)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常(chang)(chang)少(shao)。特別適合作為(wei)醫用(yong)材(cai)料。
硅橡膠的用量
據中國(guo)(guo)汽(qi)(qi)(qi)(qi)車(che)(che)(che)工(gong)業(ye)(ye)協會統(tong)計,2012年(nian)(nian),汽(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)銷分別(bie)達到1927.18萬(wan)輛和1930.64萬(wan)輛,同比(bi)分別(bie)增長4.63%和4.33%,汽(qi)(qi)(qi)(qi)車(che)(che)(che)工(gong)業(ye)(ye)硅(gui)橡膠(jiao)(jiao)的用(yong)量(liang)約達2.0萬(wan)t。根據觀研(yan)天下的新研(yan)究,增加有(you)機硅(gui)材(cai)料在(zai)汽(qi)(qi)(qi)(qi)車(che)(che)(che)零(ling)部件(jian)方面(mian)的用(yong)量(liang),可以大(da)幅度提(ti)高汽(qi)(qi)(qi)(qi)車(che)(che)(che)的安(an)全性能(neng),因此(ci),汽(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)量(liang)和單車(che)(che)(che)用(yong)量(liang)水平的提(ti)高都(dou)將推動(dong)汽(qi)(qi)(qi)(qi)車(che)(che)(che)工(gong)業(ye)(ye)對(dui)硅(gui)橡膠(jiao)(jiao)需求的增加。國(guo)(guo)家鼓(gu)勵自(zi)(zi)(zi)主(zhu)(zhu)品(pin)牌的汽(qi)(qi)(qi)(qi)車(che)(che)(che)發展,關鍵汽(qi)(qi)(qi)(qi)車(che)(che)(che)零(ling)部件(jian)實現自(zi)(zi)(zi)主(zhu)(zhu)化,《2012年(nian)(nian)度黨政(zheng)(zheng)機關公務用(yong)車(che)(che)(che)選(xuan)用(yong)車(che)(che)(che)型目錄(征(zheng)求意見稿)》為(wei)自(zi)(zi)(zi)主(zhu)(zhu)品(pin)牌擴大(da)在(zai)政(zheng)(zheng)府采(cai)購的市(shi)場(chang)份額,為(wei)改變目前(qian)國(guo)(guo)內(nei)政(zheng)(zheng)府采(cai)購以合(he)資(zi)品(pin)牌產(chan)品(pin)為(wei)主(zhu)(zhu)的局面(mian)提(ti)供了保障。促進自(zi)(zi)(zi)主(zhu)(zhu)品(pin)牌發展,國(guo)(guo)產(chan)汽(qi)(qi)(qi)(qi)車(che)(che)(che)業(ye)(ye)的繁榮將為(wei)汽(qi)(qi)(qi)(qi)車(che)(che)(che)膠(jiao)(jiao)的應用(yong)提(ti)供有(you)力保障。預測未來3年(nian)(nian),我國(guo)(guo)室溫硫化硅(gui)橡膠(jiao)(jiao)在(zai)汽(qi)(qi)(qi)(qi)車(che)(che)(che)行業(ye)(ye)將以年(nian)(nian)均20%增長。
此外,硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)是重要的(de)非石(shi)(shi)(shi)油(you)基合成橡(xiang)(xiang)膠(jiao)(jiao)(jiao),約(yue)占非石(shi)(shi)(shi)油(you)基合成橡(xiang)(xiang)膠(jiao)(jiao)(jiao)消(xiao)費(fei)量的(de)98%。但(dan)(dan)因(yin)為(wei)石(shi)(shi)(shi)油(you)價(jia)(jia)格的(de)大(da)幅上漲,同(tong)時我(wo)國在硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)關鍵原料有(you)機(ji)硅(gui)單(dan)(dan)體(ti)(ti)的(de)生產技(ji)術方面(mian)(mian)取得(de)突破,有(you)機(ji)硅(gui)單(dan)(dan)體(ti)(ti)的(de)生產技(ji)術在2005年前被幾家跨國公司壟斷,但(dan)(dan)目前我(wo)國已發展成為(wei)全球(qiu)有(you)機(ji)硅(gui)單(dan)(dan)體(ti)(ti)第1大(da)國,這2個方面(mian)(mian)原因(yin)使硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)價(jia)(jia)格從2011年起開(kai)始低于石(shi)(shi)(shi)油(you)基合成橡(xiang)(xiang)膠(jiao)(jiao)(jiao),僅約(yue)為(wei)大(da)宗石(shi)(shi)(shi)油(you)基橡(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)80%~90%,成為(wei)廉(lian)價(jia)(jia)的(de)合成橡(xiang)(xiang)膠(jiao)(jiao)(jiao),并開(kai)始大(da)規模替代石(shi)(shi)(shi)油(you)基合成橡(xiang)(xiang)膠(jiao)(jiao)(jiao)。這將極大(da)拓展有(you)機(ji)硅(gui)產業的(de)市場空間(jian),同(tong)時將帶動硅(gui)油(you)、硅(gui)烷偶聯(lian)劑和硅(gui)樹脂等(deng)其他(ta)有(you)機(ji)硅(gui)產品的(de)消(xiao)費(fei)。