硅橡膠是(shi)指主(zhu)(zhu)鏈由(you)硅(gui)(gui)(gui)(gui)(gui)和氧(yang)原子交替構成(cheng),硅(gui)(gui)(gui)(gui)(gui)原子上通常(chang)連有(you)兩個有(you)機基(ji)(ji)團的(de)(de)橡(xiang)(xiang)膠(jiao)。普通的(de)(de)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)主(zhu)(zhu)要(yao)由(you)含甲基(ji)(ji)和少(shao)量乙烯(xi)基(ji)(ji)的(de)(de)硅(gui)(gui)(gui)(gui)(gui)氧(yang)鏈節組成(cheng)。苯(ben)基(ji)(ji)的(de)(de)引入(ru)可(ke)提(ti)高(gao)(gao)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)(nai)高(gao)(gao)、低(di)溫(wen)性(xing)(xing)(xing)能(neng)(neng),三(san)氟丙(bing)基(ji)(ji)及氰基(ji)(ji)的(de)(de)引入(ru)則可(ke)提(ti)高(gao)(gao)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)(nai)溫(wen)及耐(nai)(nai)油性(xing)(xing)(xing)能(neng)(neng)。硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)耐(nai)(nai)低(di)溫(wen)性(xing)(xing)(xing)能(neng)(neng)良(liang)好(hao),一(yi)般在(zai)-55℃下(xia)仍(reng)(reng)能(neng)(neng)工(gong)作。引入(ru)苯(ben)基(ji)(ji)后,可(ke)達-73℃。硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)(nai)熱(re)性(xing)(xing)(xing)能(neng)(neng)也很突出,在(zai)180℃下(xia)可(ke)長(chang)期工(gong)作,稍高(gao)(gao)于200℃也能(neng)(neng)承受數周(zhou)或(huo)更長(chang)時間仍(reng)(reng)有(you)彈(dan)性(xing)(xing)(xing),瞬時可(ke)耐(nai)(nai)300℃以上的(de)(de)高(gao)(gao)溫(wen)。硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)透氣(qi)性(xing)(xing)(xing)好(hao),氧(yang)氣(qi)透過率在(zai)合成(cheng)聚合物中是(shi)較高(gao)(gao)的(de)(de)。此(ci)外,硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)還(huan)具有(you)生理惰性(xing)(xing)(xing)、不會導致凝血(xue)的(de)(de)突出特性(xing)(xing)(xing),因此(ci)在(zai)醫用(yong)領域應用(yong)廣泛。
主要品種
硅(gui)橡(xiang)膠(jiao)(jiao)分類的(de)方(fang)法很多,通(tong)常(chang)按固(gu)化(hua)前的(de)形(xing)態(tai)分為(wei)固(gu)體硅(gui)橡(xiang)膠(jiao)(jiao)和液(ye)體硅(gui)橡(xiang)膠(jiao)(jiao);按硫(liu)化(hua)溫(wen)(wen)度分為(wei)室(shi)溫(wen)(wen)硫(liu)化(hua)硅(gui)橡(xiang)膠(jiao)(jiao),高溫(wen)(wen)硫(liu)化(hua)硅(gui)橡(xiang)膠(jiao)(jiao);按所用單(dan)體的(de)不同(tong),可(ke)分為(wei)甲(jia)(jia)基(ji)(ji)(ji)乙(yi)烯基(ji)(ji)(ji)硅(gui)橡(xiang)膠(jiao)(jiao),甲(jia)(jia)基(ji)(ji)(ji)苯基(ji)(ji)(ji)乙(yi)烯基(ji)(ji)(ji)硅(gui)橡(xiang)膠(jiao)(jiao)、氟硅(gui),腈硅(gui)橡(xiang)膠(jiao)(jiao)等;按性能和用途(tu)的(de)不同(tong)又可(ke)分為(wei)通(tong)用型(xing)、超耐(nai)(nai)低(di)溫(wen)(wen)型(xing)、超耐(nai)(nai)高溫(wen)(wen)型(xing)、高強力型(xing)、耐(nai)(nai)油型(xing)、醫用型(xing)等等。
發展史
硅(gui)(gui)(gui)橡膠(jiao)早期(qi)是由美(mei)國(guo)(guo)以三氯(lv)化鐵(tie)為(wei)催化劑合成的(de)(de)。1945年(nian)(nian),硅(gui)(gui)(gui)橡膠(jiao)產品問世。1948年(nian)(nian),采(cai)用高比表面積的(de)(de)氣相法白炭黑補強的(de)(de)硅(gui)(gui)(gui)橡膠(jiao)研(yan)制成功,使硅(gui)(gui)(gui)橡膠(jiao)的(de)(de)性能躍(yue)升到實用階段,奠定了現代硅(gui)(gui)(gui)橡膠(jiao)生(sheng)(sheng)產技術的(de)(de)基礎(chu)。從二甲基二氯(lv)硅(gui)(gui)(gui)烷合成開始(shi)生(sheng)(sheng)產硅(gui)(gui)(gui)橡膠(jiao)的(de)(de)國(guo)(guo)家有美(mei)國(guo)(guo)。俄羅(luo)斯(si)、德國(guo)(guo)、日(ri)本、韓國(guo)(guo)和中(zhong)國(guo)(guo)等。中(zhong)國(guo)(guo)硅(gui)(gui)(gui)橡膠(jiao)的(de)(de)工業化研(yan)究(jiu)始(shi)于1957年(nian)(nian),多家研(yan)究(jiu)所(suo)和企業陸(lu)續(xu)開發出各種硅(gui)(gui)(gui)橡膠(jiao)。到2003年(nian)(nian)底(di),中(zhong)國(guo)(guo)硅(gui)(gui)(gui)橡膠(jiao)生(sheng)(sheng)產能力為(wei)135千噸(dun),其中(zhong)高溫膠(jiao)100千噸(dun)。
高溫硫化硅橡膠
高(gao)(gao)溫(wen)硫(liu)(liu)化(hua)(hua)(hua)硅(gui)橡(xiang)膠(jiao)(jiao)是(shi)指(zhi)聚硅(gui)氧(yang)(yang)烷變成彈性(xing)(xing)體的(de)(de)(de)過程是(shi)經過高(gao)(gao)溫(wen)(110-170℃)硫(liu)(liu)化(hua)(hua)(hua)成型(xing)的(de)(de)(de)。它主要以高(gao)(gao)分(fen)子量(liang)的(de)(de)(de)聚甲(jia)基(ji)乙(yi)烯基(ji)硅(gui)氧(yang)(yang)烷為生(sheng)膠(jiao)(jiao),混入補(bu)強(qiang)填料(liao)、硫(liu)(liu)化(hua)(hua)(hua)劑等,在加熱加壓(ya)下硫(liu)(liu)化(hua)(hua)(hua)成彈性(xing)(xing)體。硅(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)補(bu)強(qiang)主要是(shi)各(ge)(ge)種類型(xing)的(de)(de)(de)白炭黑,可使硫(liu)(liu)化(hua)(hua)(hua)膠(jiao)(jiao)的(de)(de)(de)強(qiang)度(du)增加數十倍。有時為了降低(di)成本或(huo)改善膠(jiao)(jiao)料(liao)性(xing)(xing)能(neng)及賦(fu)予硫(liu)(liu)化(hua)(hua)(hua)膠(jiao)(jiao)各(ge)(ge)種特殊的(de)(de)(de)性(xing)(xing)能(neng),也加入相(xiang)應(ying)的(de)(de)(de)各(ge)(ge)種添加劑。硫(liu)(liu)化(hua)(hua)(hua)劑是(shi)各(ge)(ge)種有機過氧(yang)(yang)化(hua)(hua)(hua)物或(huo)加成反應(ying)催化(hua)(hua)(hua)劑。
加工成型方法如圖所示。一次(ci)硫(liu)化(hua)(hua)的目(mu)的是(shi)進行(xing)高分(fen)子(zi)鏈的交聯反應;二次(ci)硫(liu)化(hua)(hua)的目(mu)的是(shi)進行(xing)補充交聯、驅除硫(liu)化(hua)(hua)劑(ji)分(fen)解產物和其(qi)他(ta)揮發性化(hua)(hua)合物以穩(wen)定硫(liu)化(hua)(hua)膠(jiao)(jiao)的各項性能。常用的設備有開放式煉膠(jiao)(jiao)機、捏合機及真(zhen)空密煉機。
主要性能
(1)高(gao)(gao)溫(wen)(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)顯著的(de)(de)特(te)(te)征是(shi)高(gao)(gao)溫(wen)(wen)(wen)(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然常(chang)(chang)溫(wen)(wen)(wen)(wen)(wen)下(xia)硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)強(qiang)度(du)僅是(shi)天然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)或某些合成橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)一(yi)半,但(dan)在200℃以上的(de)(de)高(gao)(gao)溫(wen)(wen)(wen)(wen)(wen)環境(jing)下(xia),硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)仍(reng)能(neng)(neng)(neng)保持一(yi)定(ding)的(de)(de)柔(rou)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(du),且力學性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)無(wu)明顯變化(hua)(hua)。(2)低溫(wen)(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)玻璃化(hua)(hua)溫(wen)(wen)(wen)(wen)(wen)度(du)一(yi)般為-70~-50℃,特(te)(te)殊配方可達(da)-100℃,表(biao)明其低溫(wen)(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)優異(yi)。這對航空(kong)、宇航工(gong)業的(de)(de)意義重(zhong)大。(3)耐(nai)(nai)(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)中Si-O-Si鍵對氧(yang)、臭氧(yang)及紫外(wai)線等十(shi)分穩定(ding),在不加任(ren)何添(tian)加劑的(de)(de)情(qing)況下(xia),就具有優良的(de)(de)耐(nai)(nai)(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有優異(yi)的(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng),耐(nai)(nai)(nai)(nai)電暈(yun)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)(nai)(nai)電弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常(chang)(chang)好。(5)物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)常(chang)(chang)溫(wen)(wen)(wen)(wen)(wen)下(xia)的(de)(de)物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)比通(tong)用(yong)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)差,但(dan)在150℃的(de)(de)高(gao)(gao)溫(wen)(wen)(wen)(wen)(wen)和(he)-50℃的(de)(de)低溫(wen)(wen)(wen)(wen)(wen)下(xia),其物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)優于通(tong)用(yong)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)(nai)(nai)油及化(hua)(hua)學試劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有中等的(de)(de)耐(nai)(nai)(nai)(nai)油、耐(nai)(nai)(nai)(nai)溶劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。(7)氣(qi)(qi)體(ti)(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。室溫(wen)(wen)(wen)(wen)(wen)下(xia)硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)對空(kong)氣(qi)(qi)、氮(dan)、氧(yang)、二氧(yang)化(hua)(hua)碳等氣(qi)(qi)體(ti)(ti)的(de)(de)透氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)高(gao)(gao)出(chu)30-50倍。(8)生理惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)無(wu)毒,無(wu)味,無(wu)嗅,與人(ren)體(ti)(ti)組織不粘(zhan)連,具有抗凝血作用(yong),對肌體(ti)(ti)組織的(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常(chang)(chang)少(shao)。特(te)(te)別適合作為醫(yi)用(yong)材料。
硅橡膠的用量
據中國汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工(gong)業(ye)(ye)(ye)協會統計,2012年(nian),汽(qi)(qi)(qi)(qi)(qi)車(che)(che)產(chan)銷分別(bie)達(da)到1927.18萬(wan)(wan)輛和1930.64萬(wan)(wan)輛,同比分別(bie)增長(chang)4.63%和4.33%,汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工(gong)業(ye)(ye)(ye)硅(gui)橡膠(jiao)的(de)用(yong)量約達(da)2.0萬(wan)(wan)t。根據觀研天下的(de)新研究,增加有機硅(gui)材(cai)料(liao)在汽(qi)(qi)(qi)(qi)(qi)車(che)(che)零部件方(fang)面(mian)的(de)用(yong)量,可以大幅度提高汽(qi)(qi)(qi)(qi)(qi)車(che)(che)的(de)安全性能,因此(ci),汽(qi)(qi)(qi)(qi)(qi)車(che)(che)產(chan)量和單(dan)車(che)(che)用(yong)量水平的(de)提高都將推(tui)動汽(qi)(qi)(qi)(qi)(qi)車(che)(che)工(gong)業(ye)(ye)(ye)對硅(gui)橡膠(jiao)需求(qiu)的(de)增加。國家鼓(gu)勵自(zi)(zi)主品(pin)(pin)牌的(de)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)發(fa)展(zhan),關(guan)鍵汽(qi)(qi)(qi)(qi)(qi)車(che)(che)零部件實現自(zi)(zi)主化(hua),《2012年(nian)度黨政機關(guan)公(gong)務(wu)用(yong)車(che)(che)選(xuan)用(yong)車(che)(che)型目錄(征求(qiu)意見(jian)稿)》為(wei)自(zi)(zi)主品(pin)(pin)牌擴大在政府采(cai)購的(de)市場份(fen)額,為(wei)改變目前國內政府采(cai)購以合資品(pin)(pin)牌產(chan)品(pin)(pin)為(wei)主的(de)局面(mian)提供(gong)了保(bao)障。促(cu)進自(zi)(zi)主品(pin)(pin)牌發(fa)展(zhan),國產(chan)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)業(ye)(ye)(ye)的(de)繁榮將為(wei)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)膠(jiao)的(de)應用(yong)提供(gong)有力保(bao)障。預測未來3年(nian),我國室溫硫(liu)化(hua)硅(gui)橡膠(jiao)在汽(qi)(qi)(qi)(qi)(qi)車(che)(che)行業(ye)(ye)(ye)將以年(nian)均20%增長(chang)。
此外,硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)是(shi)重要的(de)(de)(de)非石(shi)油(you)基(ji)(ji)合(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao),約(yue)(yue)占非石(shi)油(you)基(ji)(ji)合(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)消費量的(de)(de)(de)98%。但(dan)因為(wei)(wei)石(shi)油(you)價格的(de)(de)(de)大(da)幅上(shang)漲,同時我國在(zai)(zai)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)關鍵原料有(you)機(ji)硅(gui)(gui)(gui)單體的(de)(de)(de)生產技(ji)術方面取得突(tu)破,有(you)機(ji)硅(gui)(gui)(gui)單體的(de)(de)(de)生產技(ji)術在(zai)(zai)2005年(nian)前被(bei)幾家跨國公司壟斷,但(dan)目前我國已發展成(cheng)(cheng)(cheng)(cheng)為(wei)(wei)全球有(you)機(ji)硅(gui)(gui)(gui)單體第(di)1大(da)國,這(zhe)(zhe)2個方面原因使硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)價格從(cong)2011年(nian)起開(kai)始低于石(shi)油(you)基(ji)(ji)合(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao),僅(jin)約(yue)(yue)為(wei)(wei)大(da)宗(zong)石(shi)油(you)基(ji)(ji)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)80%~90%,成(cheng)(cheng)(cheng)(cheng)為(wei)(wei)廉價的(de)(de)(de)合(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao),并開(kai)始大(da)規模替代石(shi)油(you)基(ji)(ji)合(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)。這(zhe)(zhe)將(jiang)極大(da)拓展有(you)機(ji)硅(gui)(gui)(gui)產業的(de)(de)(de)市(shi)場空間,同時將(jiang)帶動硅(gui)(gui)(gui)油(you)、硅(gui)(gui)(gui)烷偶聯劑和硅(gui)(gui)(gui)樹(shu)脂(zhi)等(deng)其(qi)他有(you)機(ji)硅(gui)(gui)(gui)產品的(de)(de)(de)消費。