
硅橡膠是(shi)(shi)指主(zhu)鏈由硅(gui)(gui)(gui)(gui)(gui)(gui)和氧原子交替構成,硅(gui)(gui)(gui)(gui)(gui)(gui)原子上(shang)通常(chang)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)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠主(zhu)要(yao)由含甲基(ji)和少量乙烯基(ji)的(de)(de)硅(gui)(gui)(gui)(gui)(gui)(gui)氧鏈節組成。苯基(ji)的(de)(de)引(yin)入(ru)可(ke)提(ti)高(gao)硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)(nai)高(gao)、低溫(wen)性(xing)(xing)(xing)能,三氟丙(bing)基(ji)及氰基(ji)的(de)(de)引(yin)入(ru)則可(ke)提(ti)高(gao)硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)(nai)溫(wen)及耐(nai)(nai)(nai)油性(xing)(xing)(xing)能。硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠耐(nai)(nai)(nai)低溫(wen)性(xing)(xing)(xing)能良好,一般在-55℃下(xia)仍能工作。引(yin)入(ru)苯基(ji)后,可(ke)達-73℃。硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)耐(nai)(nai)(nai)熱性(xing)(xing)(xing)能也很突(tu)(tu)出,在180℃下(xia)可(ke)長期(qi)工作,稍高(gao)于200℃也能承受數周(zhou)或更長時(shi)間仍有(you)(you)彈性(xing)(xing)(xing),瞬時(shi)可(ke)耐(nai)(nai)(nai)300℃以(yi)上(shang)的(de)(de)高(gao)溫(wen)。硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠的(de)(de)透氣性(xing)(xing)(xing)好,氧氣透過率在合(he)成聚合(he)物中是(shi)(shi)較高(gao)的(de)(de)。此外,硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠還具有(you)(you)生理惰性(xing)(xing)(xing)、不會導致(zhi)凝(ning)血的(de)(de)突(tu)(tu)出特性(xing)(xing)(xing),因此在醫用領域(yu)應(ying)用廣泛。
主要品(pin)種
硅橡(xiang)膠分類的方法很多(duo),通常(chang)按(an)固化
前的(de)形態分(fen)(fen)為(wei)(wei)固(gu)體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠和(he)液體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠;按(an)(an)硫(liu)化溫(wen)度(du)分(fen)(fen)為(wei)(wei)室溫(wen)硫(liu)化硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠,高(gao)溫(wen)硫(liu)化硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠;按(an)(an)所用單體的(de)不(bu)同,可(ke)分(fen)(fen)為(wei)(wei)甲基(ji)乙烯基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠,甲基(ji)苯基(ji)乙烯基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠等;按(an)(an)性能(neng)和(he)用途的(de)不(bu)同又(you)可(ke)分(fen)(fen)為(wei)(wei)通用型(xing)(xing)、超耐(nai)低(di)溫(wen)型(xing)(xing)、超耐(nai)高(gao)溫(wen)型(xing)(xing)、高(gao)強力型(xing)(xing)、耐(nai)油型(xing)(xing)、醫用型(xing)(xing)等等。
發展史
硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)早期是由美(mei)國(guo)(guo)以三氯化(hua)鐵為(wei)催化(hua)劑(ji)合成(cheng)的(de)。1945年(nian),硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)產(chan)品(pin)問世。1948年(nian),采用高(gao)(gao)比表(biao)面積的(de)氣相(xiang)法白炭黑補(bu)強的(de)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)研(yan)制成(cheng)功,使硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)性能(neng)躍升到實用階段,奠定了現代硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)生(sheng)產(chan)技(ji)術的(de)基礎。從二甲基二氯硅(gui)(gui)(gui)烷合成(cheng)開(kai)始生(sheng)產(chan)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)國(guo)(guo)家有美(mei)國(guo)(guo)。俄羅(luo)斯(si)、德國(guo)(guo)、日本(ben)、韓國(guo)(guo)和(he)中國(guo)(guo)等。中國(guo)(guo)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)工業(ye)化(hua)研(yan)究(jiu)始于1957年(nian),多家研(yan)究(jiu)所和(he)企業(ye)陸續開(kai)發(fa)出各種(zhong)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)。到2003年(nian)底(di),中國(guo)(guo)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)生(sheng)產(chan)能(neng)力為(wei)135千噸,其中高(gao)(gao)溫(wen)膠(jiao)(jiao)100千噸。
高溫(wen)硫化硅橡膠
高溫硫(liu)化(hua)(hua)硅(gui)橡(xiang)膠(jiao)是指(zhi)聚(ju)硅(gui)氧烷(wan)變成(cheng)(cheng)彈性(xing)體的(de)過程是經過高溫(110-170℃)硫(liu)化(hua)(hua)成(cheng)(cheng)型(xing)的(de)。它(ta)主(zhu)(zhu)要(yao)以高分(fen)子量的(de)聚(ju)甲(jia)基(ji)乙烯基(ji)硅(gui)氧烷(wan)為(wei)生膠(jiao),混入補強填(tian)料、硫(liu)化(hua)(hua)劑(ji)(ji)等,在加(jia)熱加(jia)壓下硫(liu)化(hua)(hua)成(cheng)(cheng)彈性(xing)體。硅(gui)橡(xiang)膠(jiao)的(de)補強主(zhu)(zhu)要(yao)是各(ge)種(zhong)類型(xing)的(de)白炭黑,可使硫(liu)化(hua)(hua)膠(jiao)的(de)強度增加(jia)數十倍。有(you)時(shi)為(wei)了降低(di)成(cheng)(cheng)本或(huo)改(gai)善(shan)膠(jiao)料性(xing)能(neng)及賦予(yu)硫(liu)化(hua)(hua)膠(jiao)各(ge)種(zhong)特(te)殊的(de)性(xing)能(neng),也加(jia)入相應的(de)各(ge)種(zhong)添加(jia)劑(ji)(ji)。硫(liu)化(hua)(hua)劑(ji)(ji)是各(ge)種(zhong)有(you)機過氧化(hua)(hua)物或(huo)加(jia)成(cheng)(cheng)反應催化(hua)(hua)劑(ji)(ji)。
加工成(cheng)型方法如圖(tu)所示。一次硫化(hua)(hua)(hua)的(de)(de)(de)目的(de)(de)(de)是進(jin)行高分子鏈的(de)(de)(de)交聯反應(ying);二次硫化(hua)(hua)(hua)的(de)(de)(de)目的(de)(de)(de)是進(jin)行補充(chong)交聯、驅(qu)除硫化(hua)(hua)(hua)劑(ji)分解產物和其他揮發性化(hua)(hua)(hua)合物以穩(wen)定(ding)硫化(hua)(hua)(hua)膠(jiao)的(de)(de)(de)各項(xiang)性能。常用(yong)的(de)(de)(de)設備有開放式(shi)煉膠(jiao)機(ji)、捏合機(ji)及真空密煉機(ji)。
主要性(xing)能
(1)高溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)顯著的(de)(de)(de)特(te)征是高溫(wen)(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常(chang)溫(wen)(wen)(wen)下(xia)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)強度(du)僅(jin)是天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)或某些合(he)成橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)一(yi)半,但(dan)在(zai)(zai)200℃以上的(de)(de)(de)高溫(wen)(wen)(wen)環境下(xia),硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)仍(reng)能(neng)(neng)(neng)(neng)(neng)保持一(yi)定(ding)的(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈(dan)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表(biao)面硬度(du),且力(li)學(xue)(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)無明(ming)顯變(bian)化(hua)(hua)(hua)。(2)低(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)玻璃化(hua)(hua)(hua)溫(wen)(wen)(wen)度(du)一(yi)般為(wei)(wei)-70~-50℃,特(te)殊配方可(ke)達-100℃,表(biao)明(ming)其(qi)低(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優異。這對航空、宇(yu)航工業的(de)(de)(de)意義重大。(3)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)中Si-O-Si鍵對氧、臭氧及紫(zi)外線等十分(fen)穩定(ding),在(zai)(zai)不加任何添加劑(ji)的(de)(de)(de)情況下(xia),就具有(you)(you)(you)優良的(de)(de)(de)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具有(you)(you)(you)優異的(de)(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng),耐(nai)(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)(nai)電(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非常(chang)好。(5)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)常(chang)溫(wen)(wen)(wen)下(xia)的(de)(de)(de)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)比通(tong)用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)差,但(dan)在(zai)(zai)150℃的(de)(de)(de)高溫(wen)(wen)(wen)和-50℃的(de)(de)(de)低(di)溫(wen)(wen)(wen)下(xia),其(qi)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優于通(tong)用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)。(6)耐(nai)(nai)油及化(hua)(hua)(hua)學(xue)(xue)試劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具有(you)(you)(you)中等的(de)(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。(7)氣(qi)體(ti)(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。室溫(wen)(wen)(wen)下(xia)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)對空氣(qi)、氮、氧、二(er)氧化(hua)(hua)(hua)碳等氣(qi)體(ti)(ti)的(de)(de)(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)高出30-50倍。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)無毒,無味,無嗅,與人(ren)體(ti)(ti)組(zu)織不粘連,具有(you)(you)(you)抗凝(ning)血(xue)作(zuo)用,對肌體(ti)(ti)組(zu)織的(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)少。特(te)別適合(he)作(zuo)為(wei)(wei)醫(yi)用材料。
硅橡(xiang)膠的用(yong)量
據(ju)中國(guo)(guo)汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業協會統計,2012年(nian),汽(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)銷分別達到(dao)1927.18萬輛(liang)(liang)和(he)(he)1930.64萬輛(liang)(liang),同比分別增(zeng)長(chang)(chang)4.63%和(he)(he)4.33%,汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業硅(gui)橡(xiang)膠(jiao)的(de)(de)(de)(de)用(yong)量(liang)約達2.0萬t。根據(ju)觀研(yan)天下的(de)(de)(de)(de)新(xin)研(yan)究,增(zeng)加有機硅(gui)材料在汽(qi)(qi)(qi)(qi)車(che)(che)(che)零部件方面(mian)的(de)(de)(de)(de)用(yong)量(liang),可以(yi)大(da)幅度(du)提高(gao)汽(qi)(qi)(qi)(qi)車(che)(che)(che)的(de)(de)(de)(de)安全性能,因此,汽(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)量(liang)和(he)(he)單(dan)車(che)(che)(che)用(yong)量(liang)水平的(de)(de)(de)(de)提高(gao)都(dou)將推(tui)動汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業對硅(gui)橡(xiang)膠(jiao)需求的(de)(de)(de)(de)增(zeng)加。國(guo)(guo)家鼓勵自主品(pin)牌的(de)(de)(de)(de)汽(qi)(qi)(qi)(qi)車(che)(che)(che)發(fa)展(zhan),關(guan)鍵汽(qi)(qi)(qi)(qi)車(che)(che)(che)零部件實現(xian)自主化(hua),《2012年(nian)度(du)黨政(zheng)機關(guan)公務用(yong)車(che)(che)(che)選(xuan)用(yong)車(che)(che)(che)型目錄(征求意見(jian)稿)》為(wei)自主品(pin)牌擴大(da)在政(zheng)府采(cai)購的(de)(de)(de)(de)市場(chang)份額,為(wei)改(gai)變目前(qian)國(guo)(guo)內政(zheng)府采(cai)購以(yi)合資品(pin)牌產(chan)品(pin)為(wei)主的(de)(de)(de)(de)局面(mian)提供了保障(zhang)。促進自主品(pin)牌發(fa)展(zhan),國(guo)(guo)產(chan)汽(qi)(qi)(qi)(qi)車(che)(che)(che)業的(de)(de)(de)(de)繁榮將為(wei)汽(qi)(qi)(qi)(qi)車(che)(che)(che)膠(jiao)的(de)(de)(de)(de)應用(yong)提供有力保障(zhang)。預測未(wei)來3年(nian),我國(guo)(guo)室溫硫化(hua)硅(gui)橡(xiang)膠(jiao)在汽(qi)(qi)(qi)(qi)車(che)(che)(che)行業將以(yi)年(nian)均20%增(zeng)長(chang)(chang)。
此外,硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)是重要(yao)的(de)(de)(de)非(fei)石(shi)(shi)油(you)基合(he)成(cheng)橡(xiang)膠(jiao)(jiao)(jiao),約占非(fei)石(shi)(shi)油(you)基合(he)成(cheng)橡(xiang)膠(jiao)(jiao)(jiao)消費(fei)量的(de)(de)(de)98%。但因為(wei)石(shi)(shi)油(you)價(jia)格的(de)(de)(de)大(da)幅上(shang)漲,同(tong)時我國(guo)(guo)在(zai)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)關(guan)鍵原(yuan)(yuan)料有(you)機(ji)硅(gui)(gui)單(dan)體的(de)(de)(de)生(sheng)產(chan)(chan)技(ji)術方面(mian)取(qu)得突(tu)破(po),有(you)機(ji)硅(gui)(gui)單(dan)體的(de)(de)(de)生(sheng)產(chan)(chan)技(ji)術在(zai)2005年(nian)前被幾家跨(kua)國(guo)(guo)公司壟斷,但目前我國(guo)(guo)已發展成(cheng)為(wei)全(quan)球有(you)機(ji)硅(gui)(gui)單(dan)體第(di)1大(da)國(guo)(guo),這2個方面(mian)原(yuan)(yuan)因使硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)價(jia)格從2011年(nian)起開(kai)始低于(yu)石(shi)(shi)油(you)基合(he)成(cheng)橡(xiang)膠(jiao)(jiao)(jiao),僅約為(wei)大(da)宗(zong)石(shi)(shi)油(you)基橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)80%~90%,成(cheng)為(wei)廉價(jia)的(de)(de)(de)合(he)成(cheng)橡(xiang)膠(jiao)(jiao)(jiao),并(bing)開(kai)始大(da)規模(mo)替(ti)代石(shi)(shi)油(you)基合(he)成(cheng)橡(xiang)膠(jiao)(jiao)(jiao)。這將極大(da)拓展有(you)機(ji)硅(gui)(gui)產(chan)(chan)業的(de)(de)(de)市場空間(jian),同(tong)時將帶動(dong)硅(gui)(gui)油(you)、硅(gui)(gui)烷偶聯劑和(he)硅(gui)(gui)樹(shu)脂等其他(ta)有(you)機(ji)硅(gui)(gui)產(chan)(chan)品的(de)(de)(de)消費(fei)。