
硅橡膠是指主鏈(lian)由硅(gui)(gui)和氧(yang)原(yuan)子交替構成,硅(gui)(gui)原(yuan)子上通常連有(you)兩(liang)個有(you)機基(ji)團的(de)橡膠(jiao)(jiao)。普通的(de)硅(gui)(gui)橡膠(jiao)(jiao)主要由含甲基(ji)和少量乙烯基(ji)的(de)硅(gui)(gui)氧(yang)鏈(lian)節組(zu)成。苯基(ji)的(de)引(yin)入可提高(gao)硅(gui)(gui)橡膠(jiao)(jiao)的(de)耐(nai)高(gao)、低溫性(xing)能,三氟丙基(ji)及氰基(ji)的(de)引(yin)入則可提高(gao)硅(gui)(gui)橡膠(jiao)(jiao)的(de)耐(nai)溫及耐(nai)油性(xing)能。硅(gui)(gui)橡膠(jiao)(jiao)耐(nai)低溫性(xing)能良好,一般在-55℃下仍(reng)(reng)能工(gong)作。引(yin)入苯基(ji)后,可達(da)-73℃。硅(gui)(gui)橡膠(jiao)(jiao)的(de)耐(nai)熱性(xing)能也很突出(chu),在180℃下可長期工(gong)作,稍高(gao)于200℃也能承受(shou)數周或更長時(shi)(shi)間仍(reng)(reng)有(you)彈性(xing),瞬時(shi)(shi)可耐(nai)300℃以上的(de)高(gao)溫。硅(gui)(gui)橡膠(jiao)(jiao)的(de)透氣性(xing)好,氧(yang)氣透過率在合(he)成聚合(he)物中是較高(gao)的(de)。此外,硅(gui)(gui)橡膠(jiao)(jiao)還(huan)具有(you)生理惰(duo)性(xing)、不會導致(zhi)凝(ning)血的(de)突出(chu)特性(xing),因(yin)此在醫用(yong)領域(yu)應用(yong)廣泛。
主要品種
硅(gui)橡(xiang)膠分(fen)(fen)類(lei)的(de)方法(fa)很多,通常按(an)(an)固(gu)化(hua)前的(de)形態分(fen)(fen)為(wei)固(gu)體硅(gui)橡(xiang)膠和液體硅(gui)橡(xiang)膠;按(an)(an)硫(liu)化(hua)溫度分(fen)(fen)為(wei)室溫硫(liu)化(hua)硅(gui)橡(xiang)膠,高(gao)(gao)溫硫(liu)化(hua)硅(gui)橡(xiang)膠;按(an)(an)所(suo)用單體的(de)不同(tong),可分(fen)(fen)為(wei)甲基(ji)(ji)乙烯基(ji)(ji)硅(gui)橡(xiang)膠,甲基(ji)(ji)苯基(ji)(ji)乙烯基(ji)(ji)硅(gui)橡(xiang)膠、氟(fu)硅(gui),腈硅(gui)橡(xiang)膠等(deng);按(an)(an)性能(neng)和用途(tu)的(de)不同(tong)又可分(fen)(fen)為(wei)通用型(xing)(xing)、超(chao)耐低溫型(xing)(xing)、超(chao)耐高(gao)(gao)溫型(xing)(xing)、高(gao)(gao)強力型(xing)(xing)、耐油(you)型(xing)(xing)、醫(yi)用型(xing)(xing)等(deng)等(deng)。
發展史
硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)早期是由美(mei)國(guo)(guo)以三(san)氯(lv)化鐵(tie)為催(cui)化劑合(he)成的(de)(de)。1945年(nian),硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)產(chan)品(pin)問世。1948年(nian),采用(yong)(yong)高比表(biao)面(mian)積(ji)的(de)(de)氣相(xiang)法白炭(tan)黑補強的(de)(de)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)研(yan)制成功,使硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)性(xing)能(neng)躍升到實用(yong)(yong)階段,奠定了(le)現(xian)代硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)生(sheng)產(chan)技(ji)術的(de)(de)基(ji)礎(chu)。從二(er)甲基(ji)二(er)氯(lv)硅(gui)烷合(he)成開始生(sheng)產(chan)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)國(guo)(guo)家有(you)美(mei)國(guo)(guo)。俄羅斯、德國(guo)(guo)、日本、韓(han)國(guo)(guo)和中國(guo)(guo)等。中國(guo)(guo)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)工業(ye)化研(yan)究始于1957年(nian),多家研(yan)究所(suo)和企業(ye)陸續(xu)開發(fa)出(chu)各種硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)。到2003年(nian)底,中國(guo)(guo)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)生(sheng)產(chan)能(neng)力為135千噸(dun),其中高溫膠(jiao)(jiao)(jiao)100千噸(dun)。
高溫硫化硅橡膠
高溫(wen)硫(liu)(liu)(liu)化(hua)(hua)(hua)硅橡(xiang)膠(jiao)是(shi)(shi)(shi)指聚硅氧(yang)烷(wan)變成(cheng)彈(dan)性(xing)體的(de)過(guo)程是(shi)(shi)(shi)經過(guo)高溫(wen)(110-170℃)硫(liu)(liu)(liu)化(hua)(hua)(hua)成(cheng)型(xing)的(de)。它主要(yao)以高分子量的(de)聚甲基乙烯基硅氧(yang)烷(wan)為(wei)生膠(jiao),混入(ru)(ru)補強(qiang)(qiang)填料、硫(liu)(liu)(liu)化(hua)(hua)(hua)劑(ji)等,在加熱加壓(ya)下硫(liu)(liu)(liu)化(hua)(hua)(hua)成(cheng)彈(dan)性(xing)體。硅橡(xiang)膠(jiao)的(de)補強(qiang)(qiang)主要(yao)是(shi)(shi)(shi)各種類(lei)型(xing)的(de)白炭黑(hei),可使硫(liu)(liu)(liu)化(hua)(hua)(hua)膠(jiao)的(de)強(qiang)(qiang)度增加數十倍。有時為(wei)了降(jiang)低成(cheng)本或改善膠(jiao)料性(xing)能(neng)及賦予硫(liu)(liu)(liu)化(hua)(hua)(hua)膠(jiao)各種特(te)殊(shu)的(de)性(xing)能(neng),也加入(ru)(ru)相應(ying)(ying)的(de)各種添加劑(ji)。硫(liu)(liu)(liu)化(hua)(hua)(hua)劑(ji)是(shi)(shi)(shi)各種有機過(guo)氧(yang)化(hua)(hua)(hua)物或加成(cheng)反(fan)應(ying)(ying)催化(hua)(hua)(hua)劑(ji)。
加工成(cheng)型(xing)方(fang)法(fa)如圖所示。一次硫(liu)化(hua)的(de)(de)(de)目的(de)(de)(de)是進行(xing)高(gao)分子(zi)鏈的(de)(de)(de)交(jiao)聯(lian)反(fan)應;二(er)次硫(liu)化(hua)的(de)(de)(de)目的(de)(de)(de)是進行(xing)補充交(jiao)聯(lian)、驅除硫(liu)化(hua)劑分解產物和其他(ta)揮(hui)發性(xing)化(hua)合物以(yi)穩定硫(liu)化(hua)膠(jiao)的(de)(de)(de)各項性(xing)能。常用的(de)(de)(de)設(she)備(bei)有(you)開放式煉(lian)膠(jiao)機、捏合機及真空密煉(lian)機。
主要性能
(1)高溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)(de)(de)(de)(de)(de)特征(zheng)是高溫(wen)穩定性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常(chang)(chang)溫(wen)下硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)(de)(de)強度(du)僅是天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)或(huo)某些(xie)合成橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)(de)(de)一半,但在200℃以上的(de)(de)(de)(de)(de)(de)高溫(wen)環(huan)境下,硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)保持一定的(de)(de)(de)(de)(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)表面硬度(du),且力學性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)無(wu)明(ming)(ming)顯(xian)變化(hua)。(2)低(di)溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)(de)(de)玻璃化(hua)溫(wen)度(du)一般為-70~-50℃,特殊配方可達-100℃,表明(ming)(ming)其低(di)溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)異(yi)。這對(dui)航空、宇航工業的(de)(de)(de)(de)(de)(de)意義重(zhong)大。(3)耐(nai)(nai)(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)中Si-O-Si鍵對(dui)氧、臭氧及紫外線(xian)等十分穩定,在不加任何添加劑(ji)(ji)的(de)(de)(de)(de)(de)(de)情況下,就具(ju)(ju)有(you)優(you)良(liang)的(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)(ju)有(you)優(you)異(yi)的(de)(de)(de)(de)(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng),耐(nai)(nai)(nai)(nai)電暈性(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)也非常(chang)(chang)好。(5)物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)常(chang)(chang)溫(wen)下的(de)(de)(de)(de)(de)(de)物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)比通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)差,但在150℃的(de)(de)(de)(de)(de)(de)高溫(wen)和(he)-50℃的(de)(de)(de)(de)(de)(de)低(di)溫(wen)下,其物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)于通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)(nai)(nai)油及化(hua)學試劑(ji)(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)(ju)有(you)中等的(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)(nai)油、耐(nai)(nai)(nai)(nai)溶(rong)劑(ji)(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。(7)氣(qi)體透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。室溫(wen)下硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)對(dui)空氣(qi)、氮、氧、二(er)氧化(hua)碳等氣(qi)體的(de)(de)(de)(de)(de)(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)高出30-50倍。(8)生理(li)(li)惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)無(wu)毒,無(wu)味,無(wu)嗅(xiu),與(yu)人體組(zu)織(zhi)不粘(zhan)連,具(ju)(ju)有(you)抗(kang)凝血作用,對(dui)肌體組(zu)織(zhi)的(de)(de)(de)(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)(chang)少。特別適(shi)合作為醫用材料。
硅橡膠的用量
據中國汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)協(xie)會統計,2012年(nian),汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)銷分別(bie)達到(dao)1927.18萬輛和(he)1930.64萬輛,同比分別(bie)增(zeng)長4.63%和(he)4.33%,汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)硅(gui)(gui)橡膠的用(yong)量約達2.0萬t。根據觀研天下(xia)的新研究,增(zeng)加(jia)有機硅(gui)(gui)材(cai)料在(zai)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)零部件方面(mian)(mian)的用(yong)量,可以大(da)幅度提(ti)高汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)的安(an)全性能,因(yin)此,汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)產(chan)量和(he)單車(che)(che)(che)用(yong)量水平的提(ti)高都將推動汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)對硅(gui)(gui)橡膠需(xu)求的增(zeng)加(jia)。國家鼓勵自(zi)主(zhu)品牌(pai)的汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)發展,關鍵汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)零部件實現自(zi)主(zhu)化(hua),《2012年(nian)度黨政機關公(gong)務用(yong)車(che)(che)(che)選用(yong)車(che)(che)(che)型目(mu)錄(征求意見稿)》為自(zi)主(zhu)品牌(pai)擴大(da)在(zai)政府采購的市場份(fen)額,為改變目(mu)前(qian)國內政府采購以合資品牌(pai)產(chan)品為主(zhu)的局面(mian)(mian)提(ti)供(gong)了保障。促進自(zi)主(zhu)品牌(pai)發展,國產(chan)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)業(ye)的繁榮將為汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)膠的應用(yong)提(ti)供(gong)有力保障。預(yu)測未來3年(nian),我國室溫(wen)硫(liu)化(hua)硅(gui)(gui)橡膠在(zai)汽(qi)(qi)(qi)(qi)(qi)車(che)(che)(che)行(xing)業(ye)將以年(nian)均20%增(zeng)長。
此外,硅(gui)(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)是重(zhong)要的非石油(you)(you)基合(he)成(cheng)橡膠(jiao)(jiao),約(yue)(yue)占(zhan)非石油(you)(you)基合(he)成(cheng)橡膠(jiao)(jiao)消(xiao)費量的98%。但(dan)因為(wei)石油(you)(you)價(jia)格的大幅上漲(zhang),同(tong)時我(wo)國在硅(gui)(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)的關鍵原料有(you)(you)(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)單體(ti)的生(sheng)產技術(shu)方面取得突破,有(you)(you)(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)單體(ti)的生(sheng)產技術(shu)在2005年前(qian)(qian)被幾家跨國公司(si)壟斷(duan),但(dan)目前(qian)(qian)我(wo)國已(yi)發展成(cheng)為(wei)全球有(you)(you)(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)單體(ti)第(di)1大國,這2個方面原因使硅(gui)(gui)(gui)(gui)(gui)橡膠(jiao)(jiao)的價(jia)格從(cong)2011年起(qi)開始低(di)于石油(you)(you)基合(he)成(cheng)橡膠(jiao)(jiao),僅約(yue)(yue)為(wei)大宗(zong)石油(you)(you)基橡膠(jiao)(jiao)的80%~90%,成(cheng)為(wei)廉價(jia)的合(he)成(cheng)橡膠(jiao)(jiao),并開始大規模替(ti)代(dai)石油(you)(you)基合(he)成(cheng)橡膠(jiao)(jiao)。這將極大拓展有(you)(you)(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)產業的市(shi)場空間,同(tong)時將帶動硅(gui)(gui)(gui)(gui)(gui)油(you)(you)、硅(gui)(gui)(gui)(gui)(gui)烷偶聯劑和硅(gui)(gui)(gui)(gui)(gui)樹脂等其他有(you)(you)(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)產品的消(xiao)費。