
硅橡膠是(shi)指(zhi)主鏈(lian)由硅(gui)(gui)(gui)和氧原子交(jiao)替構成(cheng)(cheng),硅(gui)(gui)(gui)原子上通常連有(you)兩個有(you)機基(ji)團(tuan)的(de)(de)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)。普通的(de)(de)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)主要由含甲基(ji)和少量乙(yi)烯基(ji)的(de)(de)硅(gui)(gui)(gui)氧鏈(lian)節(jie)組成(cheng)(cheng)。苯基(ji)的(de)(de)引(yin)入(ru)可(ke)提(ti)高(gao)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)耐高(gao)、低溫性(xing)能(neng),三氟丙基(ji)及(ji)氰基(ji)的(de)(de)引(yin)入(ru)則可(ke)提(ti)高(gao)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)耐溫及(ji)耐油性(xing)能(neng)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)耐低溫性(xing)能(neng)良好,一般在-55℃下仍能(neng)工(gong)作。引(yin)入(ru)苯基(ji)后,可(ke)達-73℃。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)耐熱(re)性(xing)能(neng)也很突出(chu),在180℃下可(ke)長期工(gong)作,稍(shao)高(gao)于200℃也能(neng)承(cheng)受數周或更長時(shi)間(jian)仍有(you)彈性(xing),瞬時(shi)可(ke)耐300℃以上的(de)(de)高(gao)溫。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)透氣性(xing)好,氧氣透過率(lv)在合成(cheng)(cheng)聚(ju)合物中是(shi)較(jiao)高(gao)的(de)(de)。此外(wai),硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)還具有(you)生理惰(duo)性(xing)、不(bu)會導(dao)致凝(ning)血的(de)(de)突出(chu)特性(xing),因此在醫用領(ling)域(yu)應用廣泛。
主要品種
硅(gui)(gui)橡膠(jiao)(jiao)分(fen)(fen)類的方法很多,通常按固(gu)化(hua)前的形(xing)態分(fen)(fen)為(wei)固(gu)體硅(gui)(gui)橡膠(jiao)(jiao)和液體硅(gui)(gui)橡膠(jiao)(jiao);按硫(liu)化(hua)溫(wen)(wen)度(du)分(fen)(fen)為(wei)室(shi)溫(wen)(wen)硫(liu)化(hua)硅(gui)(gui)橡膠(jiao)(jiao),高(gao)溫(wen)(wen)硫(liu)化(hua)硅(gui)(gui)橡膠(jiao)(jiao);按所用(yong)(yong)單體的不同,可(ke)分(fen)(fen)為(wei)甲基(ji)乙烯(xi)基(ji)硅(gui)(gui)橡膠(jiao)(jiao),甲基(ji)苯基(ji)乙烯(xi)基(ji)硅(gui)(gui)橡膠(jiao)(jiao)、氟硅(gui)(gui),腈硅(gui)(gui)橡膠(jiao)(jiao)等;按性能和用(yong)(yong)途的不同又可(ke)分(fen)(fen)為(wei)通用(yong)(yong)型(xing)、超耐低溫(wen)(wen)型(xing)、超耐高(gao)溫(wen)(wen)型(xing)、高(gao)強(qiang)力型(xing)、耐油型(xing)、醫用(yong)(yong)型(xing)等等。
發展史
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)早(zao)期(qi)是由美國(guo)(guo)以三氯(lv)(lv)化(hua)鐵為催化(hua)劑(ji)合成的。1945年(nian),硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)產品問世(shi)。1948年(nian),采用高比表面積(ji)的氣相(xiang)法白(bai)炭黑(hei)補強(qiang)的硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)研(yan)制成功(gong),使(shi)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的性能躍升到實用階段,奠定了現代硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產技術(shu)的基(ji)礎。從二甲基(ji)二氯(lv)(lv)硅(gui)(gui)(gui)(gui)烷(wan)合成開始(shi)生(sheng)產硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的國(guo)(guo)家有(you)美國(guo)(guo)。俄羅斯、德國(guo)(guo)、日本、韓國(guo)(guo)和中(zhong)(zhong)國(guo)(guo)等(deng)。中(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的工業化(hua)研(yan)究(jiu)始(shi)于(yu)1957年(nian),多家研(yan)究(jiu)所和企業陸續開發出各種(zhong)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)。到2003年(nian)底,中(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產能力為135千噸(dun),其中(zhong)(zhong)高溫(wen)膠(jiao)100千噸(dun)。
高溫硫化硅橡膠(jiao)
高(gao)(gao)溫硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)硅橡膠(jiao)(jiao)是指聚硅氧烷(wan)變成(cheng)(cheng)(cheng)彈性體的(de)(de)過(guo)程是經過(guo)高(gao)(gao)溫(110-170℃)硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)成(cheng)(cheng)(cheng)型(xing)的(de)(de)。它(ta)主(zhu)要以高(gao)(gao)分子量的(de)(de)聚甲基乙烯基硅氧烷(wan)為生膠(jiao)(jiao),混入補(bu)強填料(liao)(liao)、硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)等(deng),在加(jia)(jia)熱加(jia)(jia)壓下硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)成(cheng)(cheng)(cheng)彈性體。硅橡膠(jiao)(jiao)的(de)(de)補(bu)強主(zhu)要是各(ge)種類型(xing)的(de)(de)白(bai)炭(tan)黑,可(ke)使硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)膠(jiao)(jiao)的(de)(de)強度增加(jia)(jia)數十倍。有時為了降(jiang)低(di)成(cheng)(cheng)(cheng)本或改善(shan)膠(jiao)(jiao)料(liao)(liao)性能(neng)及賦予硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)膠(jiao)(jiao)各(ge)種特殊的(de)(de)性能(neng),也加(jia)(jia)入相應(ying)的(de)(de)各(ge)種添加(jia)(jia)劑(ji)。硫(liu)(liu)(liu)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)是各(ge)種有機過(guo)氧化(hua)(hua)(hua)(hua)(hua)(hua)物(wu)或加(jia)(jia)成(cheng)(cheng)(cheng)反應(ying)催化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)。
加工成型(xing)方法如(ru)圖所示。一次(ci)硫化的(de)(de)(de)目的(de)(de)(de)是進行高分(fen)子鏈的(de)(de)(de)交(jiao)聯反應(ying);二次(ci)硫化的(de)(de)(de)目的(de)(de)(de)是進行補充交(jiao)聯、驅(qu)除硫化劑分(fen)解產物和其(qi)他揮發性(xing)化合(he)物以穩定硫化膠的(de)(de)(de)各項性(xing)能。常用的(de)(de)(de)設備有(you)開放(fang)式煉膠機、捏合(he)機及真空密煉機。
主要性能
(1)高溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)顯(xian)著(zhu)的(de)(de)特(te)征是高溫(wen)(wen)穩(wen)定性(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常溫(wen)(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)強度(du)僅(jin)是天(tian)然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)或某(mou)些合成橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)一半,但在200℃以上的(de)(de)高溫(wen)(wen)環境下(xia)(xia),硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)保(bao)持一定的(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈(dan)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表面(mian)硬度(du),且力學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)無明顯(xian)變(bian)化(hua)。(2)低溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)玻璃化(hua)溫(wen)(wen)度(du)一般為-70~-50℃,特(te)殊(shu)配方可達-100℃,表明其低溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)優(you)異(yi)。這對(dui)航(hang)空(kong)、宇航(hang)工(gong)業的(de)(de)意義(yi)重大。(3)耐(nai)(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對(dui)氧(yang)、臭氧(yang)及(ji)紫外線等十分(fen)穩(wen)定,在不加任何(he)添(tian)加劑的(de)(de)情(qing)況下(xia)(xia),就具(ju)有(you)(you)優(you)良的(de)(de)耐(nai)(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具(ju)有(you)(you)優(you)異(yi)的(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng),耐(nai)(nai)(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)(nai)(nai)電(dian)弧(hu)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常好。(5)物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)常溫(wen)(wen)下(xia)(xia)的(de)(de)物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)比(bi)通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)差,但在150℃的(de)(de)高溫(wen)(wen)和-50℃的(de)(de)低溫(wen)(wen)下(xia)(xia),其物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)優(you)于通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)。(6)耐(nai)(nai)(nai)油(you)及(ji)化(hua)學(xue)試劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普(pu)通(tong)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具(ju)有(you)(you)中(zhong)等的(de)(de)耐(nai)(nai)(nai)油(you)、耐(nai)(nai)(nai)溶劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。(7)氣(qi)體(ti)透(tou)過(guo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。室溫(wen)(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)對(dui)空(kong)氣(qi)、氮、氧(yang)、二氧(yang)化(hua)碳等氣(qi)體(ti)的(de)(de)透(tou)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)天(tian)然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)高出30-50倍(bei)。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)無毒,無味,無嗅(xiu),與人體(ti)組(zu)織不粘(zhan)連,具(ju)有(you)(you)抗凝血作用(yong),對(dui)肌體(ti)組(zu)織的(de)(de)反(fan)應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常少。特(te)別適(shi)合作為醫用(yong)材料(liao)。
硅橡膠的用(yong)量(liang)
據中國(guo)汽(qi)(qi)車(che)(che)工業(ye)協會統計,2012年(nian)(nian),汽(qi)(qi)車(che)(che)產(chan)(chan)銷分(fen)別(bie)(bie)達(da)到1927.18萬輛和(he)1930.64萬輛,同比分(fen)別(bie)(bie)增(zeng)(zeng)長4.63%和(he)4.33%,汽(qi)(qi)車(che)(che)工業(ye)硅橡膠的(de)(de)(de)用(yong)(yong)量(liang)約達(da)2.0萬t。根(gen)據觀(guan)研天下的(de)(de)(de)新研究,增(zeng)(zeng)加(jia)有(you)機(ji)硅材料在(zai)汽(qi)(qi)車(che)(che)零部件方面的(de)(de)(de)用(yong)(yong)量(liang),可以(yi)大幅度提(ti)(ti)高汽(qi)(qi)車(che)(che)的(de)(de)(de)安全(quan)性能,因此,汽(qi)(qi)車(che)(che)產(chan)(chan)量(liang)和(he)單車(che)(che)用(yong)(yong)量(liang)水平的(de)(de)(de)提(ti)(ti)高都將(jiang)推動汽(qi)(qi)車(che)(che)工業(ye)對硅橡膠需求的(de)(de)(de)增(zeng)(zeng)加(jia)。國(guo)家(jia)鼓勵自主品牌(pai)的(de)(de)(de)汽(qi)(qi)車(che)(che)發展,關(guan)鍵汽(qi)(qi)車(che)(che)零部件實(shi)現自主化,《2012年(nian)(nian)度黨政(zheng)(zheng)機(ji)關(guan)公務用(yong)(yong)車(che)(che)選用(yong)(yong)車(che)(che)型目(mu)錄(征求意見稿)》為(wei)(wei)自主品牌(pai)擴(kuo)大在(zai)政(zheng)(zheng)府采(cai)購的(de)(de)(de)市(shi)場份額,為(wei)(wei)改變目(mu)前國(guo)內政(zheng)(zheng)府采(cai)購以(yi)合資品牌(pai)產(chan)(chan)品為(wei)(wei)主的(de)(de)(de)局面提(ti)(ti)供了保障(zhang)。促進自主品牌(pai)發展,國(guo)產(chan)(chan)汽(qi)(qi)車(che)(che)業(ye)的(de)(de)(de)繁榮將(jiang)為(wei)(wei)汽(qi)(qi)車(che)(che)膠的(de)(de)(de)應用(yong)(yong)提(ti)(ti)供有(you)力保障(zhang)。預測(ce)未來(lai)3年(nian)(nian),我(wo)國(guo)室(shi)溫硫化硅橡膠在(zai)汽(qi)(qi)車(che)(che)行業(ye)將(jiang)以(yi)年(nian)(nian)均20%增(zeng)(zeng)長。
此外(wai),硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)是重要的(de)非石(shi)(shi)(shi)油(you)(you)(you)基(ji)(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao),約(yue)占非石(shi)(shi)(shi)油(you)(you)(you)基(ji)(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)消(xiao)(xiao)費量的(de)98%。但因為(wei)(wei)石(shi)(shi)(shi)油(you)(you)(you)價格的(de)大幅上(shang)漲,同(tong)時我(wo)國在(zai)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)關鍵原料(liao)有機(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)的(de)生(sheng)產技術方面取得突破(po),有機(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)的(de)生(sheng)產技術在(zai)2005年前(qian)被幾家跨國公司(si)壟斷,但目前(qian)我(wo)國已發展(zhan)成(cheng)為(wei)(wei)全球有機(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)第1大國,這(zhe)2個方面原因使(shi)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)價格從2011年起開(kai)始(shi)低于(yu)石(shi)(shi)(shi)油(you)(you)(you)基(ji)(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao),僅約(yue)為(wei)(wei)大宗石(shi)(shi)(shi)油(you)(you)(you)基(ji)(ji)(ji)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)80%~90%,成(cheng)為(wei)(wei)廉(lian)價的(de)合(he)(he)成(cheng)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao),并開(kai)始(shi)大規(gui)模替(ti)代石(shi)(shi)(shi)油(you)(you)(you)基(ji)(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。這(zhe)將(jiang)極大拓展(zhan)有機(ji)硅(gui)(gui)(gui)產業的(de)市場空(kong)間,同(tong)時將(jiang)帶動(dong)硅(gui)(gui)(gui)油(you)(you)(you)、硅(gui)(gui)(gui)烷偶聯(lian)劑和硅(gui)(gui)(gui)樹(shu)脂等其(qi)他(ta)有機(ji)硅(gui)(gui)(gui)產品的(de)消(xiao)(xiao)費。