
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(tong)(tong)常(chang)連有(you)兩個(ge)有(you)機基(ji)(ji)團(tuan)的(de)(de)(de)橡(xiang)膠(jiao)(jiao)。普通(tong)(tong)的(de)(de)(de)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)主要由含甲基(ji)(ji)和少量乙(yi)烯(xi)基(ji)(ji)的(de)(de)(de)硅(gui)(gui)氧(yang)鏈(lian)節(jie)組成。苯(ben)(ben)基(ji)(ji)的(de)(de)(de)引(yin)入(ru)可(ke)(ke)提高硅(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)耐高、低溫(wen)性(xing)能(neng),三氟(fu)丙基(ji)(ji)及氰基(ji)(ji)的(de)(de)(de)引(yin)入(ru)則(ze)可(ke)(ke)提高硅(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)耐溫(wen)及耐油性(xing)能(neng)。硅(gui)(gui)橡(xiang)膠(jiao)(jiao)耐低溫(wen)性(xing)能(neng)良好(hao)(hao),一般在-55℃下(xia)仍能(neng)工作(zuo)。引(yin)入(ru)苯(ben)(ben)基(ji)(ji)后,可(ke)(ke)達-73℃。硅(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)耐熱性(xing)能(neng)也(ye)很突出,在180℃下(xia)可(ke)(ke)長期工作(zuo),稍(shao)高于(yu)200℃也(ye)能(neng)承受數周或更長時間仍有(you)彈(dan)性(xing),瞬時可(ke)(ke)耐300℃以上的(de)(de)(de)高溫(wen)。硅(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)透(tou)氣(qi)(qi)性(xing)好(hao)(hao),氧(yang)氣(qi)(qi)透(tou)過率在合(he)成聚合(he)物中是較高的(de)(de)(de)。此(ci)外,硅(gui)(gui)橡(xiang)膠(jiao)(jiao)還(huan)具有(you)生理(li)惰(duo)性(xing)、不會導致凝血的(de)(de)(de)突出特性(xing),因(yin)此(ci)在醫用領域(yu)應(ying)用廣泛。
主要品種
硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)分(fen)(fen)類(lei)的(de)(de)方法很多,通常按固化(hua)(hua)前(qian)的(de)(de)形態分(fen)(fen)為(wei)固體(ti)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)和液(ye)體(ti)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao);按硫化(hua)(hua)溫(wen)度分(fen)(fen)為(wei)室溫(wen)硫化(hua)(hua)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao),高溫(wen)硫化(hua)(hua)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao);按所用(yong)(yong)(yong)單體(ti)的(de)(de)不同(tong)(tong),可分(fen)(fen)為(wei)甲(jia)基(ji)(ji)乙(yi)烯(xi)基(ji)(ji)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao),甲(jia)基(ji)(ji)苯基(ji)(ji)乙(yi)烯(xi)基(ji)(ji)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)、氟(fu)硅(gui),腈硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)等;按性能和用(yong)(yong)(yong)途(tu)的(de)(de)不同(tong)(tong)又可分(fen)(fen)為(wei)通用(yong)(yong)(yong)型、超耐低(di)溫(wen)型、超耐高溫(wen)型、高強力(li)型、耐油型、醫用(yong)(yong)(yong)型等等。
發展史
硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)早期是由(you)美(mei)(mei)國(guo)(guo)以(yi)三氯化(hua)鐵為催化(hua)劑合(he)成(cheng)的(de)。1945年(nian)(nian)(nian),硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)產(chan)品問世。1948年(nian)(nian)(nian),采用(yong)(yong)高比表(biao)面積的(de)氣相法白炭黑(hei)補強的(de)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)研(yan)制成(cheng)功,使硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)性能躍升到(dao)實用(yong)(yong)階段,奠(dian)定了現代硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)生(sheng)產(chan)技術(shu)的(de)基(ji)礎。從二甲(jia)基(ji)二氯硅(gui)(gui)(gui)(gui)(gui)烷(wan)合(he)成(cheng)開始生(sheng)產(chan)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)國(guo)(guo)家有(you)美(mei)(mei)國(guo)(guo)。俄羅(luo)斯、德(de)國(guo)(guo)、日(ri)本、韓國(guo)(guo)和中國(guo)(guo)等(deng)。中國(guo)(guo)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)的(de)工業(ye)化(hua)研(yan)究(jiu)始于1957年(nian)(nian)(nian),多家研(yan)究(jiu)所和企業(ye)陸續開發出(chu)各種(zhong)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)。到(dao)2003年(nian)(nian)(nian)底(di),中國(guo)(guo)硅(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)生(sheng)產(chan)能力(li)為135千噸(dun),其中高溫(wen)膠(jiao)100千噸(dun)。
高溫硫化硅橡膠
高(gao)溫硫化(hua)(hua)(hua)硅(gui)橡膠(jiao)(jiao)是(shi)指聚硅(gui)氧(yang)烷變成彈性(xing)體的(de)(de)過(guo)(guo)程是(shi)經過(guo)(guo)高(gao)溫(110-170℃)硫化(hua)(hua)(hua)成型的(de)(de)。它主要以高(gao)分子(zi)量(liang)的(de)(de)聚甲基乙烯基硅(gui)氧(yang)烷為生(sheng)膠(jiao)(jiao),混(hun)入補(bu)強(qiang)填(tian)料、硫化(hua)(hua)(hua)劑等,在加(jia)熱加(jia)壓下硫化(hua)(hua)(hua)成彈性(xing)體。硅(gui)橡膠(jiao)(jiao)的(de)(de)補(bu)強(qiang)主要是(shi)各種類型的(de)(de)白炭(tan)黑,可使硫化(hua)(hua)(hua)膠(jiao)(jiao)的(de)(de)強(qiang)度增加(jia)數(shu)十倍。有時為了降低成本(ben)或改善膠(jiao)(jiao)料性(xing)能(neng)(neng)及賦予硫化(hua)(hua)(hua)膠(jiao)(jiao)各種特(te)殊的(de)(de)性(xing)能(neng)(neng),也加(jia)入相應的(de)(de)各種添加(jia)劑。硫化(hua)(hua)(hua)劑是(shi)各種有機過(guo)(guo)氧(yang)化(hua)(hua)(hua)物或加(jia)成反應催化(hua)(hua)(hua)劑。
加工成型(xing)方法如(ru)圖所示(shi)。一次硫(liu)化(hua)(hua)的(de)(de)目(mu)的(de)(de)是(shi)(shi)進(jin)(jin)行高分子鏈的(de)(de)交聯(lian)反(fan)應;二次硫(liu)化(hua)(hua)的(de)(de)目(mu)的(de)(de)是(shi)(shi)進(jin)(jin)行補充交聯(lian)、驅(qu)除硫(liu)化(hua)(hua)劑(ji)分解產物和(he)其他(ta)揮發性化(hua)(hua)合(he)(he)物以穩定硫(liu)化(hua)(hua)膠的(de)(de)各項性能。常用(yong)的(de)(de)設備(bei)有(you)開放式(shi)煉(lian)膠機(ji)、捏合(he)(he)機(ji)及真(zhen)空密煉(lian)機(ji)。
主要性能
(1)高(gao)(gao)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)(de)特征(zheng)是高(gao)(gao)溫(wen)(wen)(wen)穩定性(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常(chang)溫(wen)(wen)(wen)下(xia)(xia)硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)強度(du)(du)(du)僅是天(tian)然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)或某些合成(cheng)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)一半,但在200℃以上的(de)(de)高(gao)(gao)溫(wen)(wen)(wen)環境下(xia)(xia),硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)保(bao)持一定的(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回(hui)彈(dan)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表(biao)面硬度(du)(du)(du),且力學(xue)(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)無明顯(xian)變(bian)化。(2)低溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)玻(bo)璃化溫(wen)(wen)(wen)度(du)(du)(du)一般為(wei)-70~-50℃,特殊(shu)配方可達-100℃,表(biao)明其低溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)優異(yi)(yi)。這對航(hang)空、宇航(hang)工業的(de)(de)意義重(zhong)大。(3)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對氧(yang)、臭(chou)氧(yang)及(ji)紫外線等(deng)十分穩定,在不(bu)加任何(he)添加劑的(de)(de)情況下(xia)(xia),就具有(you)優良的(de)(de)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)(dian)氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有(you)優異(yi)(yi)的(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng),耐(nai)(nai)電(dian)(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)(nai)電(dian)(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常(chang)好。(5)物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)常(chang)溫(wen)(wen)(wen)下(xia)(xia)的(de)(de)物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)比通用橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)差,但在150℃的(de)(de)高(gao)(gao)溫(wen)(wen)(wen)和-50℃的(de)(de)低溫(wen)(wen)(wen)下(xia)(xia),其物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)優于通用橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及(ji)化學(xue)(xue)試劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有(you)中(zhong)等(deng)的(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶(rong)劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。(7)氣(qi)體(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。室溫(wen)(wen)(wen)下(xia)(xia)硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)對空氣(qi)、氮、氧(yang)、二氧(yang)化碳等(deng)氣(qi)體(ti)的(de)(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天(tian)然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)高(gao)(gao)出30-50倍。(8)生(sheng)理(li)惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)無毒,無味,無嗅,與(yu)人體(ti)組(zu)織不(bu)粘連,具有(you)抗(kang)凝血(xue)作(zuo)用,對肌體(ti)組(zu)織的(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常(chang)少(shao)。特別適合作(zuo)為(wei)醫用材料(liao)。
硅橡膠的用量
據(ju)中國汽(qi)車工業(ye)協會統計,2012年(nian),汽(qi)車產銷分別達到(dao)1927.18萬(wan)輛(liang)和1930.64萬(wan)輛(liang),同比分別增長(chang)4.63%和4.33%,汽(qi)車工業(ye)硅(gui)橡膠的(de)(de)用(yong)量約達2.0萬(wan)t。根(gen)據(ju)觀(guan)研天(tian)下的(de)(de)新(xin)研究,增加(jia)(jia)有機硅(gui)材料在汽(qi)車零(ling)(ling)部(bu)件(jian)方(fang)面的(de)(de)用(yong)量,可以大(da)幅(fu)度(du)提(ti)(ti)(ti)高汽(qi)車的(de)(de)安全性(xing)能,因此,汽(qi)車產量和單車用(yong)量水平的(de)(de)提(ti)(ti)(ti)高都(dou)將推動汽(qi)車工業(ye)對硅(gui)橡膠需求的(de)(de)增加(jia)(jia)。國家鼓勵自(zi)主(zhu)品(pin)牌(pai)的(de)(de)汽(qi)車發展,關鍵汽(qi)車零(ling)(ling)部(bu)件(jian)實現自(zi)主(zhu)化,《2012年(nian)度(du)黨政(zheng)(zheng)機關公務用(yong)車選用(yong)車型目錄(征(zheng)求意見稿)》為自(zi)主(zhu)品(pin)牌(pai)擴大(da)在政(zheng)(zheng)府采(cai)購的(de)(de)市場份額,為改變目前國內(nei)政(zheng)(zheng)府采(cai)購以合資品(pin)牌(pai)產品(pin)為主(zhu)的(de)(de)局(ju)面提(ti)(ti)(ti)供了保障(zhang)。促進自(zi)主(zhu)品(pin)牌(pai)發展,國產汽(qi)車業(ye)的(de)(de)繁榮將為汽(qi)車膠的(de)(de)應用(yong)提(ti)(ti)(ti)供有力保障(zhang)。預測未(wei)來3年(nian),我國室溫硫化硅(gui)橡膠在汽(qi)車行業(ye)將以年(nian)均20%增長(chang)。
此外,硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)是(shi)重(zhong)要的(de)非石(shi)油(you)(you)基合(he)成橡(xiang)膠(jiao)(jiao),約占非石(shi)油(you)(you)基合(he)成橡(xiang)膠(jiao)(jiao)消費量的(de)98%。但(dan)因(yin)為石(shi)油(you)(you)價(jia)格的(de)大(da)(da)(da)幅(fu)上漲,同時我國在硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)關鍵原料有(you)(you)機硅(gui)(gui)(gui)(gui)單(dan)體的(de)生產(chan)(chan)技術方面取(qu)得突破,有(you)(you)機硅(gui)(gui)(gui)(gui)單(dan)體的(de)生產(chan)(chan)技術在2005年(nian)前(qian)被(bei)幾家(jia)跨國公司(si)壟斷(duan),但(dan)目前(qian)我國已(yi)發展(zhan)成為全球有(you)(you)機硅(gui)(gui)(gui)(gui)單(dan)體第(di)1大(da)(da)(da)國,這2個方面原因(yin)使硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)價(jia)格從2011年(nian)起開始低(di)于(yu)石(shi)油(you)(you)基合(he)成橡(xiang)膠(jiao)(jiao),僅約為大(da)(da)(da)宗石(shi)油(you)(you)基橡(xiang)膠(jiao)(jiao)的(de)80%~90%,成為廉價(jia)的(de)合(he)成橡(xiang)膠(jiao)(jiao),并開始大(da)(da)(da)規模(mo)替代石(shi)油(you)(you)基合(he)成橡(xiang)膠(jiao)(jiao)。這將極大(da)(da)(da)拓展(zhan)有(you)(you)機硅(gui)(gui)(gui)(gui)產(chan)(chan)業的(de)市場空間,同時將帶動(dong)硅(gui)(gui)(gui)(gui)油(you)(you)、硅(gui)(gui)(gui)(gui)烷偶聯劑和硅(gui)(gui)(gui)(gui)樹脂等其他有(you)(you)機硅(gui)(gui)(gui)(gui)產(chan)(chan)品的(de)消費。