
硅橡膠是(shi)指主鏈(lian)由(you)硅(gui)(gui)(gui)和氧(yang)原(yuan)子交替(ti)構成,硅(gui)(gui)(gui)原(yuan)子上通常連有兩個有機(ji)基(ji)(ji)團的(de)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)。普(pu)通的(de)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)主要由(you)含(han)甲基(ji)(ji)和少(shao)量乙烯基(ji)(ji)的(de)硅(gui)(gui)(gui)氧(yang)鏈(lian)節組成。苯基(ji)(ji)的(de)引(yin)入(ru)可(ke)提(ti)高(gao)(gao)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)耐(nai)高(gao)(gao)、低溫性(xing)能(neng),三氟丙(bing)基(ji)(ji)及氰基(ji)(ji)的(de)引(yin)入(ru)則(ze)可(ke)提(ti)高(gao)(gao)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)耐(nai)溫及耐(nai)油(you)性(xing)能(neng)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)耐(nai)低溫性(xing)能(neng)良好(hao)(hao),一般(ban)在(zai)-55℃下(xia)仍(reng)能(neng)工(gong)作。引(yin)入(ru)苯基(ji)(ji)后,可(ke)達-73℃。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)耐(nai)熱(re)性(xing)能(neng)也(ye)很突出(chu),在(zai)180℃下(xia)可(ke)長期(qi)工(gong)作,稍高(gao)(gao)于200℃也(ye)能(neng)承受數周或更長時間仍(reng)有彈(dan)性(xing),瞬(shun)時可(ke)耐(nai)300℃以(yi)上的(de)高(gao)(gao)溫。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)透氣性(xing)好(hao)(hao),氧(yang)氣透過率在(zai)合成聚合物(wu)中(zhong)是(shi)較高(gao)(gao)的(de)。此(ci)外,硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)還具有生理惰性(xing)、不會導致凝血的(de)突出(chu)特(te)性(xing),因此(ci)在(zai)醫用領域(yu)應(ying)用廣泛(fan)。
主要品種
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)分(fen)類(lei)的方法很(hen)多,通(tong)常按(an)(an)固化(hua)(hua)前的形態分(fen)為固體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)和(he)(he)液體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao);按(an)(an)硫(liu)化(hua)(hua)溫(wen)(wen)度分(fen)為室溫(wen)(wen)硫(liu)化(hua)(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao),高(gao)溫(wen)(wen)硫(liu)化(hua)(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao);按(an)(an)所用單體的不(bu)同,可(ke)分(fen)為甲基(ji)(ji)乙(yi)烯基(ji)(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao),甲基(ji)(ji)苯基(ji)(ji)乙(yi)烯基(ji)(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)等(deng);按(an)(an)性能和(he)(he)用途的不(bu)同又可(ke)分(fen)為通(tong)用型(xing)(xing)、超耐(nai)低溫(wen)(wen)型(xing)(xing)、超耐(nai)高(gao)溫(wen)(wen)型(xing)(xing)、高(gao)強力型(xing)(xing)、耐(nai)油型(xing)(xing)、醫用型(xing)(xing)等(deng)等(deng)。
發展(zhan)史
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)早期是由美國(guo)(guo)(guo)(guo)以三氯(lv)化鐵為催化劑合(he)成的(de)。1945年(nian),硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)產(chan)(chan)品(pin)問世。1948年(nian),采用(yong)高比表面積的(de)氣相法白炭黑補強的(de)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)研(yan)制成功,使硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)性能躍升到(dao)實用(yong)階(jie)段,奠定了現代硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生產(chan)(chan)技術的(de)基礎。從二(er)(er)甲基二(er)(er)氯(lv)硅(gui)(gui)(gui)(gui)烷合(he)成開始生產(chan)(chan)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)國(guo)(guo)(guo)(guo)家有(you)美國(guo)(guo)(guo)(guo)。俄(e)羅斯、德國(guo)(guo)(guo)(guo)、日本、韓國(guo)(guo)(guo)(guo)和(he)中國(guo)(guo)(guo)(guo)等。中國(guo)(guo)(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)工業(ye)化研(yan)究始于1957年(nian),多家研(yan)究所和(he)企業(ye)陸(lu)續開發出各種硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。到(dao)2003年(nian)底(di),中國(guo)(guo)(guo)(guo)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生產(chan)(chan)能力為135千(qian)噸(dun)(dun),其中高溫膠(jiao)(jiao)(jiao)(jiao)100千(qian)噸(dun)(dun)。
高溫硫(liu)化硅橡膠(jiao)
高溫(wen)硫化(hua)硅(gui)橡膠是(shi)指聚(ju)硅(gui)氧(yang)烷變成(cheng)(cheng)彈(dan)性(xing)體的過(guo)程是(shi)經過(guo)高溫(wen)(110-170℃)硫化(hua)成(cheng)(cheng)型(xing)的。它主要(yao)以高分子量的聚(ju)甲基(ji)乙烯基(ji)硅(gui)氧(yang)烷為生膠,混入(ru)(ru)補強(qiang)填料(liao)(liao)、硫化(hua)劑等,在加(jia)(jia)熱加(jia)(jia)壓下硫化(hua)成(cheng)(cheng)彈(dan)性(xing)體。硅(gui)橡膠的補強(qiang)主要(yao)是(shi)各(ge)種類型(xing)的白炭(tan)黑,可使硫化(hua)膠的強(qiang)度增(zeng)加(jia)(jia)數十倍。有(you)時為了(le)降低(di)成(cheng)(cheng)本或改善膠料(liao)(liao)性(xing)能(neng)及(ji)賦予硫化(hua)膠各(ge)種特(te)殊的性(xing)能(neng),也加(jia)(jia)入(ru)(ru)相應的各(ge)種添加(jia)(jia)劑。硫化(hua)劑是(shi)各(ge)種有(you)機過(guo)氧(yang)化(hua)物或加(jia)(jia)成(cheng)(cheng)反應催化(hua)劑。
加工成型(xing)方(fang)法如(ru)圖(tu)所示。一(yi)次(ci)硫(liu)化的目(mu)(mu)的是(shi)進行(xing)高分(fen)子(zi)鏈的交(jiao)聯(lian)反(fan)應(ying);二(er)次(ci)硫(liu)化的目(mu)(mu)的是(shi)進行(xing)補充交(jiao)聯(lian)、驅除硫(liu)化劑分(fen)解產物和(he)其(qi)他揮發性(xing)化合物以穩定硫(liu)化膠的各項性(xing)能。常用的設備有開放式煉膠機、捏合機及真空密煉機。
主要(yao)性能
(1)高(gao)(gao)(gao)溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)顯著(zhu)的(de)(de)(de)特(te)征是(shi)高(gao)(gao)(gao)溫(wen)(wen)(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖(sui)然(ran)(ran)常溫(wen)(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)強度僅是(shi)天然(ran)(ran)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)或(huo)某些合成橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)一半(ban),但在200℃以(yi)上的(de)(de)(de)高(gao)(gao)(gao)溫(wen)(wen)(wen)(wen)環境(jing)下(xia),硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)仍能(neng)保(bao)持一定(ding)的(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表(biao)面硬度,且力學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)無明顯變化。(2)低溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)玻璃化溫(wen)(wen)(wen)(wen)度一般為(wei)-70~-50℃,特(te)殊配方可達-100℃,表(biao)明其低溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)異。這對(dui)航空(kong)、宇航工業(ye)的(de)(de)(de)意義重大。(3)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵(jian)對(dui)氧、臭(chou)氧及(ji)紫外線等(deng)十分穩定(ding),在不(bu)加任何(he)添加劑的(de)(de)(de)情況下(xia),就具有(you)優(you)良的(de)(de)(de)耐(nai)(nai)候(hou)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)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)具有(you)優(you)異的(de)(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng),耐(nai)(nai)電暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)(nai)電弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常好。(5)物理(li)機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)常溫(wen)(wen)(wen)(wen)下(xia)的(de)(de)(de)物理(li)機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)比(bi)通用(yong)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)差(cha),但在150℃的(de)(de)(de)高(gao)(gao)(gao)溫(wen)(wen)(wen)(wen)和-50℃的(de)(de)(de)低溫(wen)(wen)(wen)(wen)下(xia),其物理(li)機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)優(you)于通用(yong)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及(ji)化學(xue)試劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)具有(you)中(zhong)等(deng)的(de)(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。(7)氣(qi)(qi)體(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)。室溫(wen)(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)對(dui)空(kong)氣(qi)(qi)、氮、氧、二氧化碳等(deng)氣(qi)(qi)體(ti)的(de)(de)(de)透氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)天然(ran)(ran)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)高(gao)(gao)(gao)出30-50倍。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)(jiao)無毒(du),無味,無嗅,與人體(ti)組織不(bu)粘連,具有(you)抗(kang)凝血作用(yong),對(dui)肌體(ti)組織的(de)(de)(de)反應(ying)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常少。特(te)別適合作為(wei)醫用(yong)材料。
硅(gui)橡膠的(de)用量(liang)
據(ju)中國汽(qi)(qi)(qi)車(che)(che)(che)工(gong)業協會統計,2012年,汽(qi)(qi)(qi)車(che)(che)(che)產(chan)銷分別(bie)達(da)到1927.18萬輛和(he)1930.64萬輛,同比分別(bie)增(zeng)(zeng)長(chang)4.63%和(he)4.33%,汽(qi)(qi)(qi)車(che)(che)(che)工(gong)業硅(gui)(gui)橡膠(jiao)的(de)(de)用(yong)(yong)(yong)量(liang)約達(da)2.0萬t。根據(ju)觀研天下的(de)(de)新(xin)研究,增(zeng)(zeng)加有機硅(gui)(gui)材料(liao)在汽(qi)(qi)(qi)車(che)(che)(che)零部件(jian)方面(mian)的(de)(de)用(yong)(yong)(yong)量(liang),可以(yi)大(da)幅度(du)提高汽(qi)(qi)(qi)車(che)(che)(che)的(de)(de)安(an)全性(xing)能,因此,汽(qi)(qi)(qi)車(che)(che)(che)產(chan)量(liang)和(he)單車(che)(che)(che)用(yong)(yong)(yong)量(liang)水平的(de)(de)提高都將推(tui)動(dong)汽(qi)(qi)(qi)車(che)(che)(che)工(gong)業對硅(gui)(gui)橡膠(jiao)需求的(de)(de)增(zeng)(zeng)加。國家鼓(gu)勵自(zi)(zi)主(zhu)品牌(pai)(pai)的(de)(de)汽(qi)(qi)(qi)車(che)(che)(che)發展,關鍵(jian)汽(qi)(qi)(qi)車(che)(che)(che)零部件(jian)實(shi)現自(zi)(zi)主(zhu)化(hua),《2012年度(du)黨政(zheng)機關公務(wu)用(yong)(yong)(yong)車(che)(che)(che)選用(yong)(yong)(yong)車(che)(che)(che)型目(mu)錄(征求意(yi)見(jian)稿)》為(wei)自(zi)(zi)主(zhu)品牌(pai)(pai)擴大(da)在政(zheng)府(fu)采購的(de)(de)市場份額,為(wei)改變目(mu)前國內政(zheng)府(fu)采購以(yi)合(he)資品牌(pai)(pai)產(chan)品為(wei)主(zhu)的(de)(de)局面(mian)提供了(le)保(bao)障。促進自(zi)(zi)主(zhu)品牌(pai)(pai)發展,國產(chan)汽(qi)(qi)(qi)車(che)(che)(che)業的(de)(de)繁榮將為(wei)汽(qi)(qi)(qi)車(che)(che)(che)膠(jiao)的(de)(de)應用(yong)(yong)(yong)提供有力保(bao)障。預測未來3年,我(wo)國室溫硫化(hua)硅(gui)(gui)橡膠(jiao)在汽(qi)(qi)(qi)車(che)(che)(che)行業將以(yi)年均20%增(zeng)(zeng)長(chang)。
此外(wai),硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)是重(zhong)要的(de)(de)(de)非石油(you)(you)(you)基合成(cheng)橡(xiang)膠(jiao)(jiao),約占(zhan)非石油(you)(you)(you)基合成(cheng)橡(xiang)膠(jiao)(jiao)消(xiao)費量的(de)(de)(de)98%。但因(yin)為石油(you)(you)(you)價格的(de)(de)(de)大(da)(da)幅(fu)上漲,同(tong)時(shi)我國(guo)在硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)關(guan)鍵原料(liao)有機硅(gui)(gui)(gui)(gui)單(dan)體的(de)(de)(de)生(sheng)產技術方面取(qu)得(de)突破(po),有機硅(gui)(gui)(gui)(gui)單(dan)體的(de)(de)(de)生(sheng)產技術在2005年(nian)前(qian)被(bei)幾家跨國(guo)公司壟斷(duan),但目前(qian)我國(guo)已發展成(cheng)為全球有機硅(gui)(gui)(gui)(gui)單(dan)體第1大(da)(da)國(guo),這2個方面原因(yin)使硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)價格從2011年(nian)起開始低于(yu)石油(you)(you)(you)基合成(cheng)橡(xiang)膠(jiao)(jiao),僅約為大(da)(da)宗石油(you)(you)(you)基橡(xiang)膠(jiao)(jiao)的(de)(de)(de)80%~90%,成(cheng)為廉價的(de)(de)(de)合成(cheng)橡(xiang)膠(jiao)(jiao),并開始大(da)(da)規模替代石油(you)(you)(you)基合成(cheng)橡(xiang)膠(jiao)(jiao)。這將(jiang)極大(da)(da)拓展有機硅(gui)(gui)(gui)(gui)產業的(de)(de)(de)市場空間,同(tong)時(shi)將(jiang)帶動硅(gui)(gui)(gui)(gui)油(you)(you)(you)、硅(gui)(gui)(gui)(gui)烷偶聯(lian)劑和硅(gui)(gui)(gui)(gui)樹脂等其他有機硅(gui)(gui)(gui)(gui)產品的(de)(de)(de)消(xiao)費。