
硅橡膠是(shi)指主(zhu)鏈由(you)(you)硅(gui)(gui)和氧原子(zi)交(jiao)替構成,硅(gui)(gui)原子(zi)上通常連有兩個有機基團的(de)(de)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)。普通的(de)(de)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)主(zhu)要由(you)(you)含甲基和少量乙(yi)烯基的(de)(de)硅(gui)(gui)氧鏈節組成。苯基的(de)(de)引入(ru)可提(ti)高(gao)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)高(gao)、低(di)溫性(xing)(xing)(xing)(xing)能(neng),三氟丙基及氰基的(de)(de)引入(ru)則可提(ti)高(gao)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)溫及耐(nai)油性(xing)(xing)(xing)(xing)能(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)耐(nai)低(di)溫性(xing)(xing)(xing)(xing)能(neng)良(liang)好(hao),一(yi)般(ban)在(zai)-55℃下仍(reng)能(neng)工作。引入(ru)苯基后,可達-73℃。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)(de)耐(nai)熱性(xing)(xing)(xing)(xing)能(neng)也(ye)很突(tu)出,在(zai)180℃下可長(chang)期工作,稍(shao)高(gao)于200℃也(ye)能(neng)承受(shou)數周或更長(chang)時間仍(reng)有彈性(xing)(xing)(xing)(xing),瞬時可耐(nai)300℃以上的(de)(de)高(gao)溫。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)(de)透氣(qi)(qi)性(xing)(xing)(xing)(xing)好(hao),氧氣(qi)(qi)透過率在(zai)合成聚合物(wu)中是(shi)較(jiao)高(gao)的(de)(de)。此(ci)外,硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)還具有生(sheng)理(li)惰性(xing)(xing)(xing)(xing)、不(bu)會導致凝血的(de)(de)突(tu)出特性(xing)(xing)(xing)(xing),因此(ci)在(zai)醫用(yong)領域應用(yong)廣泛。
主要品種
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)分(fen)(fen)類的(de)(de)方法很多,通(tong)常按固化前(qian)的(de)(de)形態(tai)分(fen)(fen)為(wei)固體(ti)(ti)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)和液體(ti)(ti)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao);按硫(liu)化溫(wen)度(du)分(fen)(fen)為(wei)室溫(wen)硫(liu)化硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao),高溫(wen)硫(liu)化硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao);按所(suo)用(yong)單體(ti)(ti)的(de)(de)不同,可分(fen)(fen)為(wei)甲(jia)基(ji)乙烯基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao),甲(jia)基(ji)苯基(ji)乙烯基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)等(deng);按性能和用(yong)途的(de)(de)不同又(you)可分(fen)(fen)為(wei)通(tong)用(yong)型(xing)、超耐(nai)低(di)溫(wen)型(xing)、超耐(nai)高溫(wen)型(xing)、高強(qiang)力型(xing)、耐(nai)油型(xing)、醫用(yong)型(xing)等(deng)等(deng)。
發展史
硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)早期是由美國(guo)(guo)(guo)以三(san)氯(lv)化(hua)鐵為催(cui)化(hua)劑合成(cheng)的(de)。1945年(nian)(nian),硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)產(chan)品問世。1948年(nian)(nian),采用(yong)高比表(biao)面積(ji)的(de)氣相法白炭(tan)黑補強的(de)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)研制成(cheng)功,使硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)性能躍升到(dao)實(shi)用(yong)階段,奠定了現代硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)生產(chan)技(ji)術的(de)基礎。從二甲基二氯(lv)硅(gui)(gui)烷合成(cheng)開始生產(chan)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)國(guo)(guo)(guo)家(jia)有美國(guo)(guo)(guo)。俄羅(luo)斯、德國(guo)(guo)(guo)、日(ri)本(ben)、韓國(guo)(guo)(guo)和中(zhong)國(guo)(guo)(guo)等。中(zhong)國(guo)(guo)(guo)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)工(gong)業化(hua)研究始于1957年(nian)(nian),多家(jia)研究所和企業陸(lu)續(xu)開發(fa)出各種硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)。到(dao)2003年(nian)(nian)底,中(zhong)國(guo)(guo)(guo)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)生產(chan)能力為135千噸,其(qi)中(zhong)高溫膠(jiao)(jiao)(jiao)100千噸。
高溫硫化硅橡膠
高溫硫化(hua)(hua)(hua)硅(gui)橡膠是指聚硅(gui)氧(yang)烷(wan)變成(cheng)(cheng)彈(dan)性(xing)(xing)體的過(guo)(guo)程是經(jing)過(guo)(guo)高溫(110-170℃)硫化(hua)(hua)(hua)成(cheng)(cheng)型的。它主(zhu)(zhu)要以高分子量的聚甲基(ji)乙烯基(ji)硅(gui)氧(yang)烷(wan)為生(sheng)膠,混入補強填料、硫化(hua)(hua)(hua)劑等,在加熱加壓下硫化(hua)(hua)(hua)成(cheng)(cheng)彈(dan)性(xing)(xing)體。硅(gui)橡膠的補強主(zhu)(zhu)要是各(ge)(ge)種(zhong)(zhong)類型的白炭黑,可使(shi)硫化(hua)(hua)(hua)膠的強度增加數十倍(bei)。有時為了降低(di)成(cheng)(cheng)本或(huo)改善膠料性(xing)(xing)能(neng)及賦予硫化(hua)(hua)(hua)膠各(ge)(ge)種(zhong)(zhong)特(te)殊的性(xing)(xing)能(neng),也加入相應的各(ge)(ge)種(zhong)(zhong)添加劑。硫化(hua)(hua)(hua)劑是各(ge)(ge)種(zhong)(zhong)有機過(guo)(guo)氧(yang)化(hua)(hua)(hua)物或(huo)加成(cheng)(cheng)反應催化(hua)(hua)(hua)劑。
加工成型方法(fa)如(ru)圖所(suo)示。一次硫化的(de)(de)目的(de)(de)是進行(xing)高分(fen)子(zi)鏈(lian)的(de)(de)交(jiao)聯反應;二次硫化的(de)(de)目的(de)(de)是進行(xing)補充(chong)交(jiao)聯、驅(qu)除硫化劑(ji)分(fen)解(jie)產(chan)物和其他揮發(fa)性化合物以(yi)穩定硫化膠的(de)(de)各(ge)項(xiang)性能(neng)。常用的(de)(de)設備(bei)有開放(fang)式煉膠機、捏合機及真空(kong)密煉機。
主要性能
(1)高(gao)(gao)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)顯(xian)(xian)著的(de)(de)(de)(de)特(te)征是高(gao)(gao)溫(wen)(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing),雖(sui)然(ran)(ran)常(chang)(chang)(chang)溫(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)強(qiang)度(du)(du)僅是天然(ran)(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)或某些合成(cheng)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)一(yi)(yi)半(ban),但在200℃以上的(de)(de)(de)(de)高(gao)(gao)溫(wen)(wen)(wen)環境下(xia),硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)保持一(yi)(yi)定(ding)的(de)(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)和(he)表(biao)面(mian)硬度(du)(du),且力學性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)無(wu)(wu)明顯(xian)(xian)變化(hua)。(2)低溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)(de)玻(bo)璃化(hua)溫(wen)(wen)(wen)度(du)(du)一(yi)(yi)般為-70~-50℃,特(te)殊配方(fang)可達-100℃,表(biao)明其低溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優異(yi)。這對航空(kong)、宇航工業的(de)(de)(de)(de)意義重大。(3)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對氧(yang)(yang)、臭氧(yang)(yang)及紫外線等(deng)十分穩定(ding),在不加任何(he)添(tian)加劑的(de)(de)(de)(de)情況下(xia),就(jiu)具有優良的(de)(de)(de)(de)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣(qi)(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具有優異(yi)的(de)(de)(de)(de)絕緣(yuan)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng),耐(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)電(dian)弧(hu)性(xing)(xing)(xing)(xing)(xing)(xing)也(ye)非常(chang)(chang)(chang)好。(5)物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)常(chang)(chang)(chang)溫(wen)(wen)(wen)下(xia)的(de)(de)(de)(de)物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)比通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)差,但在150℃的(de)(de)(de)(de)高(gao)(gao)溫(wen)(wen)(wen)和(he)-50℃的(de)(de)(de)(de)低溫(wen)(wen)(wen)下(xia),其物理(li)(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優于通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)油及化(hua)學試劑性(xing)(xing)(xing)(xing)(xing)(xing)。普(pu)通(tong)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具有中(zhong)等(deng)的(de)(de)(de)(de)耐(nai)油、耐(nai)溶劑性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。(7)氣(qi)(qi)(qi)體(ti)(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。室溫(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)對空(kong)氣(qi)(qi)(qi)、氮、氧(yang)(yang)、二氧(yang)(yang)化(hua)碳等(deng)氣(qi)(qi)(qi)體(ti)(ti)的(de)(de)(de)(de)透氣(qi)(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)比天然(ran)(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)高(gao)(gao)出(chu)30-50倍。(8)生理(li)(li)惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)無(wu)(wu)毒,無(wu)(wu)味(wei),無(wu)(wu)嗅(xiu),與人(ren)體(ti)(ti)組織不粘連,具有抗(kang)凝血作(zuo)用,對肌(ji)體(ti)(ti)組織的(de)(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)(chang)(chang)少。特(te)別(bie)適合作(zuo)為醫(yi)用材料。
硅橡膠的用量
據中國(guo)汽(qi)(qi)(qi)車(che)(che)(che)工業(ye)協會(hui)統計,2012年(nian)(nian),汽(qi)(qi)(qi)車(che)(che)(che)產銷分別達(da)到1927.18萬輛和1930.64萬輛,同比分別增長(chang)4.63%和4.33%,汽(qi)(qi)(qi)車(che)(che)(che)工業(ye)硅橡(xiang)膠(jiao)(jiao)的用量(liang)(liang)約達(da)2.0萬t。根(gen)據觀研天下的新研究,增加有機硅材料在汽(qi)(qi)(qi)車(che)(che)(che)零(ling)部件方面的用量(liang)(liang),可以大幅度提(ti)高汽(qi)(qi)(qi)車(che)(che)(che)的安全性能,因此,汽(qi)(qi)(qi)車(che)(che)(che)產量(liang)(liang)和單車(che)(che)(che)用量(liang)(liang)水平的提(ti)高都將(jiang)推(tui)動汽(qi)(qi)(qi)車(che)(che)(che)工業(ye)對硅橡(xiang)膠(jiao)(jiao)需求的增加。國(guo)家鼓(gu)勵自主品(pin)牌(pai)(pai)的汽(qi)(qi)(qi)車(che)(che)(che)發(fa)(fa)展(zhan),關鍵(jian)汽(qi)(qi)(qi)車(che)(che)(che)零(ling)部件實現自主化(hua),《2012年(nian)(nian)度黨政(zheng)機關公(gong)務(wu)用車(che)(che)(che)選用車(che)(che)(che)型目(mu)(mu)錄(lu)(征(zheng)求意見稿(gao))》為自主品(pin)牌(pai)(pai)擴大在政(zheng)府采購的市場份額,為改(gai)變目(mu)(mu)前國(guo)內政(zheng)府采購以合資品(pin)牌(pai)(pai)產品(pin)為主的局面提(ti)供了(le)保障。促(cu)進自主品(pin)牌(pai)(pai)發(fa)(fa)展(zhan),國(guo)產汽(qi)(qi)(qi)車(che)(che)(che)業(ye)的繁榮將(jiang)為汽(qi)(qi)(qi)車(che)(che)(che)膠(jiao)(jiao)的應用提(ti)供有力保障。預(yu)測未來(lai)3年(nian)(nian),我國(guo)室(shi)溫硫化(hua)硅橡(xiang)膠(jiao)(jiao)在汽(qi)(qi)(qi)車(che)(che)(che)行業(ye)將(jiang)以年(nian)(nian)均20%增長(chang)。
此外,硅(gui)橡(xiang)(xiang)膠是(shi)重要的(de)(de)(de)非石(shi)油(you)(you)(you)基合成(cheng)橡(xiang)(xiang)膠,約(yue)占非石(shi)油(you)(you)(you)基合成(cheng)橡(xiang)(xiang)膠消費量的(de)(de)(de)98%。但(dan)因為(wei)石(shi)油(you)(you)(you)價(jia)格(ge)的(de)(de)(de)大(da)(da)(da)幅上漲(zhang),同時(shi)我國(guo)在硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)關鍵原(yuan)料有(you)機硅(gui)單(dan)(dan)體的(de)(de)(de)生(sheng)產技術方面取得突破,有(you)機硅(gui)單(dan)(dan)體的(de)(de)(de)生(sheng)產技術在2005年(nian)前被幾家跨國(guo)公司壟斷,但(dan)目前我國(guo)已發展(zhan)成(cheng)為(wei)全球有(you)機硅(gui)單(dan)(dan)體第1大(da)(da)(da)國(guo),這2個方面原(yuan)因使(shi)硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)價(jia)格(ge)從2011年(nian)起開(kai)始(shi)低于石(shi)油(you)(you)(you)基合成(cheng)橡(xiang)(xiang)膠,僅(jin)約(yue)為(wei)大(da)(da)(da)宗石(shi)油(you)(you)(you)基橡(xiang)(xiang)膠的(de)(de)(de)80%~90%,成(cheng)為(wei)廉價(jia)的(de)(de)(de)合成(cheng)橡(xiang)(xiang)膠,并(bing)開(kai)始(shi)大(da)(da)(da)規(gui)模替(ti)代(dai)石(shi)油(you)(you)(you)基合成(cheng)橡(xiang)(xiang)膠。這將(jiang)極大(da)(da)(da)拓展(zhan)有(you)機硅(gui)產業的(de)(de)(de)市場(chang)空間(jian),同時(shi)將(jiang)帶動(dong)硅(gui)油(you)(you)(you)、硅(gui)烷偶聯劑和(he)硅(gui)樹脂等其(qi)他有(you)機硅(gui)產品的(de)(de)(de)消費。