硅橡膠是指(zhi)主(zhu)鏈由硅(gui)(gui)(gui)(gui)和氧(yang)原(yuan)子交替構(gou)成,硅(gui)(gui)(gui)(gui)原(yuan)子上通常連有兩個有機基(ji)團的(de)(de)(de)(de)(de)(de)橡(xiang)膠(jiao)。普通的(de)(de)(de)(de)(de)(de)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)主(zhu)要由含(han)甲基(ji)和少量乙烯(xi)基(ji)的(de)(de)(de)(de)(de)(de)硅(gui)(gui)(gui)(gui)氧(yang)鏈節組成。苯基(ji)的(de)(de)(de)(de)(de)(de)引(yin)入可提高(gao)(gao)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)(de)(de)(de)(de)耐(nai)高(gao)(gao)、低溫(wen)性能(neng)(neng),三氟丙基(ji)及(ji)氰(qing)基(ji)的(de)(de)(de)(de)(de)(de)引(yin)入則可提高(gao)(gao)硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)(de)(de)(de)(de)耐(nai)溫(wen)及(ji)耐(nai)油性能(neng)(neng)。硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)耐(nai)低溫(wen)性能(neng)(neng)良(liang)好,一(yi)般在(zai)-55℃下仍能(neng)(neng)工(gong)作(zuo)。引(yin)入苯基(ji)后,可達-73℃。硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)(de)(de)(de)(de)耐(nai)熱性能(neng)(neng)也很突(tu)出,在(zai)180℃下可長期工(gong)作(zuo),稍高(gao)(gao)于200℃也能(neng)(neng)承受(shou)數周(zhou)或(huo)更長時間仍有彈(dan)性,瞬(shun)時可耐(nai)300℃以上的(de)(de)(de)(de)(de)(de)高(gao)(gao)溫(wen)。硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)的(de)(de)(de)(de)(de)(de)透(tou)氣(qi)性好,氧(yang)氣(qi)透(tou)過率在(zai)合成聚合物中是較(jiao)高(gao)(gao)的(de)(de)(de)(de)(de)(de)。此外,硅(gui)(gui)(gui)(gui)橡(xiang)膠(jiao)還具(ju)有生理惰(duo)性、不會導致凝血的(de)(de)(de)(de)(de)(de)突(tu)出特性,因此在(zai)醫用領域應(ying)用廣泛。
主要品種
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)分類的方法很多(duo),通(tong)常按(an)(an)固(gu)化(hua)前的形態(tai)分為固(gu)體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)和液體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao);按(an)(an)硫化(hua)溫(wen)(wen)度(du)分為室溫(wen)(wen)硫化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao),高(gao)溫(wen)(wen)硫化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao);按(an)(an)所用(yong)單體的不同(tong),可分為甲基(ji)乙烯(xi)基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao),甲基(ji)苯基(ji)乙烯(xi)基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)、氟(fu)硅(gui)(gui)(gui)(gui),腈(jing)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)等(deng)(deng);按(an)(an)性能和用(yong)途的不同(tong)又(you)可分為通(tong)用(yong)型(xing)(xing)、超耐(nai)低(di)溫(wen)(wen)型(xing)(xing)、超耐(nai)高(gao)溫(wen)(wen)型(xing)(xing)、高(gao)強力(li)型(xing)(xing)、耐(nai)油型(xing)(xing)、醫用(yong)型(xing)(xing)等(deng)(deng)等(deng)(deng)。
發展史
硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)早期是由美(mei)國(guo)(guo)以三氯(lv)化(hua)鐵為催化(hua)劑合(he)成(cheng)的。1945年,硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)產品(pin)問世。1948年,采用高(gao)比(bi)表面積的氣相法白(bai)炭黑補強(qiang)的硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)研(yan)制(zhi)成(cheng)功,使硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的性能躍升到(dao)實用階段,奠(dian)定了現代硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生產技術的基(ji)礎。從二甲基(ji)二氯(lv)硅(gui)(gui)(gui)(gui)(gui)(gui)烷合(he)成(cheng)開始生產硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的國(guo)(guo)家(jia)有美(mei)國(guo)(guo)。俄(e)羅斯、德國(guo)(guo)、日本(ben)、韓國(guo)(guo)和中(zhong)(zhong)(zhong)國(guo)(guo)等。中(zhong)(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的工業化(hua)研(yan)究始于1957年,多(duo)家(jia)研(yan)究所和企業陸續(xu)開發出各種硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。到(dao)2003年底,中(zhong)(zhong)(zhong)國(guo)(guo)硅(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生產能力(li)為135千(qian)噸,其中(zhong)(zhong)(zhong)高(gao)溫膠(jiao)(jiao)(jiao)(jiao)100千(qian)噸。
高溫硫化硅橡膠
高(gao)溫硫化(hua)(hua)(hua)硅(gui)橡(xiang)膠是(shi)指聚硅(gui)氧(yang)烷變成(cheng)(cheng)彈(dan)性(xing)(xing)體(ti)(ti)的過程是(shi)經過高(gao)溫(110-170℃)硫化(hua)(hua)(hua)成(cheng)(cheng)型的。它(ta)主(zhu)要以高(gao)分(fen)子(zi)量的聚甲基乙烯基硅(gui)氧(yang)烷為(wei)生(sheng)膠,混入補強填料、硫化(hua)(hua)(hua)劑(ji)(ji)(ji)等,在加(jia)熱加(jia)壓下硫化(hua)(hua)(hua)成(cheng)(cheng)彈(dan)性(xing)(xing)體(ti)(ti)。硅(gui)橡(xiang)膠的補強主(zhu)要是(shi)各(ge)種類型的白炭黑(hei),可使硫化(hua)(hua)(hua)膠的強度增(zeng)加(jia)數十倍。有(you)時為(wei)了(le)降低成(cheng)(cheng)本或改善膠料性(xing)(xing)能(neng)及賦(fu)予硫化(hua)(hua)(hua)膠各(ge)種特殊的性(xing)(xing)能(neng),也加(jia)入相應的各(ge)種添加(jia)劑(ji)(ji)(ji)。硫化(hua)(hua)(hua)劑(ji)(ji)(ji)是(shi)各(ge)種有(you)機過氧(yang)化(hua)(hua)(hua)物或加(jia)成(cheng)(cheng)反應催化(hua)(hua)(hua)劑(ji)(ji)(ji)。
加工成(cheng)型方法如(ru)圖所(suo)示。一次硫化的(de)目(mu)的(de)是進行高分(fen)子鏈的(de)交聯反(fan)應;二次硫化的(de)目(mu)的(de)是進行補充交聯、驅除硫化劑分(fen)解產物和其他揮發性(xing)化合(he)物以(yi)穩(wen)定硫化膠(jiao)的(de)各項性(xing)能。常用的(de)設(she)備(bei)有開放式煉(lian)膠(jiao)機(ji)、捏合(he)機(ji)及真空密煉(lian)機(ji)。
主要性能
(1)高溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)顯(xian)著的(de)(de)特(te)(te)征(zheng)是高溫(wen)(wen)穩定性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖(sui)然常(chang)溫(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)強(qiang)度僅是天(tian)然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)或某些(xie)合(he)成橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)一(yi)(yi)半,但在200℃以上的(de)(de)高溫(wen)(wen)環境(jing)下(xia),硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)仍能(neng)(neng)(neng)(neng)保持(chi)一(yi)(yi)定的(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回(hui)彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表面硬度,且力(li)學性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)無明顯(xian)變(bian)化(hua)。(2)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)玻璃化(hua)溫(wen)(wen)度一(yi)(yi)般為-70~-50℃,特(te)(te)殊(shu)配方可(ke)達-100℃,表明其低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)(you)異。這對航空(kong)、宇航工業的(de)(de)意義重大。(3)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)中Si-O-Si鍵對氧(yang)、臭氧(yang)及(ji)紫外線等十分穩定,在不加任何添(tian)加劑(ji)(ji)的(de)(de)情(qing)況下(xia),就具(ju)有(you)優(you)(you)良的(de)(de)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具(ju)有(you)優(you)(you)異的(de)(de)絕(jue)緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng),耐(nai)電(dian)暈(yun)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐(nai)電(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非常(chang)好。(5)物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)常(chang)溫(wen)(wen)下(xia)的(de)(de)物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)比(bi)(bi)通用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)差,但在150℃的(de)(de)高溫(wen)(wen)和-50℃的(de)(de)低(di)溫(wen)(wen)下(xia),其物(wu)理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)(you)于通用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)。(6)耐(nai)油(you)及(ji)化(hua)學試劑(ji)(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具(ju)有(you)中等的(de)(de)耐(nai)油(you)、耐(nai)溶劑(ji)(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。(7)氣體透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。室溫(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)對空(kong)氣、氮、氧(yang)、二(er)氧(yang)化(hua)碳等氣體的(de)(de)透氣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)(bi)天(tian)然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)高出30-50倍。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)無毒(du),無味,無嗅,與人體組織不粘連,具(ju)有(you)抗凝血(xue)作(zuo)用,對肌(ji)體組織的(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)少。特(te)(te)別適合(he)作(zuo)為醫(yi)用材料。
硅橡膠的用量
據中國(guo)(guo)汽(qi)(qi)車(che)工業協會統(tong)計,2012年,汽(qi)(qi)車(che)產(chan)銷(xiao)分別(bie)達到1927.18萬(wan)輛和1930.64萬(wan)輛,同比分別(bie)增長4.63%和4.33%,汽(qi)(qi)車(che)工業硅(gui)橡膠(jiao)的(de)(de)(de)(de)用(yong)(yong)(yong)量(liang)約達2.0萬(wan)t。根據觀(guan)研天下的(de)(de)(de)(de)新研究,增加有機硅(gui)材料在汽(qi)(qi)車(che)零部件方面(mian)的(de)(de)(de)(de)用(yong)(yong)(yong)量(liang),可以(yi)(yi)大幅度提(ti)高(gao)汽(qi)(qi)車(che)的(de)(de)(de)(de)安全性能,因此(ci),汽(qi)(qi)車(che)產(chan)量(liang)和單車(che)用(yong)(yong)(yong)量(liang)水平(ping)的(de)(de)(de)(de)提(ti)高(gao)都將(jiang)推動汽(qi)(qi)車(che)工業對硅(gui)橡膠(jiao)需求的(de)(de)(de)(de)增加。國(guo)(guo)家鼓勵自主品(pin)牌(pai)的(de)(de)(de)(de)汽(qi)(qi)車(che)發(fa)展,關(guan)(guan)鍵汽(qi)(qi)車(che)零部件實現(xian)自主化(hua),《2012年度黨政(zheng)機關(guan)(guan)公務用(yong)(yong)(yong)車(che)選用(yong)(yong)(yong)車(che)型(xing)目錄(征求意見(jian)稿)》為(wei)自主品(pin)牌(pai)擴(kuo)大在政(zheng)府采(cai)購(gou)的(de)(de)(de)(de)市場份額,為(wei)改(gai)變(bian)目前國(guo)(guo)內政(zheng)府采(cai)購(gou)以(yi)(yi)合資品(pin)牌(pai)產(chan)品(pin)為(wei)主的(de)(de)(de)(de)局(ju)面(mian)提(ti)供了保障(zhang)(zhang)。促進自主品(pin)牌(pai)發(fa)展,國(guo)(guo)產(chan)汽(qi)(qi)車(che)業的(de)(de)(de)(de)繁榮將(jiang)為(wei)汽(qi)(qi)車(che)膠(jiao)的(de)(de)(de)(de)應用(yong)(yong)(yong)提(ti)供有力(li)保障(zhang)(zhang)。預測(ce)未來3年,我(wo)國(guo)(guo)室(shi)溫硫(liu)化(hua)硅(gui)橡膠(jiao)在汽(qi)(qi)車(che)行(xing)業將(jiang)以(yi)(yi)年均20%增長。
此外,硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)是重要的非(fei)石油(you)(you)基合成(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)(jiao),約占非(fei)石油(you)(you)基合成(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)(jiao)消費量(liang)的98%。但因(yin)為(wei)石油(you)(you)價(jia)格的大(da)(da)幅(fu)上漲,同(tong)時我國(guo)(guo)在(zai)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的關(guan)鍵原料有(you)(you)機(ji)(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)的生產技術(shu)方(fang)面取(qu)得突(tu)破,有(you)(you)機(ji)(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)的生產技術(shu)在(zai)2005年前(qian)被幾家跨國(guo)(guo)公司壟斷,但目前(qian)我國(guo)(guo)已(yi)發展成(cheng)(cheng)(cheng)為(wei)全球有(you)(you)機(ji)(ji)硅(gui)(gui)(gui)單(dan)體(ti)(ti)第1大(da)(da)國(guo)(guo),這2個方(fang)面原因(yin)使硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的價(jia)格從2011年起開始低于石油(you)(you)基合成(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)(jiao),僅約為(wei)大(da)(da)宗石油(you)(you)基橡(xiang)(xiang)膠(jiao)(jiao)的80%~90%,成(cheng)(cheng)(cheng)為(wei)廉價(jia)的合成(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)(jiao),并開始大(da)(da)規(gui)模替代石油(you)(you)基合成(cheng)(cheng)(cheng)橡(xiang)(xiang)膠(jiao)(jiao)。這將極大(da)(da)拓展有(you)(you)機(ji)(ji)硅(gui)(gui)(gui)產業的市場空(kong)間,同(tong)時將帶動(dong)硅(gui)(gui)(gui)油(you)(you)、硅(gui)(gui)(gui)烷偶聯劑和硅(gui)(gui)(gui)樹(shu)脂等其他有(you)(you)機(ji)(ji)硅(gui)(gui)(gui)產品的消費。