
硅橡膠是指主(zhu)鏈(lian)由(you)硅(gui)(gui)(gui)和(he)氧原子交替構(gou)成,硅(gui)(gui)(gui)原子上(shang)通(tong)常連有(you)(you)兩個有(you)(you)機基(ji)(ji)團的(de)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)。普通(tong)的(de)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)主(zhu)要由(you)含甲基(ji)(ji)和(he)少量乙烯基(ji)(ji)的(de)硅(gui)(gui)(gui)氧鏈(lian)節組成。苯(ben)基(ji)(ji)的(de)引(yin)入(ru)可提高(gao)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)高(gao)、低(di)溫性(xing)能(neng)(neng),三氟(fu)丙(bing)基(ji)(ji)及氰(qing)基(ji)(ji)的(de)引(yin)入(ru)則可提高(gao)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)溫及耐(nai)(nai)油(you)性(xing)能(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)耐(nai)(nai)低(di)溫性(xing)能(neng)(neng)良好,一般(ban)在(zai)(zai)-55℃下(xia)仍(reng)能(neng)(neng)工(gong)(gong)作(zuo)。引(yin)入(ru)苯(ben)基(ji)(ji)后,可達-73℃。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)熱性(xing)能(neng)(neng)也很突(tu)出(chu),在(zai)(zai)180℃下(xia)可長期工(gong)(gong)作(zuo),稍高(gao)于200℃也能(neng)(neng)承受數周(zhou)或更(geng)長時(shi)間仍(reng)有(you)(you)彈性(xing),瞬時(shi)可耐(nai)(nai)300℃以上(shang)的(de)高(gao)溫。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)透(tou)氣性(xing)好,氧氣透(tou)過率在(zai)(zai)合(he)成聚合(he)物(wu)中是較高(gao)的(de)。此(ci)外,硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)還具有(you)(you)生理惰性(xing)、不會導致(zhi)凝(ning)血(xue)的(de)突(tu)出(chu)特性(xing),因此(ci)在(zai)(zai)醫用領域應用廣泛。
主要品種
硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao)分類(lei)的(de)(de)方法很多,通常按固化前的(de)(de)形態分為(wei)(wei)固體(ti)硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao)和液體(ti)硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao);按硫(liu)(liu)化溫度(du)分為(wei)(wei)室溫硫(liu)(liu)化硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao),高溫硫(liu)(liu)化硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao);按所(suo)用(yong)單體(ti)的(de)(de)不(bu)同,可(ke)分為(wei)(wei)甲基(ji)乙(yi)烯(xi)基(ji)硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao),甲基(ji)苯基(ji)乙(yi)烯(xi)基(ji)硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao)、氟硅,腈硅橡(xiang)(xiang)膠(jiao)(jiao)(jiao)等(deng);按性能(neng)和用(yong)途的(de)(de)不(bu)同又(you)可(ke)分為(wei)(wei)通用(yong)型(xing)(xing)、超(chao)耐低溫型(xing)(xing)、超(chao)耐高溫型(xing)(xing)、高強力型(xing)(xing)、耐油型(xing)(xing)、醫用(yong)型(xing)(xing)等(deng)等(deng)。
發展史
硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)早期是由美國(guo)以三(san)氯(lv)化鐵為(wei)催化劑合成的。1945年(nian),硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)產(chan)品問世(shi)。1948年(nian),采(cai)用高比表(biao)面積的氣相法白(bai)炭(tan)黑補強的硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)研制成功(gong),使硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的性能躍升(sheng)到(dao)實用階(jie)段,奠(dian)定了現代硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生(sheng)產(chan)技術的基礎(chu)。從二甲基二氯(lv)硅(gui)(gui)(gui)烷合成開(kai)始生(sheng)產(chan)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的國(guo)家(jia)有美國(guo)。俄羅斯、德國(guo)、日本、韓國(guo)和中(zhong)國(guo)等(deng)。中(zhong)國(guo)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的工業化研究(jiu)始于(yu)1957年(nian),多家(jia)研究(jiu)所和企業陸續(xu)開(kai)發(fa)出(chu)各種硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。到(dao)2003年(nian)底(di),中(zhong)國(guo)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生(sheng)產(chan)能力為(wei)135千(qian)(qian)噸,其(qi)中(zhong)高溫膠(jiao)(jiao)(jiao)(jiao)100千(qian)(qian)噸。
高溫硫化硅橡膠
高(gao)溫硫化(hua)(hua)硅(gui)橡膠(jiao)(jiao)是(shi)指聚硅(gui)氧(yang)烷(wan)變成彈(dan)性(xing)體的過程是(shi)經過高(gao)溫(110-170℃)硫化(hua)(hua)成型的。它主(zhu)要(yao)以(yi)高(gao)分子量的聚甲基(ji)乙烯(xi)基(ji)硅(gui)氧(yang)烷(wan)為(wei)生(sheng)膠(jiao)(jiao),混(hun)入補(bu)強填料、硫化(hua)(hua)劑等(deng),在加(jia)(jia)熱加(jia)(jia)壓下硫化(hua)(hua)成彈(dan)性(xing)體。硅(gui)橡膠(jiao)(jiao)的補(bu)強主(zhu)要(yao)是(shi)各種(zhong)類型的白炭(tan)黑,可使硫化(hua)(hua)膠(jiao)(jiao)的強度增加(jia)(jia)數十倍。有時為(wei)了降低成本或改善膠(jiao)(jiao)料性(xing)能及賦予(yu)硫化(hua)(hua)膠(jiao)(jiao)各種(zhong)特殊的性(xing)能,也加(jia)(jia)入相(xiang)應的各種(zhong)添(tian)加(jia)(jia)劑。硫化(hua)(hua)劑是(shi)各種(zhong)有機過氧(yang)化(hua)(hua)物或加(jia)(jia)成反應催化(hua)(hua)劑。
加工成型方法如(ru)圖(tu)所示。一次硫化的目的是(shi)進(jin)行高分(fen)子(zi)鏈的交(jiao)聯反應;二次硫化的目的是(shi)進(jin)行補充交(jiao)聯、驅除硫化劑分(fen)解(jie)產物和(he)其(qi)他揮發(fa)性化合物以穩定硫化膠的各項性能。常用(yong)的設(she)備有開放式煉膠機、捏合機及真空密煉機。
主要性能
(1)高溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)顯著的(de)(de)(de)(de)特(te)(te)征是高溫(wen)(wen)穩(wen)定性(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常(chang)(chang)(chang)溫(wen)(wen)下硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)強度僅是天然(ran)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)或(huo)某(mou)些(xie)合成橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)一(yi)半,但在200℃以上的(de)(de)(de)(de)高溫(wen)(wen)環境下,硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)仍能(neng)(neng)(neng)(neng)保持一(yi)定的(de)(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和表(biao)面(mian)硬(ying)度,且力學性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)無(wu)明顯變化。(2)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)(de)玻璃化溫(wen)(wen)度一(yi)般為-70~-50℃,特(te)(te)殊配方可達-100℃,表(biao)明其(qi)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優異(yi)。這(zhe)對航空、宇航工業的(de)(de)(de)(de)意義重大。(3)耐候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)中Si-O-Si鍵(jian)對氧(yang)、臭氧(yang)及紫外線(xian)等(deng)十分穩(wen)定,在不(bu)(bu)加任何添(tian)加劑的(de)(de)(de)(de)情況下,就(jiu)具(ju)有(you)優良(liang)的(de)(de)(de)(de)耐候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具(ju)有(you)優異(yi)的(de)(de)(de)(de)絕(jue)緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng),耐電暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和耐電弧(hu)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非常(chang)(chang)(chang)好。(5)物(wu)(wu)理(li)機(ji)(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)常(chang)(chang)(chang)溫(wen)(wen)下的(de)(de)(de)(de)物(wu)(wu)理(li)機(ji)(ji)械(xie)性(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(cha),但在150℃的(de)(de)(de)(de)高溫(wen)(wen)和-50℃的(de)(de)(de)(de)低(di)溫(wen)(wen)下,其(qi)物(wu)(wu)理(li)機(ji)(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優于通用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)。(6)耐油及化學試(shi)劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)具(ju)有(you)中等(deng)的(de)(de)(de)(de)耐油、耐溶劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。(7)氣(qi)體(ti)(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。室(shi)溫(wen)(wen)下硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)對空氣(qi)、氮、氧(yang)、二氧(yang)化碳等(deng)氣(qi)體(ti)(ti)的(de)(de)(de)(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)(bi)天然(ran)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)。硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)無(wu)毒(du),無(wu)味,無(wu)嗅,與人(ren)體(ti)(ti)組織不(bu)(bu)粘(zhan)連,具(ju)有(you)抗凝血作用,對肌體(ti)(ti)組織的(de)(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)(chang)(chang)少(shao)。特(te)(te)別適合作為醫用材料。
硅橡膠的用量
據(ju)中國汽(qi)車(che)工業(ye)(ye)協(xie)會統計(ji),2012年(nian),汽(qi)車(che)產銷(xiao)分(fen)(fen)別達到1927.18萬(wan)輛(liang)和1930.64萬(wan)輛(liang),同比分(fen)(fen)別增(zeng)(zeng)長(chang)4.63%和4.33%,汽(qi)車(che)工業(ye)(ye)硅(gui)橡膠(jiao)的(de)(de)(de)用(yong)(yong)量(liang)(liang)(liang)約達2.0萬(wan)t。根據(ju)觀研(yan)天下的(de)(de)(de)新研(yan)究,增(zeng)(zeng)加(jia)(jia)有(you)機硅(gui)材料在(zai)汽(qi)車(che)零部(bu)件方(fang)面(mian)的(de)(de)(de)用(yong)(yong)量(liang)(liang)(liang),可以(yi)(yi)大(da)(da)幅度提(ti)高(gao)汽(qi)車(che)的(de)(de)(de)安全性能,因(yin)此(ci),汽(qi)車(che)產量(liang)(liang)(liang)和單車(che)用(yong)(yong)量(liang)(liang)(liang)水平的(de)(de)(de)提(ti)高(gao)都將推動(dong)汽(qi)車(che)工業(ye)(ye)對(dui)硅(gui)橡膠(jiao)需求的(de)(de)(de)增(zeng)(zeng)加(jia)(jia)。國家鼓勵(li)自(zi)主(zhu)品牌的(de)(de)(de)汽(qi)車(che)發展,關鍵汽(qi)車(che)零部(bu)件實現自(zi)主(zhu)化,《2012年(nian)度黨政機關公務用(yong)(yong)車(che)選用(yong)(yong)車(che)型目錄(lu)(征求意見稿)》為(wei)(wei)自(zi)主(zhu)品牌擴大(da)(da)在(zai)政府采(cai)(cai)購(gou)的(de)(de)(de)市場份額,為(wei)(wei)改變目前國內政府采(cai)(cai)購(gou)以(yi)(yi)合(he)資品牌產品為(wei)(wei)主(zhu)的(de)(de)(de)局面(mian)提(ti)供了保障(zhang)(zhang)。促進自(zi)主(zhu)品牌發展,國產汽(qi)車(che)業(ye)(ye)的(de)(de)(de)繁榮將為(wei)(wei)汽(qi)車(che)膠(jiao)的(de)(de)(de)應(ying)用(yong)(yong)提(ti)供有(you)力保障(zhang)(zhang)。預測未來3年(nian),我國室溫硫化硅(gui)橡膠(jiao)在(zai)汽(qi)車(che)行業(ye)(ye)將以(yi)(yi)年(nian)均20%增(zeng)(zeng)長(chang)。
此外(wai),硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)是重(zhong)要的(de)(de)(de)(de)(de)非石(shi)(shi)油(you)(you)基(ji)(ji)合(he)成(cheng)橡(xiang)(xiang)膠(jiao),約占非石(shi)(shi)油(you)(you)基(ji)(ji)合(he)成(cheng)橡(xiang)(xiang)膠(jiao)消費量的(de)(de)(de)(de)(de)98%。但因(yin)為(wei)(wei)石(shi)(shi)油(you)(you)價(jia)格的(de)(de)(de)(de)(de)大(da)幅上漲,同(tong)時我國(guo)在硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)關鍵(jian)原料有(you)(you)(you)機(ji)硅(gui)(gui)(gui)單體的(de)(de)(de)(de)(de)生產(chan)技術方(fang)面取(qu)得突破,有(you)(you)(you)機(ji)硅(gui)(gui)(gui)單體的(de)(de)(de)(de)(de)生產(chan)技術在2005年前(qian)被幾家跨國(guo)公(gong)司壟(long)斷,但目前(qian)我國(guo)已發展成(cheng)為(wei)(wei)全球有(you)(you)(you)機(ji)硅(gui)(gui)(gui)單體第1大(da)國(guo),這2個方(fang)面原因(yin)使硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)價(jia)格從2011年起(qi)開始(shi)(shi)低于石(shi)(shi)油(you)(you)基(ji)(ji)合(he)成(cheng)橡(xiang)(xiang)膠(jiao),僅約為(wei)(wei)大(da)宗石(shi)(shi)油(you)(you)基(ji)(ji)橡(xiang)(xiang)膠(jiao)的(de)(de)(de)(de)(de)80%~90%,成(cheng)為(wei)(wei)廉價(jia)的(de)(de)(de)(de)(de)合(he)成(cheng)橡(xiang)(xiang)膠(jiao),并開始(shi)(shi)大(da)規模(mo)替代石(shi)(shi)油(you)(you)基(ji)(ji)合(he)成(cheng)橡(xiang)(xiang)膠(jiao)。這將極大(da)拓(tuo)展有(you)(you)(you)機(ji)硅(gui)(gui)(gui)產(chan)業的(de)(de)(de)(de)(de)市場空間(jian),同(tong)時將帶(dai)動硅(gui)(gui)(gui)油(you)(you)、硅(gui)(gui)(gui)烷偶聯劑和硅(gui)(gui)(gui)樹脂等(deng)其他有(you)(you)(you)機(ji)硅(gui)(gui)(gui)產(chan)品的(de)(de)(de)(de)(de)消費。