硅橡膠是指主鏈由硅(gui)和氧(yang)原(yuan)子交(jiao)替構成(cheng),硅(gui)原(yuan)子上通常(chang)連有(you)兩個有(you)機(ji)基(ji)團(tuan)的(de)(de)(de)橡(xiang)(xiang)膠(jiao)(jiao)。普通的(de)(de)(de)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)主要(yao)由含甲基(ji)和少量乙烯基(ji)的(de)(de)(de)硅(gui)氧(yang)鏈節組成(cheng)。苯基(ji)的(de)(de)(de)引(yin)入可(ke)提高(gao)(gao)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)耐高(gao)(gao)、低溫性(xing)(xing)能(neng)(neng)(neng),三(san)氟丙基(ji)及(ji)(ji)氰基(ji)的(de)(de)(de)引(yin)入則可(ke)提高(gao)(gao)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)耐溫及(ji)(ji)耐油(you)性(xing)(xing)能(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)耐低溫性(xing)(xing)能(neng)(neng)(neng)良好(hao)(hao),一(yi)般在-55℃下(xia)仍能(neng)(neng)(neng)工(gong)作(zuo)。引(yin)入苯基(ji)后,可(ke)達-73℃。硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)耐熱性(xing)(xing)能(neng)(neng)(neng)也(ye)(ye)很(hen)突(tu)出,在180℃下(xia)可(ke)長(chang)期(qi)工(gong)作(zuo),稍(shao)高(gao)(gao)于200℃也(ye)(ye)能(neng)(neng)(neng)承受數周(zhou)或(huo)更長(chang)時間仍有(you)彈性(xing)(xing),瞬(shun)時可(ke)耐300℃以上的(de)(de)(de)高(gao)(gao)溫。硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)透氣(qi)性(xing)(xing)好(hao)(hao),氧(yang)氣(qi)透過率在合(he)成(cheng)聚(ju)合(he)物中是較(jiao)高(gao)(gao)的(de)(de)(de)。此(ci)外,硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)還具有(you)生理惰(duo)性(xing)(xing)、不會導致(zhi)凝血的(de)(de)(de)突(tu)出特性(xing)(xing),因此(ci)在醫用領域應用廣泛。
主要品種
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)分(fen)(fen)類的方法很多,通常按固(gu)化(hua)前的形態分(fen)(fen)為(wei)固(gu)體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)和液體硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao);按硫(liu)化(hua)溫(wen)(wen)(wen)度分(fen)(fen)為(wei)室溫(wen)(wen)(wen)硫(liu)化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao),高溫(wen)(wen)(wen)硫(liu)化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao);按所用單體的不同,可分(fen)(fen)為(wei)甲基(ji)(ji)乙(yi)烯(xi)基(ji)(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao),甲基(ji)(ji)苯基(ji)(ji)乙(yi)烯(xi)基(ji)(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)等;按性(xing)能(neng)和用途的不同又可分(fen)(fen)為(wei)通用型(xing)、超耐(nai)低(di)溫(wen)(wen)(wen)型(xing)、超耐(nai)高溫(wen)(wen)(wen)型(xing)、高強力(li)型(xing)、耐(nai)油型(xing)、醫用型(xing)等等。
發展史
硅(gui)橡(xiang)(xiang)膠(jiao)早期是由美國(guo)(guo)(guo)(guo)(guo)以(yi)三氯化(hua)(hua)鐵為(wei)催化(hua)(hua)劑合成的(de)。1945年,硅(gui)橡(xiang)(xiang)膠(jiao)產(chan)品問世。1948年,采用高(gao)(gao)比表面積的(de)氣(qi)相法白炭黑補強(qiang)的(de)硅(gui)橡(xiang)(xiang)膠(jiao)研(yan)制成功,使硅(gui)橡(xiang)(xiang)膠(jiao)的(de)性能(neng)躍(yue)升到(dao)實用階段,奠定了現代硅(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產(chan)技術的(de)基(ji)礎。從二甲(jia)基(ji)二氯硅(gui)烷合成開始(shi)生(sheng)產(chan)硅(gui)橡(xiang)(xiang)膠(jiao)的(de)國(guo)(guo)(guo)(guo)(guo)家有美國(guo)(guo)(guo)(guo)(guo)。俄羅斯、德國(guo)(guo)(guo)(guo)(guo)、日本(ben)、韓(han)國(guo)(guo)(guo)(guo)(guo)和中(zhong)國(guo)(guo)(guo)(guo)(guo)等。中(zhong)國(guo)(guo)(guo)(guo)(guo)硅(gui)橡(xiang)(xiang)膠(jiao)的(de)工(gong)業(ye)化(hua)(hua)研(yan)究始(shi)于(yu)1957年,多(duo)家研(yan)究所和企(qi)業(ye)陸(lu)續開發出(chu)各種硅(gui)橡(xiang)(xiang)膠(jiao)。到(dao)2003年底,中(zhong)國(guo)(guo)(guo)(guo)(guo)硅(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產(chan)能(neng)力為(wei)135千噸(dun),其(qi)中(zhong)高(gao)(gao)溫膠(jiao)100千噸(dun)。
高溫硫化硅橡膠
高(gao)溫(wen)硫(liu)化(hua)(hua)(hua)(hua)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)是(shi)指聚硅(gui)(gui)氧(yang)烷(wan)變成(cheng)(cheng)彈性體(ti)的(de)(de)(de)過(guo)程是(shi)經過(guo)高(gao)溫(wen)(110-170℃)硫(liu)化(hua)(hua)(hua)(hua)成(cheng)(cheng)型(xing)的(de)(de)(de)。它主要(yao)以高(gao)分(fen)子(zi)量的(de)(de)(de)聚甲基(ji)乙烯(xi)基(ji)硅(gui)(gui)氧(yang)烷(wan)為生膠(jiao)(jiao),混(hun)入補強(qiang)(qiang)填料、硫(liu)化(hua)(hua)(hua)(hua)劑等,在(zai)加(jia)(jia)熱加(jia)(jia)壓下硫(liu)化(hua)(hua)(hua)(hua)成(cheng)(cheng)彈性體(ti)。硅(gui)(gui)橡(xiang)膠(jiao)(jiao)的(de)(de)(de)補強(qiang)(qiang)主要(yao)是(shi)各(ge)種(zhong)(zhong)類(lei)型(xing)的(de)(de)(de)白炭(tan)黑(hei),可使硫(liu)化(hua)(hua)(hua)(hua)膠(jiao)(jiao)的(de)(de)(de)強(qiang)(qiang)度增(zeng)加(jia)(jia)數十倍。有時為了降低(di)成(cheng)(cheng)本或改(gai)善膠(jiao)(jiao)料性能及賦(fu)予硫(liu)化(hua)(hua)(hua)(hua)膠(jiao)(jiao)各(ge)種(zhong)(zhong)特殊的(de)(de)(de)性能,也加(jia)(jia)入相應(ying)的(de)(de)(de)各(ge)種(zhong)(zhong)添加(jia)(jia)劑。硫(liu)化(hua)(hua)(hua)(hua)劑是(shi)各(ge)種(zhong)(zhong)有機過(guo)氧(yang)化(hua)(hua)(hua)(hua)物或加(jia)(jia)成(cheng)(cheng)反應(ying)催化(hua)(hua)(hua)(hua)劑。
加工(gong)成型方法如圖(tu)所(suo)示。一次硫化的(de)(de)(de)目的(de)(de)(de)是進行高分子鏈(lian)的(de)(de)(de)交(jiao)聯反應;二次硫化的(de)(de)(de)目的(de)(de)(de)是進行補充交(jiao)聯、驅除硫化劑分解產(chan)物(wu)(wu)和其他揮發性化合(he)物(wu)(wu)以穩定硫化膠的(de)(de)(de)各項性能。常用的(de)(de)(de)設備有(you)開放式(shi)煉膠機(ji)、捏(nie)合(he)機(ji)及真空密煉機(ji)。
主要性能
(1)高(gao)溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)(de)(de)特征是高(gao)溫(wen)(wen)(wen)(wen)穩定(ding)(ding)性(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常溫(wen)(wen)(wen)(wen)下硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)強度僅是天然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)或(huo)某些(xie)合(he)成橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)一半(ban),但在(zai)(zai)200℃以上的(de)(de)(de)高(gao)溫(wen)(wen)(wen)(wen)環境下,硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)仍(reng)能(neng)(neng)保持一定(ding)(ding)的(de)(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)(he)表面硬(ying)度,且力學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)無明顯(xian)變化(hua)(hua)(hua)。(2)低溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)(de)玻璃化(hua)(hua)(hua)溫(wen)(wen)(wen)(wen)度一般(ban)為-70~-50℃,特殊配方可達(da)-100℃,表明其(qi)低溫(wen)(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)優異。這對(dui)(dui)航空(kong)、宇(yu)航工(gong)業的(de)(de)(de)意義(yi)重大。(3)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)中(zhong)(zhong)Si-O-Si鍵(jian)對(dui)(dui)氧(yang)、臭氧(yang)及紫外線等(deng)(deng)十分穩定(ding)(ding),在(zai)(zai)不(bu)加任何添加劑(ji)的(de)(de)(de)情況(kuang)下,就具(ju)有(you)優良(liang)的(de)(de)(de)耐(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)(dian)氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有(you)優異的(de)(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng),耐(nai)電(dian)(dian)暈(yun)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)(he)耐(nai)電(dian)(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常好。(5)物理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)常溫(wen)(wen)(wen)(wen)下的(de)(de)(de)物理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)比(bi)通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)差,但在(zai)(zai)150℃的(de)(de)(de)高(gao)溫(wen)(wen)(wen)(wen)和(he)(he)-50℃的(de)(de)(de)低溫(wen)(wen)(wen)(wen)下,其(qi)物理(li)機(ji)械性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)優于通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)油及化(hua)(hua)(hua)學(xue)試劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有(you)中(zhong)(zhong)等(deng)(deng)的(de)(de)(de)耐(nai)油、耐(nai)溶劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。(7)氣(qi)(qi)體(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。室(shi)溫(wen)(wen)(wen)(wen)下硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)對(dui)(dui)空(kong)氣(qi)(qi)、氮、氧(yang)、二氧(yang)化(hua)(hua)(hua)碳等(deng)(deng)氣(qi)(qi)體(ti)的(de)(de)(de)透氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)比(bi)天然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)高(gao)出30-50倍。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)無毒,無味(wei),無嗅(xiu),與(yu)人(ren)體(ti)組(zu)織不(bu)粘連,具(ju)有(you)抗凝血(xue)作(zuo)用(yong),對(dui)(dui)肌體(ti)組(zu)織的(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常少。特別適合(he)作(zuo)為醫用(yong)材料。
硅橡膠的用量
據中國(guo)(guo)(guo)汽(qi)(qi)(qi)車(che)工(gong)業(ye)協會統計,2012年,汽(qi)(qi)(qi)車(che)產(chan)銷分別(bie)達到1927.18萬(wan)輛和1930.64萬(wan)輛,同(tong)比分別(bie)增長4.63%和4.33%,汽(qi)(qi)(qi)車(che)工(gong)業(ye)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)用(yong)(yong)(yong)量(liang)(liang)約達2.0萬(wan)t。根據觀研天下的(de)新(xin)研究(jiu),增加(jia)有(you)機(ji)硅(gui)(gui)材料在汽(qi)(qi)(qi)車(che)零部(bu)件方(fang)面的(de)用(yong)(yong)(yong)量(liang)(liang),可以大幅(fu)度提(ti)高汽(qi)(qi)(qi)車(che)的(de)安(an)全性(xing)能,因(yin)此(ci),汽(qi)(qi)(qi)車(che)產(chan)量(liang)(liang)和單車(che)用(yong)(yong)(yong)量(liang)(liang)水(shui)平的(de)提(ti)高都(dou)將推動汽(qi)(qi)(qi)車(che)工(gong)業(ye)對硅(gui)(gui)橡(xiang)(xiang)膠(jiao)需(xu)求(qiu)的(de)增加(jia)。國(guo)(guo)(guo)家鼓勵(li)自(zi)主(zhu)品(pin)(pin)(pin)(pin)牌(pai)(pai)(pai)的(de)汽(qi)(qi)(qi)車(che)發展,關鍵汽(qi)(qi)(qi)車(che)零部(bu)件實現自(zi)主(zhu)化,《2012年度黨(dang)政機(ji)關公務用(yong)(yong)(yong)車(che)選用(yong)(yong)(yong)車(che)型目錄(征求(qiu)意見稿)》為(wei)自(zi)主(zhu)品(pin)(pin)(pin)(pin)牌(pai)(pai)(pai)擴大在政府采(cai)(cai)購的(de)市場份額(e),為(wei)改變(bian)目前(qian)國(guo)(guo)(guo)內政府采(cai)(cai)購以合資品(pin)(pin)(pin)(pin)牌(pai)(pai)(pai)產(chan)品(pin)(pin)(pin)(pin)為(wei)主(zhu)的(de)局面提(ti)供(gong)了(le)保障。促進自(zi)主(zhu)品(pin)(pin)(pin)(pin)牌(pai)(pai)(pai)發展,國(guo)(guo)(guo)產(chan)汽(qi)(qi)(qi)車(che)業(ye)的(de)繁(fan)榮將為(wei)汽(qi)(qi)(qi)車(che)膠(jiao)的(de)應用(yong)(yong)(yong)提(ti)供(gong)有(you)力(li)保障。預測未來(lai)3年,我國(guo)(guo)(guo)室(shi)溫硫化硅(gui)(gui)橡(xiang)(xiang)膠(jiao)在汽(qi)(qi)(qi)車(che)行業(ye)將以年均20%增長。
此(ci)外,硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)是重(zhong)要的(de)非(fei)石油(you)基(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao),約占非(fei)石油(you)基(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)消(xiao)費量的(de)98%。但因為(wei)石油(you)價(jia)格(ge)的(de)大(da)(da)(da)幅上漲,同時我國(guo)在硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)關鍵(jian)原料有機(ji)硅(gui)(gui)單(dan)體的(de)生產技術方面取(qu)得突破,有機(ji)硅(gui)(gui)單(dan)體的(de)生產技術在2005年前被幾家(jia)跨國(guo)公司壟斷,但目前我國(guo)已(yi)發展(zhan)成(cheng)為(wei)全球有機(ji)硅(gui)(gui)單(dan)體第1大(da)(da)(da)國(guo),這(zhe)2個(ge)方面原因使硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)價(jia)格(ge)從2011年起開始低于石油(you)基(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao),僅約為(wei)大(da)(da)(da)宗石油(you)基(ji)(ji)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)的(de)80%~90%,成(cheng)為(wei)廉價(jia)的(de)合(he)(he)成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao),并開始大(da)(da)(da)規模替代石油(you)基(ji)(ji)合(he)(he)成(cheng)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)。這(zhe)將(jiang)極大(da)(da)(da)拓展(zhan)有機(ji)硅(gui)(gui)產業的(de)市場空間,同時將(jiang)帶動硅(gui)(gui)油(you)、硅(gui)(gui)烷(wan)偶聯劑(ji)和(he)硅(gui)(gui)樹脂等其他有機(ji)硅(gui)(gui)產品(pin)的(de)消(xiao)費。