
硅橡膠是指主(zhu)鏈由(you)硅(gui)(gui)和(he)氧原(yuan)子(zi)交替構成,硅(gui)(gui)原(yuan)子(zi)上通常(chang)連(lian)有兩個有機基(ji)(ji)(ji)團(tuan)的(de)橡(xiang)(xiang)膠(jiao)。普通的(de)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)主(zhu)要由(you)含甲基(ji)(ji)(ji)和(he)少量乙烯基(ji)(ji)(ji)的(de)硅(gui)(gui)氧鏈節組成。苯(ben)基(ji)(ji)(ji)的(de)引入可提(ti)高硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)(nai)(nai)高、低(di)溫(wen)性(xing)(xing)(xing)能,三氟丙基(ji)(ji)(ji)及(ji)氰基(ji)(ji)(ji)的(de)引入則(ze)可提(ti)高硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)(nai)(nai)溫(wen)及(ji)耐(nai)(nai)(nai)(nai)油性(xing)(xing)(xing)能。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)耐(nai)(nai)(nai)(nai)低(di)溫(wen)性(xing)(xing)(xing)能良好,一般在-55℃下仍(reng)能工作。引入苯(ben)基(ji)(ji)(ji)后,可達-73℃。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐(nai)(nai)(nai)(nai)熱性(xing)(xing)(xing)能也很突出,在180℃下可長期工作,稍高于200℃也能承受(shou)數周(zhou)或更長時間仍(reng)有彈性(xing)(xing)(xing),瞬時可耐(nai)(nai)(nai)(nai)300℃以上的(de)高溫(wen)。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)透氣性(xing)(xing)(xing)好,氧氣透過率(lv)在合成聚(ju)合物中(zhong)是較高的(de)。此外,硅(gui)(gui)橡(xiang)(xiang)膠(jiao)還(huan)具有生理惰性(xing)(xing)(xing)、不會導(dao)致凝血(xue)的(de)突出特性(xing)(xing)(xing),因此在醫用領(ling)域應用廣泛。
主要品種
硅橡(xiang)膠(jiao)(jiao)分(fen)(fen)類的(de)(de)方(fang)法(fa)很多(duo),通常按固化(hua)前(qian)的(de)(de)形態分(fen)(fen)為(wei)固體(ti)硅橡(xiang)膠(jiao)(jiao)和液體(ti)硅橡(xiang)膠(jiao)(jiao);按硫(liu)化(hua)溫度分(fen)(fen)為(wei)室溫硫(liu)化(hua)硅橡(xiang)膠(jiao)(jiao),高(gao)溫硫(liu)化(hua)硅橡(xiang)膠(jiao)(jiao);按所用單體(ti)的(de)(de)不(bu)同,可分(fen)(fen)為(wei)甲基乙烯基硅橡(xiang)膠(jiao)(jiao),甲基苯基乙烯基硅橡(xiang)膠(jiao)(jiao)、氟硅,腈硅橡(xiang)膠(jiao)(jiao)等(deng);按性能(neng)和用途(tu)的(de)(de)不(bu)同又可分(fen)(fen)為(wei)通用型(xing)(xing)、超耐低溫型(xing)(xing)、超耐高(gao)溫型(xing)(xing)、高(gao)強力型(xing)(xing)、耐油型(xing)(xing)、醫(yi)用型(xing)(xing)等(deng)等(deng)。
發展史
硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)早期是(shi)由美(mei)國(guo)以(yi)三氯化鐵為(wei)催(cui)化劑合成(cheng)(cheng)的。1945年(nian),硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)產品問(wen)世。1948年(nian),采用(yong)高(gao)比表(biao)面積的氣相法白(bai)炭(tan)黑補強的硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)研(yan)(yan)制成(cheng)(cheng)功(gong),使硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的性能躍升到實用(yong)階段,奠定了現代硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)生(sheng)產技術(shu)的基礎。從二甲基二氯硅(gui)烷合成(cheng)(cheng)開始生(sheng)產硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的國(guo)家(jia)有美(mei)國(guo)。俄羅(luo)斯(si)、德國(guo)、日本、韓國(guo)和中國(guo)等。中國(guo)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的工業化研(yan)(yan)究始于(yu)1957年(nian),多家(jia)研(yan)(yan)究所和企(qi)業陸(lu)續(xu)開發出各種硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)。到2003年(nian)底(di),中國(guo)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)生(sheng)產能力為(wei)135千噸(dun),其(qi)中高(gao)溫膠(jiao)(jiao)(jiao)(jiao)(jiao)100千噸(dun)。
高溫硫化硅橡膠
高溫硫(liu)化(hua)硅(gui)橡膠(jiao)(jiao)是(shi)指聚硅(gui)氧(yang)(yang)烷變成(cheng)(cheng)彈性(xing)體的(de)(de)過程是(shi)經過高溫(110-170℃)硫(liu)化(hua)成(cheng)(cheng)型(xing)的(de)(de)。它主要以高分(fen)子量的(de)(de)聚甲基乙(yi)烯基硅(gui)氧(yang)(yang)烷為生膠(jiao)(jiao),混(hun)入補強(qiang)(qiang)填料、硫(liu)化(hua)劑(ji)等,在(zai)加(jia)(jia)熱加(jia)(jia)壓下硫(liu)化(hua)成(cheng)(cheng)彈性(xing)體。硅(gui)橡膠(jiao)(jiao)的(de)(de)補強(qiang)(qiang)主要是(shi)各(ge)種(zhong)(zhong)類型(xing)的(de)(de)白炭(tan)黑,可使硫(liu)化(hua)膠(jiao)(jiao)的(de)(de)強(qiang)(qiang)度增加(jia)(jia)數十倍。有時為了(le)降低成(cheng)(cheng)本或改善膠(jiao)(jiao)料性(xing)能及賦予(yu)硫(liu)化(hua)膠(jiao)(jiao)各(ge)種(zhong)(zhong)特殊(shu)的(de)(de)性(xing)能,也加(jia)(jia)入相應的(de)(de)各(ge)種(zhong)(zhong)添加(jia)(jia)劑(ji)。硫(liu)化(hua)劑(ji)是(shi)各(ge)種(zhong)(zhong)有機過氧(yang)(yang)化(hua)物或加(jia)(jia)成(cheng)(cheng)反(fan)應催(cui)化(hua)劑(ji)。
加工成型方(fang)法如圖所示。一次(ci)硫化(hua)(hua)的(de)(de)目的(de)(de)是進行高分(fen)子(zi)鏈的(de)(de)交(jiao)聯反(fan)應(ying);二次(ci)硫化(hua)(hua)的(de)(de)目的(de)(de)是進行補充交(jiao)聯、驅除硫化(hua)(hua)劑分(fen)解產物和其(qi)他揮發性化(hua)(hua)合(he)物以穩定(ding)硫化(hua)(hua)膠(jiao)的(de)(de)各項性能。常(chang)用的(de)(de)設備(bei)有開放式煉(lian)膠(jiao)機(ji)、捏(nie)合(he)機(ji)及真空密煉(lian)機(ji)。
主要性能
(1)高(gao)溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)顯著的(de)(de)(de)(de)特征(zheng)是(shi)(shi)高(gao)溫(wen)穩定性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然(ran)常溫(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)(de)強度(du)僅是(shi)(shi)天然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)或(huo)某些合成橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)(de)一(yi)半,但在(zai)(zai)200℃以上的(de)(de)(de)(de)高(gao)溫(wen)環境下(xia)(xia),硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)仍(reng)能(neng)(neng)(neng)(neng)(neng)(neng)保持一(yi)定的(de)(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(he)表(biao)面硬度(du),且力學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)無明顯變化(hua)(hua)。(2)低溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)(de)玻璃化(hua)(hua)溫(wen)度(du)一(yi)般(ban)為-70~-50℃,特殊配方可(ke)達(da)-100℃,表(biao)明其(qi)(qi)低溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)優(you)異。這對航空(kong)、宇航工業的(de)(de)(de)(de)意義重大。(3)耐(nai)(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對氧(yang)、臭氧(yang)及紫外線(xian)等(deng)十分穩定,在(zai)(zai)不加任何添加劑(ji)的(de)(de)(de)(de)情況下(xia)(xia),就具(ju)有(you)優(you)良的(de)(de)(de)(de)耐(nai)(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣(qi)(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具(ju)有(you)優(you)異的(de)(de)(de)(de)絕緣性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng),耐(nai)(nai)(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)(nai)電(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也非(fei)常好。(5)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)常溫(wen)下(xia)(xia)的(de)(de)(de)(de)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)比通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)差,但在(zai)(zai)150℃的(de)(de)(de)(de)高(gao)溫(wen)和(he)-50℃的(de)(de)(de)(de)低溫(wen)下(xia)(xia),其(qi)(qi)物理(li)機(ji)械(xie)(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)優(you)于(yu)通(tong)用(yong)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)。(6)耐(nai)(nai)(nai)油及化(hua)(hua)學(xue)試劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)具(ju)有(you)中(zhong)等(deng)的(de)(de)(de)(de)耐(nai)(nai)(nai)油、耐(nai)(nai)(nai)溶(rong)劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)。(7)氣(qi)(qi)(qi)體透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)。室(shi)溫(wen)下(xia)(xia)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)對空(kong)氣(qi)(qi)(qi)、氮(dan)、氧(yang)、二氧(yang)化(hua)(hua)碳等(deng)氣(qi)(qi)(qi)體的(de)(de)(de)(de)透氣(qi)(qi)(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天然(ran)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)高(gao)出30-50倍。(8)生(sheng)理(li)惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)無毒,無味(wei),無嗅,與人體組(zu)織(zhi)不粘連,具(ju)有(you)抗凝血(xue)作用(yong),對肌(ji)體組(zu)織(zhi)的(de)(de)(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非(fei)常少(shao)。特別適合作為醫用(yong)材料。
硅橡膠的用量
據(ju)中國(guo)(guo)(guo)汽(qi)(qi)(qi)車(che)(che)(che)(che)工(gong)(gong)業協會統計,2012年(nian),汽(qi)(qi)(qi)車(che)(che)(che)(che)產(chan)(chan)銷分別達(da)到1927.18萬(wan)輛和1930.64萬(wan)輛,同比(bi)分別增長(chang)4.63%和4.33%,汽(qi)(qi)(qi)車(che)(che)(che)(che)工(gong)(gong)業硅(gui)橡(xiang)(xiang)膠(jiao)的用(yong)(yong)量(liang)(liang)(liang)約達(da)2.0萬(wan)t。根據(ju)觀研天下的新研究(jiu),增加有機硅(gui)材料在(zai)汽(qi)(qi)(qi)車(che)(che)(che)(che)零部件(jian)方面(mian)的用(yong)(yong)量(liang)(liang)(liang),可以大幅(fu)度(du)(du)提高汽(qi)(qi)(qi)車(che)(che)(che)(che)的安全性能,因(yin)此,汽(qi)(qi)(qi)車(che)(che)(che)(che)產(chan)(chan)量(liang)(liang)(liang)和單(dan)車(che)(che)(che)(che)用(yong)(yong)量(liang)(liang)(liang)水平的提高都(dou)將推動汽(qi)(qi)(qi)車(che)(che)(che)(che)工(gong)(gong)業對硅(gui)橡(xiang)(xiang)膠(jiao)需求的增加。國(guo)(guo)(guo)家鼓勵自主(zhu)(zhu)品(pin)(pin)牌(pai)的汽(qi)(qi)(qi)車(che)(che)(che)(che)發(fa)展,關鍵汽(qi)(qi)(qi)車(che)(che)(che)(che)零部件(jian)實(shi)現自主(zhu)(zhu)化,《2012年(nian)度(du)(du)黨政機關公務用(yong)(yong)車(che)(che)(che)(che)選用(yong)(yong)車(che)(che)(che)(che)型(xing)目錄(征求意(yi)見稿)》為(wei)自主(zhu)(zhu)品(pin)(pin)牌(pai)擴大在(zai)政府采購(gou)(gou)的市(shi)場份額,為(wei)改變目前(qian)國(guo)(guo)(guo)內(nei)政府采購(gou)(gou)以合資品(pin)(pin)牌(pai)產(chan)(chan)品(pin)(pin)為(wei)主(zhu)(zhu)的局面(mian)提供了(le)保障。促進自主(zhu)(zhu)品(pin)(pin)牌(pai)發(fa)展,國(guo)(guo)(guo)產(chan)(chan)汽(qi)(qi)(qi)車(che)(che)(che)(che)業的繁(fan)榮將為(wei)汽(qi)(qi)(qi)車(che)(che)(che)(che)膠(jiao)的應用(yong)(yong)提供有力保障。預測未(wei)來3年(nian),我(wo)國(guo)(guo)(guo)室(shi)溫硫化硅(gui)橡(xiang)(xiang)膠(jiao)在(zai)汽(qi)(qi)(qi)車(che)(che)(che)(che)行業將以年(nian)均(jun)20%增長(chang)。
此(ci)外(wai),硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)是重要的(de)(de)(de)非石(shi)油(you)(you)(you)基(ji)(ji)合(he)(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)(jiao),約占非石(shi)油(you)(you)(you)基(ji)(ji)合(he)(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)(jiao)消費量的(de)(de)(de)98%。但因為(wei)石(shi)油(you)(you)(you)價(jia)格的(de)(de)(de)大(da)幅(fu)上漲,同時我國在(zai)(zai)硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)關鍵原(yuan)料(liao)有(you)機(ji)(ji)硅(gui)(gui)單(dan)體(ti)(ti)的(de)(de)(de)生產技(ji)術方面(mian)取得突破,有(you)機(ji)(ji)硅(gui)(gui)單(dan)體(ti)(ti)的(de)(de)(de)生產技(ji)術在(zai)(zai)2005年(nian)前被幾(ji)家跨國公司壟(long)斷,但目前我國已發展成(cheng)(cheng)(cheng)(cheng)為(wei)全球有(you)機(ji)(ji)硅(gui)(gui)單(dan)體(ti)(ti)第1大(da)國,這2個(ge)方面(mian)原(yuan)因使硅(gui)(gui)橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)價(jia)格從2011年(nian)起開始低于石(shi)油(you)(you)(you)基(ji)(ji)合(he)(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)(jiao),僅約為(wei)大(da)宗石(shi)油(you)(you)(you)基(ji)(ji)橡(xiang)膠(jiao)(jiao)(jiao)的(de)(de)(de)80%~90%,成(cheng)(cheng)(cheng)(cheng)為(wei)廉(lian)價(jia)的(de)(de)(de)合(he)(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)(jiao),并開始大(da)規模替(ti)代石(shi)油(you)(you)(you)基(ji)(ji)合(he)(he)成(cheng)(cheng)(cheng)(cheng)橡(xiang)膠(jiao)(jiao)(jiao)。這將極大(da)拓展有(you)機(ji)(ji)硅(gui)(gui)產業的(de)(de)(de)市場空間,同時將帶(dai)動(dong)硅(gui)(gui)油(you)(you)(you)、硅(gui)(gui)烷偶聯劑(ji)和硅(gui)(gui)樹(shu)脂等其他(ta)有(you)機(ji)(ji)硅(gui)(gui)產品的(de)(de)(de)消費。