
硅橡膠是指主(zhu)鏈由硅(gui)和氧原子交替(ti)構成(cheng),硅(gui)原子上通常連(lian)有兩個(ge)有機基(ji)團(tuan)的(de)(de)(de)(de)橡(xiang)(xiang)膠。普通的(de)(de)(de)(de)硅(gui)橡(xiang)(xiang)膠主(zhu)要由含甲基(ji)和少(shao)量乙烯基(ji)的(de)(de)(de)(de)硅(gui)氧鏈節組成(cheng)。苯基(ji)的(de)(de)(de)(de)引(yin)入(ru)可(ke)提高硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)(de)耐高、低溫(wen)性(xing)(xing)(xing)(xing)能(neng),三氟(fu)丙(bing)基(ji)及氰基(ji)的(de)(de)(de)(de)引(yin)入(ru)則可(ke)提高硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)(de)耐溫(wen)及耐油性(xing)(xing)(xing)(xing)能(neng)。硅(gui)橡(xiang)(xiang)膠耐低溫(wen)性(xing)(xing)(xing)(xing)能(neng)良好,一般在-55℃下仍(reng)(reng)能(neng)工作。引(yin)入(ru)苯基(ji)后,可(ke)達-73℃。硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)(de)耐熱性(xing)(xing)(xing)(xing)能(neng)也(ye)很突出(chu),在180℃下可(ke)長(chang)(chang)期工作,稍高于200℃也(ye)能(neng)承受數周或更長(chang)(chang)時間仍(reng)(reng)有彈(dan)性(xing)(xing)(xing)(xing),瞬時可(ke)耐300℃以上的(de)(de)(de)(de)高溫(wen)。硅(gui)橡(xiang)(xiang)膠的(de)(de)(de)(de)透氣性(xing)(xing)(xing)(xing)好,氧氣透過率(lv)在合成(cheng)聚(ju)合物中是較(jiao)高的(de)(de)(de)(de)。此外,硅(gui)橡(xiang)(xiang)膠還(huan)具(ju)有生理惰(duo)性(xing)(xing)(xing)(xing)、不(bu)會導致凝血的(de)(de)(de)(de)突出(chu)特(te)性(xing)(xing)(xing)(xing),因此在醫用(yong)領(ling)域應用(yong)廣(guang)泛。
主要品種
硅(gui)橡膠分類的方(fang)法很多,通常按固(gu)化
前的(de)形態分(fen)為(wei)固體(ti)硅橡(xiang)膠和(he)液(ye)體(ti)硅橡(xiang)膠;按硫(liu)化溫(wen)度分(fen)為(wei)室溫(wen)硫(liu)化硅橡(xiang)膠,高溫(wen)硫(liu)化硅橡(xiang)膠;按所用單體(ti)的(de)不(bu)同(tong),可分(fen)為(wei)甲(jia)基(ji)(ji)乙烯基(ji)(ji)硅橡(xiang)膠,甲(jia)基(ji)(ji)苯基(ji)(ji)乙烯基(ji)(ji)硅橡(xiang)膠、氟(fu)硅,腈硅橡(xiang)膠等(deng);按性能和(he)用途的(de)不(bu)同(tong)又可分(fen)為(wei)通用型(xing)(xing)(xing)(xing)、超(chao)耐(nai)低溫(wen)型(xing)(xing)(xing)(xing)、超(chao)耐(nai)高溫(wen)型(xing)(xing)(xing)(xing)、高強力型(xing)(xing)(xing)(xing)、耐(nai)油型(xing)(xing)(xing)(xing)、醫用型(xing)(xing)(xing)(xing)等(deng)等(deng)。
發(fa)展史
硅(gui)(gui)橡(xiang)(xiang)膠(jiao)早期是由美(mei)國(guo)以三氯化鐵為催化劑(ji)合(he)(he)成的(de)(de)。1945年,硅(gui)(gui)橡(xiang)(xiang)膠(jiao)產(chan)(chan)品(pin)問世。1948年,采用高(gao)比(bi)表面(mian)積的(de)(de)氣相法白(bai)炭(tan)黑補強的(de)(de)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)研制成功(gong),使(shi)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)性能躍升(sheng)到實用階(jie)段,奠定了現代硅(gui)(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產(chan)(chan)技術(shu)的(de)(de)基礎(chu)。從(cong)二甲基二氯硅(gui)(gui)烷合(he)(he)成開(kai)(kai)始(shi)生(sheng)產(chan)(chan)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)國(guo)家有(you)美(mei)國(guo)。俄羅(luo)斯(si)、德(de)國(guo)、日(ri)本、韓國(guo)和中(zhong)國(guo)等。中(zhong)國(guo)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)(de)工業化研究始(shi)于(yu)1957年,多家研究所和企業陸續(xu)開(kai)(kai)發(fa)出各(ge)種硅(gui)(gui)橡(xiang)(xiang)膠(jiao)。到2003年底,中(zhong)國(guo)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)生(sheng)產(chan)(chan)能力為135千噸(dun)(dun),其中(zhong)高(gao)溫膠(jiao)100千噸(dun)(dun)。
高溫硫化硅橡膠
高溫(wen)硫化(hua)(hua)(hua)硅橡膠(jiao)是指聚硅氧(yang)(yang)烷(wan)變成(cheng)(cheng)彈性(xing)體的(de)(de)(de)過程是經過高溫(wen)(110-170℃)硫化(hua)(hua)(hua)成(cheng)(cheng)型的(de)(de)(de)。它主(zhu)要(yao)以高分子量的(de)(de)(de)聚甲基(ji)乙烯基(ji)硅氧(yang)(yang)烷(wan)為(wei)生膠(jiao),混入補(bu)強填料(liao)、硫化(hua)(hua)(hua)劑等,在加(jia)熱加(jia)壓下硫化(hua)(hua)(hua)成(cheng)(cheng)彈性(xing)體。硅橡膠(jiao)的(de)(de)(de)補(bu)強主(zhu)要(yao)是各種(zhong)類型的(de)(de)(de)白炭(tan)黑,可使硫化(hua)(hua)(hua)膠(jiao)的(de)(de)(de)強度增加(jia)數十倍。有(you)(you)時為(wei)了降低(di)成(cheng)(cheng)本(ben)或(huo)(huo)改善膠(jiao)料(liao)性(xing)能(neng)及賦予硫化(hua)(hua)(hua)膠(jiao)各種(zhong)特殊(shu)的(de)(de)(de)性(xing)能(neng),也加(jia)入相應的(de)(de)(de)各種(zhong)添(tian)加(jia)劑。硫化(hua)(hua)(hua)劑是各種(zhong)有(you)(you)機(ji)過氧(yang)(yang)化(hua)(hua)(hua)物或(huo)(huo)加(jia)成(cheng)(cheng)反應催化(hua)(hua)(hua)劑。
加工(gong)成型方法(fa)如圖(tu)所示(shi)。一(yi)次(ci)硫(liu)化(hua)的(de)(de)目(mu)的(de)(de)是(shi)進行高分(fen)子鏈的(de)(de)交聯(lian)反應;二次(ci)硫(liu)化(hua)的(de)(de)目(mu)的(de)(de)是(shi)進行補充交聯(lian)、驅除(chu)硫(liu)化(hua)劑(ji)分(fen)解產物和其他揮發性(xing)化(hua)合物以穩定(ding)硫(liu)化(hua)膠的(de)(de)各項性(xing)能。常(chang)用的(de)(de)設備有(you)開放式煉膠機、捏合機及真空密煉機。
主要性能(neng)
(1)高溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)特征(zheng)是(shi)高溫(wen)穩定性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing),雖然常溫(wen)下硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)強度僅是(shi)天(tian)然橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)或某些(xie)合成橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)一(yi)半,但在200℃以(yi)上的(de)高溫(wen)環境下,硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)保持一(yi)定的(de)柔韌性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)表面硬度,且(qie)力學(xue)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)無(wu)明(ming)顯(xian)變(bian)化(hua)(hua)。(2)低溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)玻璃化(hua)(hua)溫(wen)度一(yi)般(ban)為-70~-50℃,特殊配方(fang)可達(da)-100℃,表明(ming)其低溫(wen)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)異。這對航空、宇航工業的(de)意義重大。(3)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)中Si-O-Si鍵對氧、臭(chou)氧及紫外(wai)線等(deng)十分穩定,在不加(jia)任何添加(jia)劑的(de)情況下,就具(ju)有優(you)良的(de)耐(nai)(nai)候性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。(4)電氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有優(you)異的(de)絕緣(yuan)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng),耐(nai)(nai)電暈性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)電弧性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)也(ye)非常好。(5)物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)常溫(wen)下的(de)物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)比通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)差,但在150℃的(de)高溫(wen)和(he)-50℃的(de)低溫(wen)下,其物理機(ji)械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)優(you)于通(tong)用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及化(hua)(hua)學(xue)試劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)具(ju)有中等(deng)的(de)耐(nai)(nai)油、耐(nai)(nai)溶(rong)劑性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。(7)氣(qi)體(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)。室溫(wen)下硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)對空氣(qi)、氮、氧、二氧化(hua)(hua)碳等(deng)氣(qi)體(ti)的(de)透氣(qi)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)比天(tian)然橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)高出30-50倍。(8)生理惰(duo)性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)無(wu)毒,無(wu)味(wei),無(wu)嗅(xiu),與人體(ti)組織不粘(zhan)連,具(ju)有抗(kang)凝血作用,對肌體(ti)組織的(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)(xing)非常少。特別適(shi)合作為醫用材料。
硅(gui)橡膠的用量
據(ju)中(zhong)國(guo)(guo)汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)協會統(tong)計(ji),2012年(nian),汽(qi)(qi)(qi)(qi)車(che)(che)(che)產銷分別達到1927.18萬輛和1930.64萬輛,同比分別增(zeng)(zeng)長(chang)4.63%和4.33%,汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)硅橡膠(jiao)的用(yong)量約達2.0萬t。根據(ju)觀研天下的新研究,增(zeng)(zeng)加(jia)有(you)(you)機硅材料在汽(qi)(qi)(qi)(qi)車(che)(che)(che)零(ling)部件方面(mian)的用(yong)量,可(ke)以(yi)大幅度提(ti)(ti)(ti)高汽(qi)(qi)(qi)(qi)車(che)(che)(che)的安(an)全(quan)性能,因此,汽(qi)(qi)(qi)(qi)車(che)(che)(che)產量和單(dan)車(che)(che)(che)用(yong)量水平的提(ti)(ti)(ti)高都將(jiang)(jiang)推動汽(qi)(qi)(qi)(qi)車(che)(che)(che)工業(ye)對(dui)硅橡膠(jiao)需求的增(zeng)(zeng)加(jia)。國(guo)(guo)家鼓勵自(zi)(zi)(zi)主品(pin)牌的汽(qi)(qi)(qi)(qi)車(che)(che)(che)發(fa)展(zhan),關鍵汽(qi)(qi)(qi)(qi)車(che)(che)(che)零(ling)部件實(shi)現自(zi)(zi)(zi)主化,《2012年(nian)度黨政(zheng)機關公務用(yong)車(che)(che)(che)選用(yong)車(che)(che)(che)型目(mu)錄(征求意見稿(gao))》為自(zi)(zi)(zi)主品(pin)牌擴大在政(zheng)府采(cai)(cai)購(gou)的市場份(fen)額,為改(gai)變(bian)目(mu)前國(guo)(guo)內(nei)政(zheng)府采(cai)(cai)購(gou)以(yi)合資品(pin)牌產品(pin)為主的局面(mian)提(ti)(ti)(ti)供了保障。促進自(zi)(zi)(zi)主品(pin)牌發(fa)展(zhan),國(guo)(guo)產汽(qi)(qi)(qi)(qi)車(che)(che)(che)業(ye)的繁榮將(jiang)(jiang)為汽(qi)(qi)(qi)(qi)車(che)(che)(che)膠(jiao)的應用(yong)提(ti)(ti)(ti)供有(you)(you)力(li)保障。預測未來3年(nian),我(wo)國(guo)(guo)室溫硫化硅橡膠(jiao)在汽(qi)(qi)(qi)(qi)車(che)(che)(che)行業(ye)將(jiang)(jiang)以(yi)年(nian)均20%增(zeng)(zeng)長(chang)。
此外,硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)是重要的(de)(de)(de)非石(shi)油(you)基(ji)合(he)成橡(xiang)(xiang)膠(jiao)(jiao),約占非石(shi)油(you)基(ji)合(he)成橡(xiang)(xiang)膠(jiao)(jiao)消費(fei)量的(de)(de)(de)98%。但因為(wei)石(shi)油(you)價(jia)格(ge)的(de)(de)(de)大幅(fu)上(shang)漲,同時(shi)我(wo)國在(zai)硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)關鍵(jian)原(yuan)(yuan)料有(you)機硅(gui)(gui)(gui)單體(ti)的(de)(de)(de)生(sheng)產(chan)(chan)技術方面(mian)取得突破,有(you)機硅(gui)(gui)(gui)單體(ti)的(de)(de)(de)生(sheng)產(chan)(chan)技術在(zai)2005年(nian)前(qian)被幾(ji)家(jia)跨國公司(si)壟斷(duan),但目前(qian)我(wo)國已發展(zhan)成為(wei)全球有(you)機硅(gui)(gui)(gui)單體(ti)第1大國,這2個方面(mian)原(yuan)(yuan)因使硅(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)價(jia)格(ge)從2011年(nian)起開(kai)始低于石(shi)油(you)基(ji)合(he)成橡(xiang)(xiang)膠(jiao)(jiao),僅約為(wei)大宗石(shi)油(you)基(ji)橡(xiang)(xiang)膠(jiao)(jiao)的(de)(de)(de)80%~90%,成為(wei)廉價(jia)的(de)(de)(de)合(he)成橡(xiang)(xiang)膠(jiao)(jiao),并開(kai)始大規模替代石(shi)油(you)基(ji)合(he)成橡(xiang)(xiang)膠(jiao)(jiao)。這將極大拓展(zhan)有(you)機硅(gui)(gui)(gui)產(chan)(chan)業(ye)的(de)(de)(de)市場空間,同時(shi)將帶動硅(gui)(gui)(gui)油(you)、硅(gui)(gui)(gui)烷偶聯(lian)劑和硅(gui)(gui)(gui)樹脂等(deng)其他有(you)機硅(gui)(gui)(gui)產(chan)(chan)品的(de)(de)(de)消費(fei)。