硅橡膠是指主鏈由硅(gui)(gui)(gui)和(he)氧(yang)原(yuan)子(zi)交(jiao)替構成,硅(gui)(gui)(gui)原(yuan)子(zi)上(shang)通(tong)常連(lian)有(you)兩(liang)個有(you)機基(ji)(ji)(ji)團的(de)(de)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)。普(pu)通(tong)的(de)(de)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)主要由含甲基(ji)(ji)(ji)和(he)少量乙烯基(ji)(ji)(ji)的(de)(de)硅(gui)(gui)(gui)氧(yang)鏈節組成。苯基(ji)(ji)(ji)的(de)(de)引入可(ke)提高硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)耐(nai)(nai)(nai)(nai)高、低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)能(neng)(neng)(neng),三氟(fu)丙基(ji)(ji)(ji)及氰(qing)基(ji)(ji)(ji)的(de)(de)引入則(ze)可(ke)提高硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)耐(nai)(nai)(nai)(nai)溫(wen)(wen)及耐(nai)(nai)(nai)(nai)油性(xing)(xing)(xing)(xing)能(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)耐(nai)(nai)(nai)(nai)低(di)溫(wen)(wen)性(xing)(xing)(xing)(xing)能(neng)(neng)(neng)良好(hao),一般在-55℃下(xia)仍能(neng)(neng)(neng)工作。引入苯基(ji)(ji)(ji)后,可(ke)達-73℃。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)耐(nai)(nai)(nai)(nai)熱(re)性(xing)(xing)(xing)(xing)能(neng)(neng)(neng)也很突(tu)出(chu),在180℃下(xia)可(ke)長期工作,稍(shao)高于200℃也能(neng)(neng)(neng)承受(shou)數周或更(geng)長時(shi)間仍有(you)彈性(xing)(xing)(xing)(xing),瞬(shun)時(shi)可(ke)耐(nai)(nai)(nai)(nai)300℃以上(shang)的(de)(de)高溫(wen)(wen)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)的(de)(de)透氣性(xing)(xing)(xing)(xing)好(hao),氧(yang)氣透過率在合(he)成聚合(he)物中是較(jiao)高的(de)(de)。此(ci)外,硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)還(huan)具有(you)生(sheng)理(li)惰(duo)性(xing)(xing)(xing)(xing)、不(bu)會導致凝血的(de)(de)突(tu)出(chu)特性(xing)(xing)(xing)(xing),因(yin)此(ci)在醫(yi)用領域應(ying)用廣泛。
主要品種
硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)分(fen)(fen)類的方法很(hen)多,通常按固(gu)(gu)化(hua)(hua)前(qian)的形態分(fen)(fen)為固(gu)(gu)體(ti)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)和(he)(he)液體(ti)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao);按硫(liu)化(hua)(hua)溫(wen)(wen)度(du)分(fen)(fen)為室(shi)溫(wen)(wen)硫(liu)化(hua)(hua)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao),高溫(wen)(wen)硫(liu)化(hua)(hua)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao);按所用(yong)單(dan)體(ti)的不同,可分(fen)(fen)為甲基(ji)乙(yi)烯基(ji)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao),甲基(ji)苯基(ji)乙(yi)烯基(ji)硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)、氟硅(gui)(gui)(gui),腈硅(gui)(gui)(gui)橡(xiang)膠(jiao)(jiao)等(deng);按性(xing)能和(he)(he)用(yong)途的不同又可分(fen)(fen)為通用(yong)型(xing)(xing)(xing)、超耐(nai)低溫(wen)(wen)型(xing)(xing)(xing)、超耐(nai)高溫(wen)(wen)型(xing)(xing)(xing)、高強力型(xing)(xing)(xing)、耐(nai)油型(xing)(xing)(xing)、醫用(yong)型(xing)(xing)(xing)等(deng)等(deng)。
發展史
硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)早期是(shi)由美國以(yi)三氯(lv)化(hua)鐵(tie)為催化(hua)劑(ji)合成的(de)(de)。1945年(nian)(nian),硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)產品問(wen)世。1948年(nian)(nian),采(cai)用高(gao)比表面積的(de)(de)氣(qi)相(xiang)法白(bai)炭黑補強的(de)(de)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)研(yan)制成功,使(shi)硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)性能(neng)躍升到(dao)實(shi)用階段(duan),奠定了現代硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生(sheng)產技術的(de)(de)基礎。從二甲基二氯(lv)硅(gui)烷合成開始生(sheng)產硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)國家有美國。俄羅斯、德國、日(ri)本(ben)、韓(han)國和中國等。中國硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)的(de)(de)工(gong)業化(hua)研(yan)究(jiu)始于1957年(nian)(nian),多家研(yan)究(jiu)所和企業陸續(xu)開發(fa)出各(ge)種硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)。到(dao)2003年(nian)(nian)底,中國硅(gui)橡(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)生(sheng)產能(neng)力為135千(qian)噸,其中高(gao)溫膠(jiao)(jiao)(jiao)(jiao)100千(qian)噸。
高溫硫化硅橡膠
高溫(wen)硫化(hua)(hua)硅橡(xiang)膠是指聚硅氧烷(wan)(wan)變成(cheng)(cheng)彈性體的(de)(de)(de)過程是經過高溫(wen)(110-170℃)硫化(hua)(hua)成(cheng)(cheng)型的(de)(de)(de)。它(ta)主要以高分子量的(de)(de)(de)聚甲(jia)基乙烯基硅氧烷(wan)(wan)為生膠,混入(ru)補強填料(liao)、硫化(hua)(hua)劑等,在加(jia)熱加(jia)壓下硫化(hua)(hua)成(cheng)(cheng)彈性體。硅橡(xiang)膠的(de)(de)(de)補強主要是各(ge)種(zhong)類型的(de)(de)(de)白炭黑,可使硫化(hua)(hua)膠的(de)(de)(de)強度增加(jia)數(shu)十倍。有時(shi)為了降低(di)成(cheng)(cheng)本或改(gai)善膠料(liao)性能及賦予硫化(hua)(hua)膠各(ge)種(zhong)特(te)殊的(de)(de)(de)性能,也加(jia)入(ru)相(xiang)應的(de)(de)(de)各(ge)種(zhong)添加(jia)劑。硫化(hua)(hua)劑是各(ge)種(zhong)有機過氧化(hua)(hua)物或加(jia)成(cheng)(cheng)反應催化(hua)(hua)劑。
加(jia)工成(cheng)型方法如圖所示。一(yi)次硫化(hua)的(de)目的(de)是進(jin)行高分子鏈的(de)交(jiao)(jiao)聯反應;二次硫化(hua)的(de)目的(de)是進(jin)行補充交(jiao)(jiao)聯、驅(qu)除硫化(hua)劑(ji)分解產(chan)物(wu)和其他揮發性化(hua)合物(wu)以穩定硫化(hua)膠(jiao)的(de)各項性能。常用的(de)設(she)備有(you)開(kai)放(fang)式煉(lian)膠(jiao)機、捏合機及真空密(mi)煉(lian)機。
主要性能
(1)高溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)顯著的(de)(de)特征(zheng)是(shi)高溫(wen)(wen)穩定(ding)性(xing)(xing)(xing)(xing)(xing)(xing),雖然常(chang)(chang)溫(wen)(wen)下(xia)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)強度(du)(du)僅是(shi)天然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)或某(mou)些合成橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)一(yi)半(ban),但在(zai)200℃以上的(de)(de)高溫(wen)(wen)環(huan)境下(xia),硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)(neng)保持一(yi)定(ding)的(de)(de)柔(rou)韌性(xing)(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)(xing)和(he)表面硬度(du)(du),且力(li)學性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)無明顯變化(hua)(hua)。(2)低溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)玻璃化(hua)(hua)溫(wen)(wen)度(du)(du)一(yi)般為(wei)-70~-50℃,特殊(shu)配方可達(da)-100℃,表明其低溫(wen)(wen)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優(you)異。這對(dui)航(hang)空、宇航(hang)工(gong)業的(de)(de)意義重大。(3)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)中Si-O-Si鍵對(dui)氧、臭氧及紫外(wai)線等十分穩定(ding),在(zai)不(bu)加任何添加劑(ji)的(de)(de)情況下(xia),就具有優(you)良的(de)(de)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)(xing)。(4)電(dian)氣性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有優(you)異的(de)(de)絕緣(yuan)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng),耐(nai)(nai)電(dian)暈性(xing)(xing)(xing)(xing)(xing)(xing)和(he)耐(nai)(nai)電(dian)弧性(xing)(xing)(xing)(xing)(xing)(xing)也非常(chang)(chang)好。(5)物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)常(chang)(chang)溫(wen)(wen)下(xia)的(de)(de)物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)比通(tong)用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)差,但在(zai)150℃的(de)(de)高溫(wen)(wen)和(he)-50℃的(de)(de)低溫(wen)(wen)下(xia),其物(wu)理(li)機械(xie)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)優(you)于通(tong)用橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油(you)及化(hua)(hua)學試劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)。普通(tong)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)具有中等的(de)(de)耐(nai)(nai)油(you)、耐(nai)(nai)溶劑(ji)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。(7)氣體(ti)透過性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)。室溫(wen)(wen)下(xia)硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)對(dui)空氣、氮、氧、二氧化(hua)(hua)碳等氣體(ti)的(de)(de)透氣性(xing)(xing)(xing)(xing)(xing)(xing)比天然橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)高出30-50倍。(8)生理(li)惰性(xing)(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)無毒,無味(wei),無嗅(xiu),與(yu)人體(ti)組織不(bu)粘連(lian),具有抗凝(ning)血作(zuo)用,對(dui)肌(ji)體(ti)組織的(de)(de)反應性(xing)(xing)(xing)(xing)(xing)(xing)非常(chang)(chang)少。特別適合作(zuo)為(wei)醫用材料。
硅橡膠的用量
據(ju)中國汽(qi)(qi)(qi)(qi)車(che)(che)工業協會統計,2012年(nian),汽(qi)(qi)(qi)(qi)車(che)(che)產銷分別(bie)達到1927.18萬輛和(he)1930.64萬輛,同(tong)比(bi)分別(bie)增長4.63%和(he)4.33%,汽(qi)(qi)(qi)(qi)車(che)(che)工業硅橡膠的(de)(de)(de)用(yong)量約達2.0萬t。根據(ju)觀研天下的(de)(de)(de)新研究(jiu),增加(jia)(jia)有(you)機硅材料在汽(qi)(qi)(qi)(qi)車(che)(che)零部件方面的(de)(de)(de)用(yong)量,可(ke)以大幅度提(ti)(ti)高汽(qi)(qi)(qi)(qi)車(che)(che)的(de)(de)(de)安(an)全性能,因此(ci),汽(qi)(qi)(qi)(qi)車(che)(che)產量和(he)單車(che)(che)用(yong)量水平的(de)(de)(de)提(ti)(ti)高都將推動汽(qi)(qi)(qi)(qi)車(che)(che)工業對硅橡膠需(xu)求的(de)(de)(de)增加(jia)(jia)。國家鼓(gu)勵(li)自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)的(de)(de)(de)汽(qi)(qi)(qi)(qi)車(che)(che)發展,關鍵汽(qi)(qi)(qi)(qi)車(che)(che)零部件實現自(zi)主(zhu)(zhu)化(hua),《2012年(nian)度黨政(zheng)機關公務用(yong)車(che)(che)選(xuan)用(yong)車(che)(che)型目(mu)錄(lu)(征求意見(jian)稿)》為(wei)自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)擴大在政(zheng)府采購的(de)(de)(de)市(shi)場份額,為(wei)改變目(mu)前國內政(zheng)府采購以合(he)資品(pin)牌(pai)(pai)產品(pin)為(wei)主(zhu)(zhu)的(de)(de)(de)局面提(ti)(ti)供(gong)了保障(zhang)。促進(jin)自(zi)主(zhu)(zhu)品(pin)牌(pai)(pai)發展,國產汽(qi)(qi)(qi)(qi)車(che)(che)業的(de)(de)(de)繁榮將為(wei)汽(qi)(qi)(qi)(qi)車(che)(che)膠的(de)(de)(de)應用(yong)提(ti)(ti)供(gong)有(you)力保障(zhang)。預測未來3年(nian),我國室溫硫化(hua)硅橡膠在汽(qi)(qi)(qi)(qi)車(che)(che)行業將以年(nian)均20%增長。
此外,硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)是重要的(de)非石油(you)(you)基(ji)合成(cheng)(cheng)橡(xiang)(xiang)膠(jiao),約占非石油(you)(you)基(ji)合成(cheng)(cheng)橡(xiang)(xiang)膠(jiao)消費量的(de)98%。但(dan)因為(wei)(wei)石油(you)(you)價格的(de)大幅上漲,同(tong)時(shi)我國在硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)關(guan)鍵原料有(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)單體的(de)生產技(ji)(ji)術方面(mian)取得(de)突破(po),有(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)單體的(de)生產技(ji)(ji)術在2005年前(qian)被幾家跨國公司(si)壟斷(duan),但(dan)目(mu)前(qian)我國已發(fa)展成(cheng)(cheng)為(wei)(wei)全球有(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)單體第1大國,這2個(ge)方面(mian)原因使硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)價格從2011年起開始低于石油(you)(you)基(ji)合成(cheng)(cheng)橡(xiang)(xiang)膠(jiao),僅約為(wei)(wei)大宗(zong)石油(you)(you)基(ji)橡(xiang)(xiang)膠(jiao)的(de)80%~90%,成(cheng)(cheng)為(wei)(wei)廉價的(de)合成(cheng)(cheng)橡(xiang)(xiang)膠(jiao),并開始大規(gui)模(mo)替代石油(you)(you)基(ji)合成(cheng)(cheng)橡(xiang)(xiang)膠(jiao)。這將(jiang)極大拓展有(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)產業(ye)的(de)市場空間,同(tong)時(shi)將(jiang)帶動(dong)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)油(you)(you)、硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)烷(wan)偶聯劑和(he)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)樹脂(zhi)等其他有(you)機(ji)(ji)硅(gui)(gui)(gui)(gui)(gui)(gui)(gui)產品的(de)消費。