
硅橡膠是(shi)指主(zhu)鏈(lian)由硅(gui)(gui)和(he)(he)氧(yang)原子交替(ti)構成(cheng),硅(gui)(gui)原子上(shang)(shang)通常(chang)連(lian)有(you)兩個有(you)機基(ji)(ji)團(tuan)的(de)橡(xiang)(xiang)膠(jiao)。普(pu)通的(de)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)主(zhu)要由含甲基(ji)(ji)和(he)(he)少(shao)量(liang)乙(yi)烯基(ji)(ji)的(de)硅(gui)(gui)氧(yang)鏈(lian)節組成(cheng)。苯基(ji)(ji)的(de)引(yin)入可(ke)(ke)提高(gao)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐高(gao)、低溫性(xing)(xing)(xing)能(neng)(neng)(neng),三氟丙基(ji)(ji)及氰基(ji)(ji)的(de)引(yin)入則可(ke)(ke)提高(gao)硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐溫及耐油性(xing)(xing)(xing)能(neng)(neng)(neng)。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)耐低溫性(xing)(xing)(xing)能(neng)(neng)(neng)良好,一(yi)般在-55℃下仍能(neng)(neng)(neng)工(gong)作(zuo)。引(yin)入苯基(ji)(ji)后(hou),可(ke)(ke)達-73℃。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)耐熱性(xing)(xing)(xing)能(neng)(neng)(neng)也(ye)很突(tu)出,在180℃下可(ke)(ke)長(chang)期(qi)工(gong)作(zuo),稍高(gao)于(yu)200℃也(ye)能(neng)(neng)(neng)承(cheng)受數周或更長(chang)時間仍有(you)彈性(xing)(xing)(xing),瞬時可(ke)(ke)耐300℃以(yi)上(shang)(shang)的(de)高(gao)溫。硅(gui)(gui)橡(xiang)(xiang)膠(jiao)的(de)透(tou)氣性(xing)(xing)(xing)好,氧(yang)氣透(tou)過(guo)率在合(he)成(cheng)聚合(he)物中是(shi)較高(gao)的(de)。此(ci)外,硅(gui)(gui)橡(xiang)(xiang)膠(jiao)還具有(you)生理惰性(xing)(xing)(xing)、不會導致凝血的(de)突(tu)出特性(xing)(xing)(xing),因此(ci)在醫用領(ling)域應用廣泛。
主要品種
硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)分(fen)類的方(fang)法很多,通(tong)常按固(gu)化(hua)前的形態分(fen)為(wei)固(gu)體(ti)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)和液體(ti)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao);按硫(liu)化(hua)溫(wen)(wen)度分(fen)為(wei)室溫(wen)(wen)硫(liu)化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao),高(gao)(gao)溫(wen)(wen)硫(liu)化(hua)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao);按所用(yong)單體(ti)的不(bu)同,可分(fen)為(wei)甲基(ji)乙烯(xi)(xi)基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao),甲基(ji)苯(ben)基(ji)乙烯(xi)(xi)基(ji)硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)、氟硅(gui)(gui)(gui)(gui),腈硅(gui)(gui)(gui)(gui)橡(xiang)(xiang)膠(jiao)等;按性能(neng)和用(yong)途(tu)的不(bu)同又可分(fen)為(wei)通(tong)用(yong)型(xing)(xing)、超耐(nai)(nai)低(di)溫(wen)(wen)型(xing)(xing)、超耐(nai)(nai)高(gao)(gao)溫(wen)(wen)型(xing)(xing)、高(gao)(gao)強力型(xing)(xing)、耐(nai)(nai)油型(xing)(xing)、醫用(yong)型(xing)(xing)等等。
發展史
硅(gui)橡(xiang)膠(jiao)(jiao)早期是由美國(guo)(guo)以三氯化(hua)鐵(tie)為(wei)催化(hua)劑合成的(de)。1945年(nian),硅(gui)橡(xiang)膠(jiao)(jiao)產(chan)品問(wen)世。1948年(nian),采(cai)用(yong)高比表面積的(de)氣相法白(bai)炭黑補強的(de)硅(gui)橡(xiang)膠(jiao)(jiao)研制成功,使硅(gui)橡(xiang)膠(jiao)(jiao)的(de)性(xing)能躍升到實用(yong)階段(duan),奠(dian)定了現代硅(gui)橡(xiang)膠(jiao)(jiao)生(sheng)產(chan)技術的(de)基礎(chu)。從二(er)甲(jia)基二(er)氯硅(gui)烷合成開(kai)始生(sheng)產(chan)硅(gui)橡(xiang)膠(jiao)(jiao)的(de)國(guo)(guo)家(jia)有(you)美國(guo)(guo)。俄(e)羅斯、德國(guo)(guo)、日本、韓國(guo)(guo)和中(zhong)(zhong)國(guo)(guo)等(deng)。中(zhong)(zhong)國(guo)(guo)硅(gui)橡(xiang)膠(jiao)(jiao)的(de)工業(ye)化(hua)研究(jiu)始于1957年(nian),多家(jia)研究(jiu)所和企業(ye)陸續(xu)開(kai)發出(chu)各種硅(gui)橡(xiang)膠(jiao)(jiao)。到2003年(nian)底,中(zhong)(zhong)國(guo)(guo)硅(gui)橡(xiang)膠(jiao)(jiao)生(sheng)產(chan)能力為(wei)135千(qian)(qian)噸(dun),其中(zhong)(zhong)高溫膠(jiao)(jiao)100千(qian)(qian)噸(dun)。
高溫硫化硅橡膠
高溫硫化(hua)(hua)硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)是(shi)(shi)指聚硅(gui)氧烷變成(cheng)彈性(xing)體的過(guo)程是(shi)(shi)經過(guo)高溫(110-170℃)硫化(hua)(hua)成(cheng)型的。它主(zhu)要(yao)以高分子量(liang)的聚甲基乙(yi)烯基硅(gui)氧烷為生(sheng)膠(jiao)(jiao)(jiao),混(hun)入(ru)補強填料、硫化(hua)(hua)劑等,在(zai)加熱加壓下硫化(hua)(hua)成(cheng)彈性(xing)體。硅(gui)橡(xiang)(xiang)膠(jiao)(jiao)(jiao)的補強主(zhu)要(yao)是(shi)(shi)各種類型的白炭黑,可使(shi)硫化(hua)(hua)膠(jiao)(jiao)(jiao)的強度增加數(shu)十倍(bei)。有(you)時為了降低成(cheng)本或改善膠(jiao)(jiao)(jiao)料性(xing)能(neng)及賦予硫化(hua)(hua)膠(jiao)(jiao)(jiao)各種特殊的性(xing)能(neng),也加入(ru)相應的各種添加劑。硫化(hua)(hua)劑是(shi)(shi)各種有(you)機過(guo)氧化(hua)(hua)物或加成(cheng)反(fan)應催化(hua)(hua)劑。
加工成型方(fang)法如圖(tu)所示。一次硫化(hua)(hua)的(de)目的(de)是進行高分子(zi)鏈的(de)交聯(lian)(lian)反應;二次硫化(hua)(hua)的(de)目的(de)是進行補充(chong)交聯(lian)(lian)、驅除硫化(hua)(hua)劑分解產(chan)物(wu)和其他(ta)揮發性(xing)(xing)化(hua)(hua)合物(wu)以穩定硫化(hua)(hua)膠(jiao)的(de)各(ge)項性(xing)(xing)能。常(chang)用的(de)設備有開(kai)放式煉膠(jiao)機(ji)、捏(nie)合機(ji)及真空密(mi)煉機(ji)。
主要性能
(1)高溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)顯(xian)著的(de)(de)特征是(shi)高溫(wen)(wen)(wen)穩定性(xing)(xing)(xing)(xing)(xing),雖然(ran)常(chang)溫(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)強(qiang)度(du)僅(jin)是(shi)天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)或某(mou)些合成橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)一(yi)半,但在(zai)(zai)200℃以上的(de)(de)高溫(wen)(wen)(wen)環境下(xia),硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)仍能(neng)(neng)(neng)(neng)(neng)(neng)(neng)保持一(yi)定的(de)(de)柔韌性(xing)(xing)(xing)(xing)(xing)、回彈性(xing)(xing)(xing)(xing)(xing)和表面硬度(du),且(qie)力學性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)無(wu)明(ming)顯(xian)變化。(2)低(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)的(de)(de)玻璃化溫(wen)(wen)(wen)度(du)一(yi)般(ban)為(wei)-70~-50℃,特殊配(pei)方可達-100℃,表明(ming)其(qi)低(di)溫(wen)(wen)(wen)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)優(you)異(yi)。這(zhe)對(dui)航空(kong)、宇航工業(ye)的(de)(de)意義重大。(3)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)中(zhong)Si-O-Si鍵對(dui)氧(yang)、臭(chou)氧(yang)及(ji)紫外線等十分(fen)穩定,在(zai)(zai)不加任何(he)添加劑(ji)的(de)(de)情況下(xia),就具有(you)優(you)良的(de)(de)耐(nai)(nai)候(hou)性(xing)(xing)(xing)(xing)(xing)。(4)電氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)具有(you)優(you)異(yi)的(de)(de)絕(jue)緣性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng),耐(nai)(nai)電暈性(xing)(xing)(xing)(xing)(xing)和耐(nai)(nai)電弧性(xing)(xing)(xing)(xing)(xing)也非常(chang)好。(5)物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)常(chang)溫(wen)(wen)(wen)下(xia)的(de)(de)物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)比(bi)通用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)差,但在(zai)(zai)150℃的(de)(de)高溫(wen)(wen)(wen)和-50℃的(de)(de)低(di)溫(wen)(wen)(wen)下(xia),其(qi)物理機械性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)優(you)于(yu)通用橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)。(6)耐(nai)(nai)油及(ji)化學試劑(ji)性(xing)(xing)(xing)(xing)(xing)。普通硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)具有(you)中(zhong)等的(de)(de)耐(nai)(nai)油、耐(nai)(nai)溶(rong)劑(ji)性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)。(7)氣(qi)(qi)體透過性(xing)(xing)(xing)(xing)(xing)能(neng)(neng)(neng)(neng)(neng)(neng)(neng)。室溫(wen)(wen)(wen)下(xia)硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)對(dui)空(kong)氣(qi)(qi)、氮、氧(yang)、二(er)氧(yang)化碳等氣(qi)(qi)體的(de)(de)透氣(qi)(qi)性(xing)(xing)(xing)(xing)(xing)比(bi)天(tian)然(ran)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)高出30-50倍。(8)生理惰(duo)性(xing)(xing)(xing)(xing)(xing)。硅(gui)(gui)(gui)橡(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)膠(jiao)(jiao)(jiao)(jiao)(jiao)(jiao)無(wu)毒,無(wu)味,無(wu)嗅(xiu),與人體組織不粘連,具有(you)抗凝血(xue)作(zuo)用,對(dui)肌體組織的(de)(de)反(fan)應(ying)性(xing)(xing)(xing)(xing)(xing)非常(chang)少(shao)。特別適合作(zuo)為(wei)醫用材料。
硅橡膠的用量
據(ju)中國(guo)(guo)汽(qi)(qi)(qi)車(che)(che)(che)工(gong)(gong)業(ye)協會(hui)統計,2012年,汽(qi)(qi)(qi)車(che)(che)(che)產銷分別(bie)(bie)達到1927.18萬(wan)輛和(he)1930.64萬(wan)輛,同比分別(bie)(bie)增(zeng)(zeng)長(chang)4.63%和(he)4.33%,汽(qi)(qi)(qi)車(che)(che)(che)工(gong)(gong)業(ye)硅(gui)(gui)橡(xiang)膠(jiao)的(de)(de)(de)用(yong)(yong)量(liang)約(yue)達2.0萬(wan)t。根(gen)據(ju)觀研(yan)天下的(de)(de)(de)新(xin)研(yan)究,增(zeng)(zeng)加有機(ji)硅(gui)(gui)材(cai)料在汽(qi)(qi)(qi)車(che)(che)(che)零(ling)部件方面的(de)(de)(de)用(yong)(yong)量(liang),可以(yi)大幅度提(ti)高汽(qi)(qi)(qi)車(che)(che)(che)的(de)(de)(de)安全性能,因此,汽(qi)(qi)(qi)車(che)(che)(che)產量(liang)和(he)單車(che)(che)(che)用(yong)(yong)量(liang)水平(ping)的(de)(de)(de)提(ti)高都將推動(dong)汽(qi)(qi)(qi)車(che)(che)(che)工(gong)(gong)業(ye)對硅(gui)(gui)橡(xiang)膠(jiao)需求的(de)(de)(de)增(zeng)(zeng)加。國(guo)(guo)家鼓勵自主(zhu)品牌的(de)(de)(de)汽(qi)(qi)(qi)車(che)(che)(che)發展,關(guan)鍵(jian)汽(qi)(qi)(qi)車(che)(che)(che)零(ling)部件實現自主(zhu)化(hua),《2012年度黨政(zheng)機(ji)關(guan)公務用(yong)(yong)車(che)(che)(che)選用(yong)(yong)車(che)(che)(che)型目錄(征求意見稿(gao))》為(wei)自主(zhu)品牌擴大在政(zheng)府采(cai)購的(de)(de)(de)市場份額,為(wei)改變目前(qian)國(guo)(guo)內(nei)政(zheng)府采(cai)購以(yi)合資品牌產品為(wei)主(zhu)的(de)(de)(de)局(ju)面提(ti)供了保障(zhang)。促(cu)進自主(zhu)品牌發展,國(guo)(guo)產汽(qi)(qi)(qi)車(che)(che)(che)業(ye)的(de)(de)(de)繁榮(rong)將為(wei)汽(qi)(qi)(qi)車(che)(che)(che)膠(jiao)的(de)(de)(de)應用(yong)(yong)提(ti)供有力保障(zhang)。預(yu)測未來3年,我國(guo)(guo)室溫硫(liu)化(hua)硅(gui)(gui)橡(xiang)膠(jiao)在汽(qi)(qi)(qi)車(che)(che)(che)行(xing)業(ye)將以(yi)年均20%增(zeng)(zeng)長(chang)。
此(ci)外,硅(gui)橡(xiang)膠(jiao)是重要的(de)非石(shi)(shi)(shi)油(you)(you)基(ji)合(he)成(cheng)橡(xiang)膠(jiao),約占非石(shi)(shi)(shi)油(you)(you)基(ji)合(he)成(cheng)橡(xiang)膠(jiao)消(xiao)(xiao)費量的(de)98%。但因為(wei)石(shi)(shi)(shi)油(you)(you)價格(ge)的(de)大(da)幅上(shang)漲(zhang),同時(shi)我(wo)國在(zai)硅(gui)橡(xiang)膠(jiao)的(de)關鍵原(yuan)(yuan)料有(you)機硅(gui)單體的(de)生產(chan)技(ji)術方面取得突破,有(you)機硅(gui)單體的(de)生產(chan)技(ji)術在(zai)2005年(nian)前被幾(ji)家跨國公(gong)司壟斷,但目(mu)前我(wo)國已發展(zhan)成(cheng)為(wei)全球有(you)機硅(gui)單體第1大(da)國,這2個方面原(yuan)(yuan)因使(shi)硅(gui)橡(xiang)膠(jiao)的(de)價格(ge)從2011年(nian)起(qi)開(kai)始低(di)于石(shi)(shi)(shi)油(you)(you)基(ji)合(he)成(cheng)橡(xiang)膠(jiao),僅約為(wei)大(da)宗石(shi)(shi)(shi)油(you)(you)基(ji)橡(xiang)膠(jiao)的(de)80%~90%,成(cheng)為(wei)廉(lian)價的(de)合(he)成(cheng)橡(xiang)膠(jiao),并(bing)開(kai)始大(da)規模替(ti)代石(shi)(shi)(shi)油(you)(you)基(ji)合(he)成(cheng)橡(xiang)膠(jiao)。這將極大(da)拓展(zhan)有(you)機硅(gui)產(chan)業的(de)市(shi)場空(kong)間,同時(shi)將帶動硅(gui)油(you)(you)、硅(gui)烷偶聯(lian)劑和硅(gui)樹脂等(deng)其他(ta)有(you)機硅(gui)產(chan)品的(de)消(xiao)(xiao)費。