第30卷第6期沈陽工業(yè)大學(xué)學(xué)報(bào)vo.30N.62008年12月Jourmal of Shenyang University of TechnologD,2008文章編號(hào):1000-1646(2008)06-0712-04、化學(xué)工程烯烴聚合物的制備李三喜,婁麗,王松,張愛玲(沈陽工業(yè)大學(xué)理學(xué)院,沈陽110178)要:以可再生大豆油為原料通過醇解、環(huán)氧化、丙烯酸酯化等一系列化學(xué)反應(yīng)制備丙烯酸長鏈烷基酯,再用共聚單體苯乙烯與丙烯酸長鏈烷基酯在一定條件下進(jìn)行共聚,合成含長鏈烷基支鏈的苯乙烯烯酸酯共聚物并研究了反應(yīng)溫度、原料用量、反應(yīng)時(shí)間等因素對(duì)醇解反應(yīng)、環(huán)氧化反應(yīng)的影響通過紅外光譜法對(duì)合成各階段產(chǎn)物結(jié)構(gòu)進(jìn)行表征鑒定產(chǎn)物的結(jié)構(gòu)結(jié)果表明,合成的聚合物不但可以生物降解降解后產(chǎn)生的小分子還可參加生物代謝循環(huán)并且被同化吸收,從而可以克服原始石油基聚合物因廢棄后不能生物降解所造成的環(huán)境污染問題關(guān)鍵詞:大豆油;醇解;丙烯酸酯;苯乙烯;共聚物中圖分類號(hào):TQ150.45文獻(xiàn)標(biāo)志碼:APreparation of alkene polymerLI San-xi, LOU Li, WANG Song, ZHANG Ai-ling(School of Science, Shenyang University of Technology, Shenyang 110178, China)Abstract: The long chain alky acrylate was fabricated using recycled soybean oil as raw material through aseries of chemical reactions such as alcoholization, epoxydation, acrylic esterification. This long chain alkyacrylate was then used to prepare the styrene copolymer. The effect of reaction temperature, materialdosage and reaction time on alcoholization and epoxydation reactions were studied. The structure of thereaction products was identified by IR. The result shows that comparing with the traditionalpetroleum-based macromolecular products, the synthesized polymer is biodegradable, and the generatedsmall molecule can participate in the biological metabolism circulation and be assimilated. Thus, theenvironment pollution problem caused by non-biodegradability of traditional oil-based synthetic polymer canKey words: soybean oil; alcoholysis; acrylate; styrene; copolymer目前,大部分合成高分子材料采用不可再生資烴聚合物的研究起步較晚{4-源的石油為原料,如塑料、橡膠等高分子材料,其廢大豆油主要是由各種飽和或不飽和脂肪酸甘棄物難以自然降解帶來嚴(yán)重的環(huán)境污染問題為油三酯組成的混合物(每個(gè)分子含3~4個(gè)雙鍵)此天然材料的應(yīng)用再度引起人們的重視-2].我很早就用作醇酸樹脂涂料的原料6-7.但是,大國對(duì)于大豆油的利用已有很長時(shí)間,如生物柴油,豆油中天然存在的雙鍵活性較弱,難以通過自由環(huán)氧大豆油等工業(yè)化生產(chǎn)3].又由于大豆油分子的基反應(yīng)而制備相對(duì)高分子質(zhì)量的聚合物,因此以鏈很大聚合過程中容易產(chǎn)生空間位阻,高溫下往大豆Vd于涂料等薄層材料,或者作為不飽和脂肪酸基之間易發(fā)生復(fù)雜的聚合反應(yīng)而生材料中國煤化工材料的主體本成聚合度不同的產(chǎn)物國內(nèi)以大豆油為原料制備烯文CNMHG物其合成過程收稿日期:2008-06-16.基金項(xiàng)目:遼寧省科學(xué)技術(shù)基金資助項(xiàng)目(20072045);遼寧省教育廳基金資助項(xiàng)目(206060)作者簡介:李三喜(1962-),男湖南安鄉(xiāng)人教授博士,主要從事烯烴催化聚合及高性能有機(jī)/無機(jī)復(fù)合材料等方面的研究第6期李三喜,等:烯烴聚合物的制備713為:將大豆油醇解生成帶雙鍵的長鏈烷烴將雙鍵環(huán)氧化后與丙烯酸酯化,生成的丙烯酸長鏈烷基酯與苯乙烯合成烯烴聚合物,此聚合物可以制備結(jié)構(gòu)性材料1實(shí)驗(yàn)部分1.1原材料及試劑大豆油,食用級(jí);甲酸,分析純;苯乙烯,分析00.51.01.5純;無水甲醇,分析純;丙烯酸,分析純;N,N二甲催化劑加入量%基芐胺,化學(xué)純圖1催化劑質(zhì)量分?jǐn)?shù)對(duì)醇解反應(yīng)產(chǎn)率的影響12合成過程ig. 1 Eiect of mass ratio of catalyst on alcoholysis reaction以大豆油為原料合成烯烴共聚物的主要工藝從圖1可以看出,當(dāng)催化劑加入量在0.5%過程:①在裝有攪拌器、溫度計(jì)、冷凝管的三口燒1.0%時(shí),醇解產(chǎn)率隨著其質(zhì)量分?jǐn)?shù)的增加而增加瓶中,加入一定量的大豆油,加熱至一定溫度后,當(dāng)質(zhì)量分?jǐn)?shù)達(dá)到10%時(shí),產(chǎn)率有所下降.這是由在攪拌下加入催化劑和甲醇恒溫反應(yīng)1~2h后于甲醇呈現(xiàn)極弱的酸性,其電離常數(shù)很小,因此在將反應(yīng)混和物倒入分液漏斗中進(jìn)行分離,取上層催化劑質(zhì)量分?jǐn)?shù)達(dá)到10%后,甲醇的離解已趨于溶液,通過蒸餾中和除去甲醇和過量的酸然后用飽和繼續(xù)增大催化劑用量不僅不會(huì)增加甲醇的離適量的溫水進(jìn)行洗滌、干燥、過濾得到淺黃色、澄解和活性親核試劑甲氧基的濃度,而且會(huì)因?yàn)閴A性清透明粗酯;②將粗酯、雙氧水和甲酸加入上述催化劑質(zhì)量分?jǐn)?shù)升高,導(dǎo)致副反應(yīng)發(fā)生因此在實(shí)裝置,在酸性條件下進(jìn)行烷基長鏈環(huán)氧化反應(yīng),經(jīng)際應(yīng)用中,取堿性催化劑質(zhì)量分?jǐn)?shù)為1.0%過4~5h反應(yīng)后,水洗至中性減壓蒸餾除水,得2.12反應(yīng)溫度的影響環(huán)氧化長鏈烷烴;③環(huán)氧化長鏈烷烴和丙烯酸在在0~60℃溫度范圍內(nèi),醇解反應(yīng)產(chǎn)率隨溫N,N二甲基芐胺催化下,于90~95℃溫度酯化度升高而增加,醇解反應(yīng)產(chǎn)率最高的溫度點(diǎn)為5-6h,生成丙烯酸長鏈烷烴再與苯乙烯聚合反60℃;當(dāng)反應(yīng)溫度超過60℃,引起醇解反應(yīng)產(chǎn)率應(yīng)4h,得到試驗(yàn)產(chǎn)物苯乙烯/丙烯酸酯共聚物明顯下降,因此,在本實(shí)驗(yàn)條件下,醇解反應(yīng)最佳13分析測試溫度為60℃.圖2為反應(yīng)溫度對(duì)醇解產(chǎn)率的影環(huán)氧值:鹽酸丙酮法,環(huán)氧基物質(zhì)量為100g響圖2表明,在0~60℃溫度范圍內(nèi)醇解反應(yīng)產(chǎn)樹脂8.紅外光譜分析:采用北京市第二光學(xué)儀率隨著溫度的升高而升高這是由于隨著溫度的升器廠生產(chǎn)的WQF30傅立葉變換紅外光譜儀,定高反應(yīng)物活性增大,反應(yīng)速度加快,導(dǎo)致產(chǎn)率升性表征物質(zhì)的結(jié)構(gòu)高.而溫度超過60℃以后,產(chǎn)率有所下降這是因?yàn)闇囟壤^續(xù)升髙,超過甲醇的沸點(diǎn),導(dǎo)致反應(yīng)系統(tǒng)2結(jié)果與討論中的大量甲醇揮發(fā)至氣相中,使液相中甲醇濃度降低,致使反應(yīng)產(chǎn)率下降溫度過低使反應(yīng)減慢,產(chǎn)2.1反應(yīng)因素對(duì)醇解反應(yīng)產(chǎn)率的影響醇解反應(yīng)是一個(gè)多步可逆過程,氫氧化鈉與甲醇相互作用得到甲醇鈉的同時(shí)也生成了水,水繼續(xù)電離得到OH,OH再與甘油三酯發(fā)生反應(yīng),生成游離脂肪酸、甘油一酯和甘油二酯因此催化劑質(zhì)量分?jǐn)?shù)反應(yīng)溫度、反應(yīng)時(shí)間、醇油比對(duì)醇解反應(yīng)都有影響211催化劑質(zhì)量分?jǐn)?shù)對(duì)醇解反應(yīng)的影響中國煤化工在本實(shí)驗(yàn)中,堿性催化劑質(zhì)量分?jǐn)?shù)在0.5%CNMHG 801%之間,反應(yīng)產(chǎn)率明顯增加超過1%,反應(yīng)產(chǎn)率逐漸下降圖1為催化劑質(zhì)量分?jǐn)?shù)對(duì)醇解反應(yīng)產(chǎn)圖2反應(yīng)溫度對(duì)醇解產(chǎn)率的影響率的影響Fig2 Influence of temperature on alcoholysis reaction714沈陽工業(yè)大學(xué)學(xué)報(bào)第30卷率降低,因此本實(shí)驗(yàn)選取最佳反應(yīng)溫度為60℃由圖4表明在60min內(nèi)醇解反應(yīng)產(chǎn)率隨著時(shí)213反應(yīng)醇油比的影響間的增長而增大這是由于隨著時(shí)間的增加,正反應(yīng)在本實(shí)驗(yàn)中,醇油比在1:1~6:1范圍內(nèi),醇速率增大,導(dǎo)致產(chǎn)率升高而時(shí)間超過60min以后,逆解反應(yīng)產(chǎn)率隨其比值升高而增加,醇解反應(yīng)產(chǎn)率反應(yīng)速率加快產(chǎn)率降低所以反應(yīng)時(shí)間在60min最高比值為6:1;當(dāng)醇油比超過6:1時(shí),醇解反應(yīng)時(shí),正逆反應(yīng)速度相等使得產(chǎn)率趨于穩(wěn)定產(chǎn)率增長變慢,因此在本實(shí)驗(yàn)條件下,醇油比最佳2.15紅外譜圖表征分析比值為6:1.圖3為醇油比對(duì)醇解反應(yīng)產(chǎn)率的影圖5為大豆油樣品與長鏈烷烴對(duì)比紅外譜響圖3表明,在低于6:1范圍內(nèi),醇解反應(yīng)產(chǎn)率圖,圖5中的a與b基本上相似,但是在1171~隨著比值的升高而升高;而比值超過6:1以后,產(chǎn)1246cm-1位置上的CO基團(tuán)的特征峰發(fā)生了略率有所下降這是由于醇解反應(yīng)是一個(gè)可逆反應(yīng),微地偏移,說明豆油分子在醇解反應(yīng)中CO基團(tuán)在反應(yīng)過程中,隨著反應(yīng)物甲醇濃度的增大,會(huì)促附近發(fā)生了結(jié)構(gòu)變化,豆油的長分子鏈發(fā)生了斷使反應(yīng)向正方向進(jìn)行.當(dāng)超過甲醇的濃度達(dá)到最裂在1435cm-1的位置出現(xiàn)了甲基的峰,證明了大值時(shí),反應(yīng)產(chǎn)率增長變慢,因此本實(shí)驗(yàn)選取最佳在長鏈烯烴的結(jié)構(gòu)中生成了甲基結(jié)構(gòu),這正符合醇油比為6:1了醇解反應(yīng)產(chǎn)物的結(jié)構(gòu):豆油分子的長鏈斷開,在斷開處形成了甲基化劃兇435117醇油比180圖3醇油比對(duì)醇解反應(yīng)產(chǎn)率的影響400035003000250020001500100ig. 3 Effect of methyl alcohol and soybean波數(shù)/cm圖5大豆油樣品與長鏈烷烴對(duì)比紅外譜圖2.14反應(yīng)時(shí)間對(duì)醇解反應(yīng)產(chǎn)率的影響Fig 5 FTIR of soybean oil and long chain alkane在本實(shí)驗(yàn)中,反應(yīng)在60min內(nèi),醇解反應(yīng)產(chǎn)a.豆油樣品b.長鏈烷烴率隨時(shí)間增加而增大,醇解反應(yīng)產(chǎn)率最高的反應(yīng)22環(huán)氧化反應(yīng)時(shí)間為60min;當(dāng)反應(yīng)時(shí)間超過60min時(shí),醇解利用雙氧水具有微酸性,在一定溫度下起引反應(yīng)產(chǎn)率明顯下降,因此在本實(shí)驗(yàn)條件下,醇解反發(fā)劑作用過氧甲酸釋放出的氧原子能與豆油基應(yīng)最佳時(shí)間為60min圖4為醇解反應(yīng)時(shí)間與產(chǎn)長鏈烷烴中的不飽和鍵充分接觸,從而使環(huán)氧化率的關(guān)系反應(yīng)向產(chǎn)物方向進(jìn)行22,1雙氧水用量的影響雙氧水是形成過氧酸的關(guān)鍵原料,它的用量多少直接影響氧化的效果在本實(shí)驗(yàn)條件下,隨著雙氧水用量增加,反應(yīng)產(chǎn)率明顯增加,但是雙氧水量劃兇過大,對(duì)實(shí)驗(yàn)又有副反應(yīng)圖6為雙氧水用量對(duì)環(huán)氧化值的影響由圖6可知在反應(yīng)過程中,當(dāng)雙氧水加入量為100%時(shí),對(duì)環(huán)氧化反應(yīng)最適合若雙M凵中國煤化工化能力下降:若雙氧反應(yīng)時(shí)間/minCNMHG一方移動(dòng)能保元火叫戰(zhàn)瞅存在,有利于環(huán)圖4醇解反應(yīng)時(shí)間與產(chǎn)率的關(guān)系氧反應(yīng)進(jìn)行但雙氧水不能過量太多,若過量太多Fig 4 Influnce of time on alcoholysis reaction則容易產(chǎn)生副反應(yīng),同時(shí)會(huì)造成浪費(fèi)第6期李三喜,等:烯烴聚合物的制備715乙烯上單取代的乙烯基雙鍵打開形成自由基,丙烯酸長鏈烷基酯末端雙鍵打開形成自由基,兩種自由基單體在引發(fā)劑的作用下發(fā)生聚合反應(yīng)圖迴8為紅外譜圖分析,由圖8中b,c相比而知,b在1111-1022cm1位置時(shí),環(huán)氧基團(tuán)的特征峰消失了,說明環(huán)氧基團(tuán)已經(jīng)被打開,在1600cm1和985cm-附近出現(xiàn)了新的峰,這是末端雙鍵的特征峰在1035cm-附近出現(xiàn)了OH的特征峰,說6080100120明該步反應(yīng)已將環(huán)氧基團(tuán)打開,生成了丙烯酸長HO加入量%鏈烷基酯,與預(yù)計(jì)的產(chǎn)物基本一致而且通過此譜圖6雙氧水用量對(duì)環(huán)氧化值的影響圖可以看出該步反應(yīng)進(jìn)行的很徹底b的紅外譜Fg6 Effect o mess ratio of ho2 epoxy value of product圖與d的紅外譜圖相比,930cm-1附近的峰消失雙氧水若用量過大,則會(huì)發(fā)生下述副反應(yīng)了,說明在反應(yīng)過程中羧基結(jié)構(gòu)被破壞了,參加了酯化反應(yīng)在圖8a譜圖上292030003026cm位置出現(xiàn)了苯乙烯聚合的特征峰,說明苯乙烯與丙烯酸長222環(huán)氧化長鏈烷烴紅外譜圖鏈烷基酯發(fā)生了聚合反應(yīng)生成了含長鏈側(cè)基的丙如圖7所示,在1730cm-4附近出現(xiàn)的特征烯酸酯共聚物與e譜圖相比,1600cm-1和峰為R1OOR2結(jié)構(gòu)伸縮振動(dòng)的特征峰,1458、985cm-附近末端雙鍵的特征峰消失了,也足以證1436、1363cm1出現(xiàn)的峰為甲基和亞甲基的特明丙烯酸長鏈烷基酯與苯乙烯發(fā)生了聚合反應(yīng)征峰,1247、1195、1172cm-l處的峰值為CO基團(tuán)伸縮振動(dòng)的特征峰.1111、1087、1022cm-1處出現(xiàn)的為環(huán)氧基團(tuán)伸縮振動(dòng)的特征峰,與長鏈烯烴的紅外譜圖相比較,300895cm位置的雙鍵峰消失,在1111-1022cm-1的位置出現(xiàn)了新的峰,該峰為環(huán)氧基團(tuán)的特征峰,說明環(huán)氧化反應(yīng)將長鏈烯烴的雙鍵打開,生成了環(huán)氧基團(tuán),并且從圖30087b中可以看出,3008.95cm位置的雙鍵峰基本消失了,說明在環(huán)氧化過程中雙鍵反應(yīng)的很徹底,環(huán)氧化程度很高0001000波數(shù)/cm1圖8聚合物紅外對(duì)比譜圖Fig 8 FTIR of copolymers苯乙烯丙烯酸長鏈酯b.丙烯酸長鏈烷基酯ec.環(huán)氧化長鏈烷烴d.丙烯酸e.苯乙烯3結(jié)論30081)采用醇解、環(huán)氧化丙烯酸酯化等合成工藝合成豆油基苯乙烯烯酸酯共聚物的工藝是4000350030002500200015001000500可行的波數(shù)/cm2)制備豆油基苯乙烯/烯酸酯共聚物過程圖7長鏈烷烴與環(huán)氧化長鏈烷烴對(duì)比紅外譜圖中,醇中國煤化工甲量為體系的Fig 7 FTIR of 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