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桐油基衍生物鈉鹽的表面張力、CMC值測定、乳液穩定性、固化膜性能測試（二）

來源：化工進展瀏覽 34 次發布時間:2024-01-09

2結果與討論

2.1丙(bing)烯酸(suan)酯改性桐油基衍生物的合成

2.1.1桐油酸(suan)酐的合(he)成

桐(tong)(tong)(tong)(tong)油(you)(you)中的(de)(de)(de)共軛不(bu)(bu)飽和鍵(jian)與(yu)馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)易發(fa)生Diels-Alder（D-A）反(fan)(fan)(fan)(fan)應(ying)(ying)，生成(cheng)桐(tong)(tong)(tong)(tong)油(you)(you)酸(suan)(suan)(suan)(suan)酐(gan)，反(fan)(fan)(fan)(fan)應(ying)(ying)條(tiao)件(jian)對產物(wu)(wu)的(de)(de)(de)分(fen)(fen)布具(ju)有重要影(ying)響。由于(yu)桐(tong)(tong)(tong)(tong)油(you)(you)為(wei)(wei)混合物(wu)(wu)，每分(fen)(fen)子中有3條(tiao)不(bu)(bu)飽和鏈，控制MA的(de)(de)(de)加(jia)入(ru)量及(ji)(ji)反(fan)(fan)(fan)(fan)應(ying)(ying)條(tiao)件(jian)，可(ke)以控制桐(tong)(tong)(tong)(tong)油(you)(you)二酸(suan)(suan)(suan)(suan)酐(gan)（TM2）和桐(tong)(tong)(tong)(tong)油(you)(you)三(san)酸(suan)(suan)(suan)(suan)酐(gan)（TM3）的(de)(de)(de)形成(cheng)。文獻報道大多數桐(tong)(tong)(tong)(tong)油(you)(you)和馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)反(fan)(fan)(fan)(fan)應(ying)(ying)以有機(ji)錫為(wei)(wei)催(cui)化劑(ji)，經過(guo)研究發(fa)現，溫度(du)對馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)與(yu)桐(tong)(tong)(tong)(tong)油(you)(you)反(fan)(fan)(fan)(fan)應(ying)(ying)影(ying)響較大，溫度(du)低反(fan)(fan)(fan)(fan)應(ying)(ying)很慢，有機(ji)錫催(cui)化劑(ji)并不(bu)(bu)能明(ming)顯降(jiang)低反(fan)(fan)(fan)(fan)應(ying)(ying)溫度(du)。在無催(cui)化劑(ji)的(de)(de)(de)條(tiao)件(jian)下(xia)，以紅(hong)外(wai)(wai)光(guang)譜跟蹤80℃、100℃、120℃及(ji)(ji)140℃下(xia)桐(tong)(tong)(tong)(tong)油(you)(you)與(yu)3倍量的(de)(de)(de)馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)反(fan)(fan)(fan)(fan)應(ying)(ying)的(de)(de)(de)情況，結果表明(ming)80℃下(xia)反(fan)(fan)(fan)(fan)應(ying)(ying)緩慢，100℃反(fan)(fan)(fan)(fan)應(ying)(ying)1h后(hou)桐(tong)(tong)(tong)(tong)油(you)(you)的(de)(de)(de)共軛三(san)鍵(jian)的(de)(de)(de)紅(hong)外(wai)(wai)吸收(shou)峰幾(ji)乎完(wan)全(quan)消失，反(fan)(fan)(fan)(fan)應(ying)(ying)程度(du)能達到96%。桐(tong)(tong)(tong)(tong)油(you)(you)及(ji)(ji)桐(tong)(tong)(tong)(tong)油(you)(you)酸(suan)(suan)(suan)(suan)酐(gan)的(de)(de)(de)FTIR如圖1所示，991cm–1為(wei)(wei)桐(tong)(tong)(tong)(tong)油(you)(you)共軛三(san)鍵(jian)的(de)(de)(de)面外(wai)(wai)彎(wan)曲振動(dong)紅(hong)外(wai)(wai)吸收(shou)峰，兩倍量馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)與(yu)桐(tong)(tong)(tong)(tong)油(you)(you)反(fan)(fan)(fan)(fan)應(ying)(ying)的(de)(de)(de)產物(wu)(wu)（TM2）中991cm–1的(de)(de)(de)吸收(shou)峰明(ming)顯減弱但(dan)未消失，3倍量馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)與(yu)桐(tong)(tong)(tong)(tong)油(you)(you)反(fan)(fan)(fan)(fan)應(ying)(ying)的(de)(de)(de)產物(wu)(wu)中該峰完(wan)全(quan)消失，說明(ming)桐(tong)(tong)(tong)(tong)油(you)(you)分(fen)(fen)子上(shang)的(de)(de)(de)共軛三(san)鍵(jian)可(ke)以同馬(ma)(ma)來酸(suan)(suan)(suan)(suan)酐(gan)反(fan)(fan)(fan)(fan)應(ying)(ying)形成(cheng)三(san)酸(suan)(suan)(suan)(suan)酐(gan)TM3。

圖1桐油、TM2和(he)TM3的紅外(wai)光(guang)譜圖

桐(tong)油(you)(you)及桐(tong)油(you)(you)酸酐的(de)(de)1H NMR見圖2，從(cong)圖中(zhong)可以(yi)看出，隨著加成反(fan)應的(de)(de)進行，桐(tong)油(you)(you)中(zhong)的(de)(de)烯鍵上(shang)(shang)(shang)的(de)(de)氫(qing)(qing)信號(hao)(hao)（8～13），TM2烯鍵上(shang)(shang)(shang)的(de)(de)氫(qing)(qing)信號(hao)(hao)（11～17）及TM3烯鍵上(shang)(shang)(shang)的(de)(de)氫(qing)(qing)信號(hao)(hao)（11～13）明(ming)顯減弱(ruo)，峰型也發(fa)生(sheng)很大(da)變化。依(yi)據圖2(b)中(zhong)的(de)(de)各(ge)(ge)峰積(ji)分(fen)(fen)面積(ji)比(bi)例確定桐(tong)油(you)(you)與(yu)兩(liang)個馬來酸酐反(fan)應形成TM2，進一步與(yu)馬來酸酐反(fan)應，共軛三烯的(de)(de)氫(qing)(qing)信號(hao)(hao)[圖2(b)中(zhong)14～17]完全消失。由于(yu)桐(tong)油(you)(you)結(jie)構較(jiao)復雜，1H NMR歸屬較(jiao)困(kun)難，TM 2經1H-1H COSY譜（圖3）分(fen)(fen)析，從(cong)圖3中(zhong)可以(yi)看出，信號(hao)(hao)3和(he)(he)6相(xiang)關(guan)(guan)，為甘油(you)(you)酯(zhi)緊連的(de)(de)兩(liang)個亞甲基氫(qing)(qing)；6′和(he)(he)8相(xiang)關(guan)(guan)，為新生(sheng)成的(de)(de)六元(yuan)環相(xiang)鄰(lin)的(de)(de)兩(liang)個氫(qing)(qing)；5和(he)(he)5′分(fen)(fen)別(bie)與(yu)12和(he)(he)12′相(xiang)關(guan)(guan)，7和(he)(he)13、13′相(xiang)關(guan)(guan)，9和(he)(he)10相(xiang)關(guan)(guan)，11和(he)(he)14相(xiang)關(guan)(guan)，14和(he)(he)17相(xiang)關(guan)(guan)，12、17與(yu)15、16相(xiang)關(guan)(guan)。結(jie)合圖2(b)、圖2(c)中(zhong)信號(hao)(hao)7、8、9的(de)(de)積(ji)分(fen)(fen)比(bi)例分(fen)(fen)別(bie)為1∶2∶2及3∶6∶4，及TM2的(de)(de)1H-1H COSY譜分(fen)(fen)析，TM2及TM3結(jie)構各(ge)(ge)質子(zi)信號(hao)(hao)歸屬如圖2所示。

2.1.2丙烯酸酯(zhi)改性(xing)桐油及衍生物的(de)合(he)成

在100℃以三乙(yi)胺為催化劑(ji)，桐(tong)油三酸(suan)酐與(yu)甲(jia)基丙(bing)烯酸(suan)β羥(qian)乙(yi)酯以摩爾比1∶1、1∶2、1∶3反(fan)(fan)(fan)(fan)應(ying)1.5h后(hou)，選擇性地(di)合成(cheng)了(le)桐(tong)油三酸(suan)酐單β羥(qian)乙(yi)酯（TM3H1），桐(tong)油三酸(suan)酐二(er)β羥(qian)乙(yi)酯（TM3H2）和桐(tong)油三酸(suan)酐三β羥(qian)乙(yi)酯（TM3H3），產物(wu)經(jing)紅外光譜和核(he)磁共振氫(qing)譜表征(zheng)。桐(tong)油三酸(suan)酐與(yu)3倍(bei)甲(jia)基丙(bing)烯酸(suan)β羥(qian)乙(yi)酯反(fan)(fan)(fan)(fan)應(ying)前后(hou)的FTIR如圖4所示，加入HEMA時，體系中在3508cm–1的羥(qian)基吸(xi)收(shou)峰，1848cm–1、1778cm–1、1035cm–1的酸(suan)酐特征(zheng)吸(xi)收(shou)峰反(fan)(fan)(fan)(fan)應(ying)后(hou)幾(ji)乎消失，說明甲(jia)基丙(bing)烯酸(suan)β羥(qian)乙(yi)酯中的羥(qian)基與(yu)酸(suan)酐完全反(fan)(fan)(fan)(fan)應(ying)，生(sheng)成(cheng)了(le)目標產物(wu)TM3H3。

2.2多子乳(ru)化劑表面張力測試

將桐(tong)油(you)三酸酐和(he)桐(tong)油(you)三酸酐與甲基(ji)丙(bing)烯酸β羥乙酯(zhi)反(fan)應后的(de)產(chan)物(wu)TM3H1及(ji)(ji)TM3H2水(shui)解，形成(cheng)(cheng)羧(suo)基(ji)官能(neng)團(tuan)數(shu)為(wei)4～6的(de)丙(bing)烯酸酯(zhi)改性的(de)桐(tong)油(you)基(ji)衍(yan)生(sheng)(sheng)物(wu)，TM3H3含有(you)3個羧(suo)基(ji)。將羧(suo)酸改性的(de)桐(tong)油(you)用(yong)堿(jian)等當(dang)量(liang)中(zhong)和(he)，形成(cheng)(cheng)含3～6個羧(suo)酸鈉基(ji)團(tuan)的(de)桐(tong)油(you)基(ji)衍(yan)生(sheng)(sheng)物(wu)，簡(jian)稱為(wei)3～6子(zi)(zi)乳(ru)化(hua)(hua)劑(ji)。桐(tong)油(you)及(ji)(ji)乳(ru)化(hua)(hua)劑(ji)的(de)表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)測試結果如圖5所示，與純水(shui)（實測表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)69mN/m）相比，4種多子(zi)(zi)乳(ru)化(hua)(hua)劑(ji)均能(neng)降低水(shui)的(de)表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)。表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)隨其濃(nong)(nong)度(du)的(de)增加而下降，當(dang)乳(ru)化(hua)(hua)劑(ji)濃(nong)(nong)度(du)大于(yu)2.5mmol時，溶(rong)液(ye)的(de)表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)隨濃(nong)(nong)度(du)的(de)變化(hua)(hua)趨于(yu)平穩，逐漸接近水(shui)平。乳(ru)化(hua)(hua)劑(ji)濃(nong)(nong)度(du)為(wei)1.5mmol/L時，3～6子(zi)(zi)乳(ru)化(hua)(hua)劑(ji)表(biao)(biao)面(mian)張(zhang)力(li)(li)(li)分別為(wei)50.2mN/m、48.8mN/m、47.2mN/m和(he)45.2mN/m。