丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi)的(de)(de)(de)(de)(de)(de)生(sheng)(sheng)产(chan)(chan)(chan)方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)有(you)(you)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水解(jie)法(fa)(fa)(fa)(fa)(fa)(fa)(fa),β-丙(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)、雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)(he)(he)(he)改良(liang)(liang)雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)、氰乙(yi)(yi)醇(chun)(chun)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)(he)(he)(he)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)直(zhi)接氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)。
1.氰乙(yi)(yi)醇(chun)(chun)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 以(yi)氯(lv)乙(yi)(yi)醇(chun)(chun)和(he)(he)(he)(he)氰化(hua)(hua)(hua)(hua)钠为(wei)(wei)原料(liao),反应(ying)(ying)生(sheng)(sheng)成(cheng)(cheng)氰乙(yi)(yi)醇(chun)(chun)、氰乙(yi)(yi)醇(chun)(chun)在硫(liu)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)存在下(xia)(xia)(xia)水解(jie)生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)。
2.丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水解(jie)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 由于(yu)(yu)(yu)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)来(lai)源丰富(fu),便(bian)发展了用(yong)(yong)(yong)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)作原料(liao)生(sheng)(sheng)产(chan)(chan)(chan)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi)的(de)(de)(de)(de)(de)(de)方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)。现已工(gong)业化(hua)(hua)(hua)(hua)的(de)(de)(de)(de)(de)(de)方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)有(you)(you)Societe Ugine法(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)(he)(he)(he)Standard Oil Co(O-hio)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)。将(jiang)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)与(yu)(yu)硫(liu)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)一(yi)(yi)(yi)起(qi)加(jia)热(re)到90℃,使(shi)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水解(jie)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酰(xian)胺的(de)(de)(de)(de)(de)(de)硫(liu)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)盐,硫(liu)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)盐进(jin)一(yi)(yi)(yi)步酯(zhi)(zhi)化(hua)(hua)(hua)(hua)生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi)。近年有(you)(you)专(zhuan)利报道,以(yi)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)为(wei)(wei)原料(liao),采(cai)用(yong)(yong)(yong)一(yi)(yi)(yi)步法(fa)(fa)(fa)(fa)(fa)(fa)(fa)生(sheng)(sheng)产(chan)(chan)(chan),酯(zhi)(zhi)的(de)(de)(de)(de)(de)(de)收(shou)(shou)率可(ke)(ke)达95%。
3.β-丙(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 以(yi)乙(yi)(yi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)(或丙(bing)(bing)(bing)(bing)(bing)(bing)酮)为(wei)(wei)原料(liao),磷(lin)(lin)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)三乙(yi)(yi)酯(zhi)(zhi)为(wei)(wei)催(cui)(cui)化(hua)(hua)(hua)(hua)剂,在625-730℃下(xia)(xia)(xia)裂解(jie)生(sheng)(sheng)成(cheng)(cheng)乙(yi)(yi)烯(xi)(xi)(xi)(xi)(xi)(xi)酮。然(ran)后(hou)与(yu)(yu)无水甲醋在AICI3或BF3催(cui)(cui)化(hua)(hua)(hua)(hua)剂存在下(xia)(xia)(xia),在25℃进(jin)行气(qi)相反应(ying)(ying),生(sheng)(sheng)成(cheng)(cheng)β-丙(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi):如(ru)目的(de)(de)(de)(de)(de)(de)产(chan)(chan)(chan)物(wu)是(shi)(shi)(shi)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan),则将(jiang)丙(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)与(yu)(yu)热(re)的(de)(de)(de)(de)(de)(de)100%磷(lin)(lin)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)接触,便(bian)异构成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan);若目的(de)(de)(de)(de)(de)(de)产(chan)(chan)(chan)物(wu)是(shi)(shi)(shi)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi),则粗丙(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)可(ke)(ke)不(bu)经(jing)提纯,直(zhi)接与(yu)(yu)相应(ying)(ying)的(de)(de)(de)(de)(de)(de)醇(chun)(chun)及硫(liu)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)反应(ying)(ying)。
4.雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)(he)(he)(he)改良(liang)(liang)雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 第二次世(shi)界大战期(qi)间,Reppe在研(yan)究工(gong)作中(zhong)发现了两(liang)种方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)使(shi)乙(yi)(yi)炔(gui)、一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan)与(yu)(yu)水或醇(chun)(chun)反应(ying)(ying)合(he)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)或丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酯(zhi)(zhi)。即(ji)“化(hua)(hua)(hua)(hua)学(xue)计量法(fa)(fa)(fa)(fa)(fa)(fa)(fa)”和(he)(he)(he)(he)“催(cui)(cui)化(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)”,后(hou)来(lai)经(jing)过(guo)发展成(cheng)(cheng)为(wei)(wei)Rohm&Hass公司在生(sheng)(sheng)产(chan)(chan)(chan)中(zhong)采(cai)用(yong)(yong)(yong)的(de)(de)(de)(de)(de)(de)改进(jin)的(de)(de)(de)(de)(de)(de)雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)(he)(he)(he)Dow-Badiche公司采(cai)用(yong)(yong)(yong)的(de)(de)(de)(de)(de)(de)高压雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)。
(1)化(hua)(hua)(hua)(hua)学(xue)计量法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)是(shi)(shi)(shi)使(shi)乙(yi)(yi)炔(gui)、羰基镍(提供(gong)一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan))与(yu)(yu)水或醇(chun)(chun)在比较温(wen)和(he)(he)(he)(he)条件(jian)下(xia)(xia)(xia)(40℃,0.101MPa)反应(ying)(ying),生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)或丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi):
(2)催(cui)(cui)化(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 乙(yi)(yi)炔(gui)、一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan)、醇(chun)(chun)在羰基镍催(cui)(cui)化(hua)(hua)(hua)(hua)剂存在下(xia)(xia)(xia),于(yu)(yu)(yu)150℃、1.50-3MPa下(xia)(xia)(xia)进(jin)行反应(ying)(ying)制(zhi)(zhi)得(de)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)酯(zhi)(zhi):
(3)改良(liang)(liang)雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此法(fa)(fa)(fa)(fa)(fa)(fa)(fa)是(shi)(shi)(shi)上(shang)述两(liang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)的(de)(de)(de)(de)(de)(de)结合(he),在化(hua)(hua)(hua)(hua)学(xue)计量法(fa)(fa)(fa)(fa)(fa)(fa)(fa)反应(ying)(ying)开始(shi)后(hou),通(tong)入(ru)一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan)和(he)(he)(he)(he)乙(yi)(yi)炔(gui),反应(ying)(ying)即(ji)可(ke)(ke)连续(xu)进(jin)行,反应(ying)(ying)所需的(de)(de)(de)(de)(de)(de)一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan)有(you)(you)80%可(ke)(ke)用(yong)(yong)(yong)气(qi)体(ti)一(yi)(yi)(yi)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan),而羰基镍只(zhi)需提供(gong)20%。
(4)高压雷(lei)(lei)佩(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此法(fa)(fa)(fa)(fa)(fa)(fa)(fa)的(de)(de)(de)(de)(de)(de)特点是(shi)(shi)(shi)用(yong)(yong)(yong)四氢(qing)呋(fu)(fu)喃(nan)(nan)为(wei)(wei)溶剂,将(jiang)反应(ying)(ying)所需的(de)(de)(de)(de)(de)(de)乙(yi)(yi)炔(gui)先溶解(jie)在四氢(qing)呋(fu)(fu)喃(nan)(nan)中(zhong),这样可(ke)(ke)减(jian)少高压处理乙(yi)(yi)炔(gui)的(de)(de)(de)(de)(de)(de)危险,同时(shi)不(bu)用(yong)(yong)(yong)羰基镍,只(zhi)需用(yong)(yong)(yong)镍盐作催(cui)(cui)化(hua)(hua)(hua)(hua)剂,在200-225℃和(he)(he)(he)(he)8.11-10.13MPa下(xia)(xia)(xia)进(jin)行反应(ying)(ying)。
(5)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)直(zhi)接氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa) 丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)气(qi)相空(kong)气(qi)催(cui)(cui)化(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)是(shi)(shi)(shi)生(sheng)(sheng)产(chan)(chan)(chan)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)及其酯(zhi)(zhi)类的(de)(de)(de)(de)(de)(de)最(zui)新方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)。原料(liao)消(xiao)耗(hao)定(ding)额:丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)770kg/t、正丁醇(chun)(chun)610kg/t。
5.制(zhi)(zhi)法(fa)(fa)(fa)(fa)(fa)(fa)(fa): 于(yu)(yu)(yu)装有(you)(you)韦氏(shi)分馏柱(带蒸馏装置(zhi))、搅拌器、通(tong)气(qi)导管的(de)(de)(de)(de)(de)(de)反应(ying)(ying)瓶中(zhong),加(jia)入(ru)正丁醇(chun)(chun)371g(5.0mol),丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)甲酯(zhi)(zhi)
(2)861g(10.0mol),对(dui)苯二酚20g和(he)(he)(he)(he)对(dui)甲苯磺(huang)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)10g,通(tong)入(ru)二氧(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)碳(tan)气(qi)体(ti),搅拌下(xia)(xia)(xia)油(you)浴加(jia)热(re)回(hui)流。首先蒸出的(de)(de)(de)(de)(de)(de)是(shi)(shi)(shi)甲醇(chun)(chun)-丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)甲酯(zhi)(zhi)的(de)(de)(de)(de)(de)(de)共沸(fei)物(wu)(62~63℃),控制(zhi)(zhi)蒸馏头温(wen)度不(bu)超过(guo)65℃。约(yue)8~10h当(dang)甲醇(chun)(chun)的(de)(de)(de)(de)(de)(de)产(chan)(chan)(chan)生(sheng)(sheng)很(hen)缓慢时(shi),减(jian)压蒸出过(guo)量的(de)(de)(de)(de)(de)(de)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)甲酯(zhi)(zhi),而后(hou)减(jian)压收(shou)(shou)集39℃/1.33kPa的(de)(de)(de)(de)(de)(de)馏分,得(de)丙(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)(suan)(suan)(suan)正丁酯(zhi)(zhi)①
(1)500~600g,收(shou)(shou)率78%~94%。注:①该方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)采(cai)用(yong)(yong)(yong)了酯(zhi)(zhi)过(guo)量的(de)(de)(de)(de)(de)(de)方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)进(jin)行酯(zhi)(zhi)交换(huan)反应(ying)(ying),酯(zhi)(zhi)回(hui)收(shou)(shou)后(hou)可(ke)(ke)循环使(shi)用(yong)(yong)(yong)。利用(yong)(yong)(yong)该方(fang)(fang)(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)可(ke)(ke)以(yi)合(he)成(cheng)(cheng)如(ru)下(xia)(xia)(xia)各种酯(zhi)(zhi)(表I-9-
1 参考书485页)。