亚磷酸三(2-氯乙基)酯和NN-双羟乙基苯胺的连续制备研究

硕士学位论文IV第一章绪论1.1研究背景环氧化合物[1-2]是化工工业中一类重要的生产原料ADDINEN.CITE<EndNote><Cite><Author>姚本镇</Author><Year>2011</Year><RecNum>143</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>143</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586848854">143</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">李丽芳</style><styleface="normal"font="default"size="100%"></style><styleface="normal"font="default"charset="134"size="100%">姚本镇</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">环氧乙烷下游产品研究开发进展</style></title><secondary-title><styleface="normal"font="default"size="100%"></style><styleface="normal"font="default"charset="134"size="100%">石油化工技术与经济</style></secondary-title></titles><pages>21-27</pages><volume>27</volume><number>06</number><dates><year>2011</year></dates><urls></urls></record></Cite></EndNote>[1]。由于其结构的不稳定性，分子内部张力较大，分子内的环氧结构极易与许多含有活泼基团的化合物进行开环加成反应，从而合成出众多重要的化工产品ADDINEN.CITEADDINEN.CITE.DATA[2-4]。环氧化合物中环氧乙烷每年全球的消耗量为2400万吨，被广泛应用医药、洗涤、电子、农药、纺织、造纸、汽车等方面，可以制造合成纤维、汽车防冻剂、增塑剂以及炸药等一系列的化工产品。环氧乙烷与三氯化磷反应生成的亚磷酸三(2-氯乙基)酯，是合成乙烯利ADDINEN.CITE<EndNote><Cite><Author>Steffens</Author><Year>2005</Year><RecNum>70</RecNum><DisplayText><styleface="superscript">[5]</style></DisplayText><record><rec-number>70</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586762371">70</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Steffens,C.A.</author><author>Giehl,R.F.H.</author><author>Brackmann,A.</author></authors></contributors><titles><title>'Gala'applestoredincontrolledatmosphereandtreatedwithaminoethoxyvinylglycineandethephon</title><secondary-title>PesquisaAgropecuariaBrasileira</secondary-title></titles><periodical><full-title>PesquisaAgropecuariaBrasileira</full-title></periodical><pages>837-843</pages><volume>40</volume><number>9</number><dates><year>2005</year><pub-dates><date>Sep</date></pub-dates></dates><isbn>0100-204X</isbn><accession-num>WOS:000233432900001</accession-num><urls><related-urls><url><GotoISI>://WOS:000233432900001</url></related-urls></urls><electronic-resource-num>10.1590/s0100-204x2005000900001</electronic-resource-num></record></Cite></EndNote>[5]和磷系阻燃剂的重要中间体。环氧乙烷与苯胺反应生成的N，N-双羟乙基苯胺是化工领域的一种重要有机中间体，被广泛应用于医药和染料行业ADDINEN.CITE<EndNote><Cite><Author>杨凤玲</Author><Year>2000</Year><RecNum>144</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>144</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586849057">144</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">贾廷奎</style><styleface="normal"font="default"size="100%"></style><styleface="normal"font="default"charset="134"size="100%">李金成</style><styleface="normal"font="default"size="100%"></style><styleface="normal"font="default"charset="134"size="100%">师红娟</style><styleface="normal"font="default"size="100%"></style><styleface="normal"font="default"charset="134"size="100%">杨凤玲</style></author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">N_N_</style><styleface="normal"font="default"charset="134"size="100%">双羟乙基苯胺的合成及应用</style></title><secondary-title>2000</secondary-title></titles><periodical><full-title>2000</full-title></periodical><pages>14-17</pages><volume>2</volume><number>04</number><dates><year>2000</year></dates><urls></urls></record></Cite></EndNote>[6]。这类反应均为强放热反应，在釜式反应中不但需要强烈的搅拌以防止体系局部过热，还需要大量的冷却循环介质以及时移除体系中的热量。此外，这类反应在温度过高时还容易引发一系列副反应导致产品品质降低。环氧乙烷是一种易燃物质且强致癌的物质，在空气中的爆炸范围为3-100%。釜内温度过高对生产存在较大的安全隐患ADDINEN.CITEADDINEN.CITE.DATA[7-9]，近年来多次出现以环氧乙烷为原料的生产出现不同程度的安全事故。鉴于这些强放热反应对产品品质以及生产安全性和经济性带来的影响，人们设计了很多反应器类型，例如列管式反应器ADDINEN.CITE<EndNote><Cite><Author>Tang</Author><Year>2008</Year><RecNum>20</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>20</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1584018785">20</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tang,Zhiyong</author><author>Wang,Lianyuan</author><author>Yang,Jichu</author></authors></contributors><titles><title>Transesterificationofrapeseedoilcatalyzedbyliquidorganicamineinsupercriticalmethanolinacontinuoustubular-flowreactor</title><secondary-title>EuropeanJournalofLipidScienceandTechnology</secondary-title></titles><periodical><full-title>EuropeanJournalofLipidScienceandTechnology</full-title></periodical><pages>747-753</pages><volume>110</volume><number>8</number><dates><year>2008</year></dates><isbn>14387697 14389312</isbn><urls></urls><electronic-resource-num>10.1002/ejlt.200700256</electronic-resource-num></record></Cite></EndNote>[10]、塔式反应器ADDINEN.CITE<EndNote><Cite><Author>Bouyahiaoui</Author><Year>2020</Year><RecNum>63</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>63</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586760869">63</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bouyahiaoui,Hiba</author><author>Azzi,Abdelwahid</author><author>Zeghloul,Ammar</author><author>Hasan,AbbasH.</author><author>Al-Sarkhi,Abdelsalam</author><author>Parsi,Mazdak</author></authors></contributors><titles><title>Verticalupwardanddownwardchurnflow:Similaritiesanddifferences</title><secondary-title>JournalofNaturalGasScienceandEngineering</secondary-title></titles><periodical><full-title>JournalofNaturalGasScienceandEngineering</full-title></periodical><volume>73</volume><section>103080</section><dates><year>2020</year></dates><isbn>18755100</isbn><urls></urls><electronic-resource-num>10.1016/j.jngse.2019.103080</electronic-resource-num></record></Cite></EndNote>[11]、流化床反应器ADDINEN.CITEADDINEN.CITE.DATA[12-14]、振荡流反应器ADDINEN.CITEADDINEN.CITE.DATA[15-20]、降膜反应器ADDINEN.CITEADDINEN.CITE.DATA[21-22]以及微反应器ADDINEN.CITEADDINEN.CITE.DATA[23-26]。根据每种反应器的特点可适用于特定的反应类型。本章对以环氧化合物为原料参与的反应所用到的反应器进行了总结，也对本文所研究的两个产品，进行文献介绍，在此基础上提出本文的研究目的和内容。1.2亚磷酸三(2-氯乙基)的合成路线及工艺亚磷酸三(2-氯乙基)酯ADDINEN.CITE<EndNote><Cite><Author>Mironova</Author><Year>1995</Year><RecNum>73</RecNum><DisplayText><styleface="superscript">[27]</style></DisplayText><record><rec-number>73</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586763416">73</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mironova,O.Y.</author><author>Yanilkin,V.V.</author><author>Kormachev,V.V.</author></authors></contributors><titles><title>Electrochemicalbehavioroftris(2-chloroethyl)phosphateandtris(2-chloroethyl)phosphite</title><secondary-title>ZhurnalObshcheiKhimii</secondary-title></titles><periodical><full-title>ZhurnalObshcheiKhimii</full-title></periodical><pages>2001-2004</pages><volume>65</volume><number>12</number><dates><year>1995</year><pub-dates><date>1995</date></pub-dates></dates><isbn>0044-460X</isbn><accession-num>WOS:A1995UL16300012</accession-num><urls><related-urls><url><GotoISI>://WOS:A1995UL16300012</url></related-urls></urls></record></Cite></EndNote>[27]作为化工领域中的一种重要有机中间体。在农药领域，亚磷酸三(2-氯乙基)酯通常用于制备乙烯利。乙烯利是一种优质、高效的植物生长调节剂，具有促进果实成熟、刺激\t"/item/%E4%B9%99%E7%83%AF%E5%88%A9/_blank"伤流、调节部分植物\t"/item/%E4%B9%99%E7%83%AF%E5%88%A9/_blank"性别转化等功能ADDINEN.CITEADDINEN.CITE.DATA[28-31]。在消防领域，亚磷酸三(2-氯乙基)酯可作为合成四(2-氯乙基)亚乙基二磷酸酯阻燃剂ADDINEN.CITE<EndNote><Cite><Author>朱广军</Author><Year>1994</Year><RecNum>71</RecNum><DisplayText><styleface="superscript">[32]</style></DisplayText><record><rec-number>71</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586762565">71</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">朱广军</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">阻燃剂</style><styleface="normal"font="default"size="100%">1_2_</style><styleface="normal"font="default"charset="134"size="100%">亚乙基四</style><styleface="normal"font="default"size="100%">_2_</style><styleface="normal"font="default"charset="134"size="100%">氯乙基</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">二磷酸酯的新合成法</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">化学通报</style></secondary-title></titles><periodical><full-title>化学通报</full-title></periodical><pages>35-36</pages><volume>2</volume><number>10</number><dates><year>1994</year></dates><urls></urls></record></Cite></EndNote>[32]的重要原料。四(2-氯乙基)亚乙基二磷酸酯通常作为一些有机聚合物的阻燃添加剂，具有相容性好、耐挥发、耐迁移、阻燃效果持久和毒性低等特点。1.2.1环氧乙烷与三氯化磷的合成路线1946年KabachnikMI和RossiiskayaPA首次报道了乙烯利的合成。通过环氧乙烷和三氯化磷作为初始原料，在低温下进行酯化反应得到亚磷酸三(2-氯乙基)酯，然后再经过高温重排、酸解反应合成乙烯利。在亚磷酸三(2-氯乙基)酯的反应过程中一分子三氯化磷先与一分子环氧乙烷开环加成生成一分子单酯，这过程反应迅速并且放出大量热。然后一分子单酯与一分子环氧乙烷继续反应生成一分子二酯，二酯分子与环氧乙烷分子继续反应最终生成亚磷酸三(2-氯乙基)酯分子，如图1-1。各产物生成的速率:单酯>二酯>三酯，如图1-2。1995年姬学仪和朱德湘等人ADDINEN.CITE<EndNote><Cite><Author>姬学仪</Author><Year>1995</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[33]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586592951">36</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">姬学仪</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">亚磷酸三</style><styleface="normal"font="default"size="100%">_2_</style><styleface="normal"font="default"charset="134"size="100%">氯乙基</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">酯的合成研究</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">江苏化工</style></secondary-title></titles><periodical><full-title>江苏化工</full-title></periodical><pages>4-7</pages><volume>23</volume><number>3</number><dates><year>1995</year></dates><urls></urls></record></Cite></EndNote>[33]ADDINEN.CITE<EndNote><Cite><Author>姬学仪</Author><Year>1995</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586592951">36</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">姬学仪</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">亚磷酸三</style><styleface="normal"font="default"size="100%">_2_</style><styleface="normal"font="default"charset="134"size="100%">氯乙基</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">酯的合成研究</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">江苏化工</style></secondary-title></titles><periodical><full-title>江苏化工</full-title></periodical><pages>4-7</pages><volume>23</volume><number>3</number><dates><year>1995</year></dates><urls></urls></record></Cite></EndNote>在无催化剂条件下，环氧乙烷以液态形式与三氯化磷反应制得亚磷酸三(2-氯乙基)酯，粗产品经提纯使得产品收率和纯度分别达到98.5%和99.99%。同年吴少林ADDINEN.CITE<EndNote><Cite><Author>吴少林</Author><Year>1995</Year><RecNum>37</RecNum><DisplayText><styleface="superscript">[34]</style></DisplayText><record><rec-number>37</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586593394">37</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">吴少林</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">亚磷酸三</style><styleface="normal"font="default"size="100%">_2_</style><styleface="normal"font="default"charset="134"size="100%">氯乙基</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">酯异构新工艺</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">化学世界</style></secondary-title></titles><periodical><full-title>化学世界</full-title></periodical><pages>367-370</pages><volume>7</volume><dates><year>1995</year></dates><urls></urls></record></Cite></EndNote>[34]采用环氧乙烷以气体形态与三氯化磷在25-30℃下制备亚磷酸三(2-氯乙基)酯。图1-1环氧乙烷与三氯化磷反应合成亚磷酸三(2-氯乙基)酯路线Figure1-1Synthesisoftris(2-chloroethyl)phosphitebyreactionofethyleneoxidewithphosphorustrichloride图1-2釜式反应下不同摩尔比的产物分布情况ADDINEN.CITE<EndNote><Cite><Author>姬学仪</Author><Year>1995</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[33]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586592951">36</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">姬学仪</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">亚磷酸三</style><styleface="normal"font="default"size="100%">_2_</style><styleface="normal"font="default"charset="134"size="100%">氯乙基</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">酯的合成研究</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">江苏化工</style></secondary-title></titles><periodical><full-title>江苏化工</full-title></periodical><pages>4-7</pages><volume>23</volume><number>3</number><dates><year>1995</year></dates><urls></urls></record></Cite></EndNote>[33]Figure1-2Distributionofproductswithdifferentmolarratiosinthekettlereaction1.2.2氯乙醇与三氯化磷的合成路线以氯乙醇与三氯化磷作为原料在一定条件下反应可制得亚磷酸三(2-氯乙基)酯，并且伴随氯化氢生成。部分氯化氢溶于反应液中会与亚磷酸三(2-氯乙基)酯发生反应，从而降低了产品中亚磷酸三(2-氯乙基)酯的含量。由于该反应选择性低下，仅为40%，并且在反应过程中需要对氯化氢进行吸收处理，增加了生产工序。从而一直未用于工业化生产，也很少有该合成路线的文献报道。1.2.3亚磷酸三(2-氯乙基)酯的合成工艺在工业上有两种亚磷酸三(2-氯乙基)酯的生产工艺，分别为传统釜式工艺和微通道工艺。釜式生产工艺是将环氧乙烷气体通入到装有三氯化磷的一级反应釜内，通过冷却系统使釜内温度维持在30℃左右，保温8小时后转移到二级反应釜内，釜内温度维持在40℃左右，进一步保温8小时后再一次转移至三级反应釜内，釜内温度为50-60℃内保温8小时，以确保反应完全。该酯化反应是强放热反应，在生产中存在一些问题:(1)由于反应釜的体积较大，换热面积极为有限ADDINEN.CITE<EndNote><Cite><Author>陈晓君</Author><Year>2011</Year><RecNum>93</RecNum><DisplayText><styleface="superscript">[35]</style></DisplayText><record><rec-number>93</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586781267">93</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">陈晓君</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">外夹套反应釜与外半管反应釜热交换形式的对比分析</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">广东化工</style></secondary-title></titles><periodical><full-title>广东化工</full-title></periodical><pages>166-178</pages><volume>38</volume><number>07</number><dates><year>2011</year></dates><urls></urls></record></Cite></EndNote>[35]。为了避免反应釜内的温度过高，环氧乙烷的通气速率仅为100~300kg/h，故生产一批亚磷酸三(2-氯乙基)酯的反应周期较长，生产效率低下。(2)由于亚磷酸三(2-氯乙基)酯本身不太稳定，在高温度下易发生副反应生成二聚体ADDINEN.CITE<EndNote><Cite><Author>Talos</Author><Year>2006</Year><RecNum>72</RecNum><DisplayText><styleface="superscript">[36]</style></DisplayText><record><rec-number>72</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586763416">72</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Talos,I.</author><author>Lupea,A.X.</author><author>Mihaila,C.T.</author><author>Bandur,G.</author></authors></contributors><titles><title>Thermicisomerizationfortris(2-chloroethyl)phosphiteandconsecutivetransformations</title><secondary-title>RevistaDeChimie</secondary-title></titles><periodical><full-title>RevistaDeChimie</full-title></periodical><pages>138-142</pages><volume>57</volume><number>2</number><dates><year>2006</year><pub-dates><date>Feb</date></pub-dates></dates><isbn>0034-7752</isbn><accession-num>WOS:000236716500006</accession-num><urls><related-urls><url><GotoISI>://WOS:000236716500006</url></related-urls></urls></record></Cite></EndNote>[36]，其中不对称的二聚体在第三步酸解反应中仍可以转变为乙烯利产品，但是对称二聚体则无法进行酸解，成为产品中的杂质。亚磷酸三(2-氯乙基)酯还极易与水发生水解反应，长时间存放于釜内容易受潮转变为副产物，进一步降低最终产品质量。因此，采用釜式生产工艺得到的亚磷酸三(2-氯乙基)酯的含量最高仅能达到90%，严重制约了乙烯利原药的品质。除了釜式生产工艺，绍兴市东湖生化有限公司开发了一种利用微通道制备亚磷酸三(2-氯乙基)酯的生产工艺ADDINEN.CITE<EndNote><Cite><RecNum>141</RecNum><DisplayText><styleface="superscript">[37]</style></DisplayText><record><rec-number>141</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586848124">141</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors></contributors><titles><title><CN104119374A.pdf></title></titles><dates></dates><urls></urls></record></Cite></EndNote>[37]。将液态环氧乙烷和三氯化磷通过连续泵输送至耦合管道式预混合器进行预混合(混合压力为0.01~2MPa)，然后混合后的反应液再进入到微通道反应装置，同时开启微通道反应系统的冷媒冷却设备，反应完全后，收集微通道反应装置的流出液，即为亚磷酸三(2-氯乙基)酯产品原液。该装置能够稳定连续制得流量为200~2000kg/h，含量为98%以上的产品。该微通道反应装置由1~10组微通道反应器串联构成，微通道反应器由50~500根管路组成，每根管路为Ф4mmx200mm的直管，每根管路盘旋在微通道反应器内，微通道反应器的直径为60mm，长为2000mm，见图1-3。图1-3微通道反应装置图ADDINEN.CITE<EndNote><Cite><RecNum>141</RecNum><DisplayText><styleface="superscript">[37]</style></DisplayText><record><rec-number>141</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586848124">141</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors></contributors><titles><title><CN104119374A.pdf></title></titles><dates></dates><urls></urls></record></Cite></EndNote>[37]Figure1-3Microchannelreactiondevicediagram1.3N，N-双羟乙基的合成路线及工艺N，N-双羟乙基苯胺是化工领域中一种重要的有机中间体。在医药领域可被用于合成芳胺类活性药，如N-甲基溶肉瘤素ADDINEN.CITE<EndNote><Cite><Author>Sidhu</Author><Year>1989</Year><RecNum>77</RecNum><DisplayText><styleface="superscript">[38]</style></DisplayText><record><rec-number>77</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586764926">77</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sidhu,M.K.</author><author>Kumar,S.</author></authors></contributors><auth-address>SIDHU,MK(reprintauthor),UNIVMED&DENTNEWJERSEY,NEWJERSEYMEDSCH,DEPTBIOCHEM&MOLECBIOL,185SORANGEAVE,NEWARK,NJ07103,USA.</auth-address><titles><title>SYNTHESISANDSECRETIONOFPLASMINOGENACTIVATORSANDCOLLAGENASESINHUMAN-CELLSTRANSFORMEDBYKIRSTENMURINESARCOMA-VIRUSANDN-METHYL-N'-NITRO-N-NITROSOGUANIDINE</title><secondary-title>CancerLetters</secondary-title><alt-title>CancerLett.</alt-title></titles><periodical><full-title>CancerLetters</full-title><abbr-1>CancerLett.</abbr-1></periodical><alt-periodical><full-title>CancerLetters</full-title><abbr-1>CancerLett.</abbr-1></alt-periodical><pages>45-51</pages><volume>47</volume><number>1-2</number><keywords><keyword>Oncology</keyword></keywords><dates><year>1989</year><pub-dates><date>Sep</date></pub-dates></dates><isbn>0304-3835</isbn><accession-num>WOS:A1989AW58800006</accession-num><work-type>Article</work-type><urls><related-urls><url><GotoISI>://WOS:A1989AW58800006</url></related-urls></urls><electronic-resource-num>10.1016/0304-3835(89)90175-4</electronic-resource-num><language>English</language></record></Cite></EndNote>[38]、抗瘤氨酸ADDINEN.CITE<EndNote><Cite><Author>Minotti</Author><Year>2004</Year><RecNum>78</RecNum><DisplayText><styleface="superscript">[39]</style></DisplayText><record><rec-number>78</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586765186">78</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Minotti,G.</author><author>Menna,P.</author><author>Salvatorelli,E.</author><author>Cairo,G.</author><author>Gianni,L.</author></authors></contributors><titles><title>Anthracyclines:Molecularadvancesandpharmacologicdevelopmentsinantitumoractivityandcardiotoxicity</title><secondary-title>PharmacologicalReviews</secondary-title></titles><periodical><full-title>PharmacologicalReviews</full-title></periodical><pages>185-229</pages><volume>56</volume><number>2</number><dates><year>2004</year><pub-dates><date>Jun</date></pub-dates></dates><isbn>0031-6997</isbn><accession-num>WOS:000222021100002</accession-num><urls><related-urls><url><GotoISI>://WOS:000222021100002</url></related-urls></urls><electronic-resource-num>10.1124/pr.56.2.6</electronic-resource-num></record></Cite></EndNote>[39]和活性抗生药。在染料行业中N，N-双羟乙基苯胺和许多偶氮类物质直接耦合制成染料。在聚合工业中N，N-双羟乙基苯胺和过氧化苯甲酰合成醋酸乙烯聚合的引发剂，被用于不饱和树脂聚合过程的硬化加速剂和交联剂以及聚脲烷泡沫的链增长剂，使制得的聚合体具有较高的承载能力。在油漆工业中N，N-双羟乙基苯胺用于制造丙烯酸漆的交联剂，制得的漆和芳酮复配成耐晒能力的油漆。它还和糠胺等可配制成油漆清除剂，加速油漆的清除。在胶粘剂工业中，N，N-双羟乙基苯胺能配制储存稳定性好的厌氧型压敏粘合材料。它还可以和异氰酸酯等配制成建筑材料粘合剂和建筑路面粘合剂。1.3.1苯胺与环氧乙烷的合成路线LiCZ和ZhouSF等人ADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2000</Year><RecNum>34</RecNum><DisplayText><styleface="superscript">[40]</style></DisplayText><record><rec-number>34</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1584627536">34</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,C.Z.</author><author>Zhou,S.F.</author><author>Fan,X.Z.</author><author>Zhu,Z.F.</author><author>Ding,Y.F.</author><author>Zhao,H.</author><author>Xia,C.G.</author><author>Wang,L.F.</author></authors></contributors><titles><title>Synthesis,characterization,andantitumouractivityofisonicotinamido-4-bis(2-chloroethyl)aminobenzaldiminecomplexesofsometransitionmetals</title><secondary-title>ChemicalPapers-ChemickeZvesti</secondary-title></titles><periodical><full-title>ChemicalPapers-ChemickeZvesti</full-title></periodical><pages>239-244</pages><volume>54</volume><number>4</number><dates><year>2000</year></dates><isbn>0366-6352</isbn><urls></urls></record></Cite></EndNote>[40]在异烟酰胺基-4-双(2-氯乙基)氨基苯甲二胺的合成路线中所需的N，N-双羟乙基苯胺中间体是由环氧乙烷气体通入到含有1wt%乙酸的苯胺溶液(温度<5℃)中，然后在2h内将溶液温度缓慢升温至70℃后保温20h。反应结束后低压条件下分离，得到N，N-双羟乙基苯胺粗品，产率为90%，异烟酰胺基-4-双(2-氯乙基)氨基苯甲二胺合成路线见图1-4。图1-4异烟酰胺基-4-双(2-氯乙基)氨基苯甲二胺的合成路线ADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2000</Year><RecNum>34</RecNum><DisplayText><styleface="superscript">[40]</style></DisplayText><record><rec-number>34</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1584627536">34</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,C.Z.</author><author>Zhou,S.F.</author><author>Fan,X.Z.</author><author>Zhu,Z.F.</author><author>Ding,Y.F.</author><author>Zhao,H.</author><author>Xia,C.G.</author><author>Wang,L.F.</author></authors></contributors><titles><title>Synthesis,characterization,andantitumouractivityofisonicotinamido-4-bis(2-chloroethyl)aminobenzaldiminecomplexesofsometransitionmetals</title><secondary-title>ChemicalPapers-ChemickeZvesti</secondary-title></titles><periodical><full-title>ChemicalPapers-ChemickeZvesti</full-title></periodical><pages>239-244</pages><volume>54</volume><number>4</number><dates><year>2000</year></dates><isbn>0366-6352</isbn><urls></urls></record></Cite></EndNote>[40]Figure1-4Isonicotinamido-4-bis(2-chloroethyl)aminobenzidinediaminesynthesisroute方线文和周丽珍等人ADDINEN.CITE<EndNote><Cite><Author>Fang</Author><Year>2013</Year><RecNum>38</RecNum><DisplayText><styleface="superscript">[41]</style></DisplayText><record><rec-number>38</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586593875">38</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Fang,Xianwen</author><author>Zhou,Lizhen</author><author>Cheng,Zhao</author><author>Yang,Meipan</author><author>Yang,Bingqin</author></authors></contributors><titles><title>Synthesis,CrystalStruturesandAntitumorActivityofNovelNitrogenMustard-LinkedChalcones</title><secondary-title>ChineseJournalofOrganicChemistry</secondary-title></titles><periodical><full-title>ChineseJournalofOrganicChemistry</full-title></periodical><volume>33</volume><number>3</number><section>523</section><dates><year>2013</year></dates><isbn>0253-2786</isbn><urls></urls><electronic-resource-num>10.6023/cjoc201211041</electronic-resource-num></record></Cite></EndNote>[41]在含氮芥基查尔酮类衍生物的制备中所需的N，N-双羟乙基苯胺中间体，采用以丙酸作为催化剂，将环氧乙烷气体通入到-5℃的苯胺溶液中过夜反应，TLC监测至苯胺原料点消失，将反应液倒入分液漏斗中，静置分层，有机相用饱和Na2CO3水洗，无水MgSO4干燥过夜，减压蒸出溶剂，残余物经硅胶柱色谱，得白色固体。N，N-双羟乙基苯胺收率为90%。查尔酮化合物的合成路线，见图1-5。图1-5查尔酮化合物的合成路线ADDINEN.CITE<EndNote><Cite><Author>Fang</Author><Year>2013</Year><RecNum>38</RecNum><DisplayText><styleface="superscript">[41]</style></DisplayText><record><rec-number>38</rec-number><foreign-keys><keyapp="EN"db-id="ztw92e5faa05tdewp53pr99ur9fra52awtpd"timestamp="1586593875">38</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Fang,Xianwen</author><author>Zhou,Lizhen</author><author>Cheng,Zhao</author><author>Yang,Meipan</author><author>Yang,Bingqin</author></authors></contributors><titles><title>Synthesis,CrystalStruturesandAntitumorActivityofNovelNitrogenMustard-LinkedChalcones</title><secondary-title>ChineseJournalofOrganicChemistry</secondary-title></titles><periodical><full-title>ChineseJournalofOrganicChemistry</full-title></periodical><volume>33</volume><number>3</number><section>523</section><dates><year>2013</year></dat