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CN108947937A - 丙烯酰胺和甲酰胺型化合物的联产制备方法 - Google Patents

丙烯酰胺和甲酰胺型化合物的联产制备方法 Download PDF

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CN108947937A
CN108947937A CN201710376213.8A CN201710376213A CN108947937A CN 108947937 A CN108947937 A CN 108947937A CN 201710376213 A CN201710376213 A CN 201710376213A CN 108947937 A CN108947937 A CN 108947937A
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formic acid
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王智刚
丁浩宇
胡朗希
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SHENZHEN YOUWEI CHEMICAL TECHNOLOGY Co Ltd
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Abstract

本发明涉及新材料精细化学品领域，特别涉及一类甲酰胺型和单或多官能度丙烯酰胺型化合物的温和高效且经济性联合生产新工艺技术。上述物质均是应用广泛的化学材料，其中甲酰胺是重要的溶剂或原材料，丙烯酰胺则是重要的含烯不饱和型可辐射聚合单体化合物。

Description

丙烯酰胺和甲酰胺型化合物的联产制备方法
【技术领域】
本发明涉及新材料精细化学品领域，特别涉及一类甲酰胺型和单或多官能度丙烯酰胺型化合物的温和高效且经济性联合生产新工艺技术。上述物质均是应用广泛的化学材料，其中甲酰胺是重要的溶剂或原材料，丙烯酰胺则是重要的含烯不饱和型可辐射聚合单体化合物。
【背景技术】
单或多官能度的丙烯酰胺类化合物是重要的含烯不饱和可聚合型有机化学品，与传统可聚合型丙烯酸酯或苯乙烯型化合物相比，拥有如下的优越性能：其一是反应活性高，通常拥有比官能度相当的丙烯酸酯显著高超的聚合反应活性；其二是生物安全性，突出体现在较低的气味和/或皮肤生理刺激性；其三是兼具优良的油溶性和水溶性；其四是较低的粘度特性，使得在以无溶剂喷涂施工为主导的涂装领域应用潜力巨大。上述性能使得其尤其在作为辐射固化反应性单体，树脂前体，或医药新材料领域，有着日趋广泛的应用。另一方面，为从业技术人员众所周知的，由于有机胺对丙烯酸(酯)碳碳不饱和双键的较高迈克尔加成反应(Michael Addition)活性，因此与丙烯酸酯型化合物的制备技术迥然不同，单或多官能度的丙烯酰胺类化合物不能经由相应的丙烯酸和胺前体直接缩合而来，文献已披露的丙烯酰胺类化合物合成技术相当有限，例如日本专利JP09-279395，JP49-66625，JP05-163279，国际专利WO2015/146876，中国申请CN103992294；以及论文TetrahedronLett.2003，44，7485，山东化工，2015，44，33，应用化工，2015，44，1257，和Can.J.Chem.1976，266)。这些方法或者使用高温裂解等苛刻和危险工艺，或者工艺条件效率低下成本高昂。目前业界只有日本兴人化学(Konjin Chem)公司使用高温真空裂解工艺实现了单官能度丙烯酰胺的工业化生产。
甲酰胺型化合物是性能优良的溶剂，精细化学品原材料，电子化学品材料，以及石油开采助剂等，用途极为广泛。甲酰胺型化合物通常不适合经由甲酸和胺直接缩合制备(合成化学，2014，22，250)，相关的制备技术文献研究披露例如：中国专利CN2012104656754，CN2013105013840，CN2013104152600，和WO2016131371A等，这些已知技术使用氯代烃等腐蚀性原材料或压力条件以及使用不易制备和循环利用的金属催化剂。
由上当前的技术状况总结可知，仍然亟需发展简单温和，高效安全，绿色环保，且具备经济竞争力的生产新工艺来制造系列丙烯酰胺类和甲酰胺类化合物，以应对产业领域对上述产品日益增长的需求。本项申请的要旨在于，出其不意地发明了一种全新的环境友好工艺，首次使得通过一个反应流程低成本和环境友好型地同时制备上述两类重要价值的化学品。
【发明内容】
本项申请现已意外地发现，经由下面方程式(I)描述的反应技术，自结构式A所示的取代丙酰胺原料出发和试剂B在适当的反应条件Conditions作用，即可制备一系列结构式C和/或D所示的目标产物。
在上述方程式(I)中，R1和R2分别独立的是氢，含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团，该基团可以为1-6个非连续的氧原子，氮原子，硫原子，氟原子，硅原子，羰基，羟基，胺基，羧基，双键，三键，硅氧基，或C6-C24芳环取代；或者，R1和R2分别独立的是C6-C24芳基，该芳基可以含有0-4个C1-C24烷基，OC1-C24烷氧基，SC1-C24烷硫基，NHC1-C24烷胺基，N(C1-C24)2烷胺基，或卤素取代基；R1和R2之间也可以形成一个C3-C12环结构，该环结构可以为1-4个非连续的氧原子，氮原子，硫原子，双键，或羰基间断。
R3或R4的定义彼此独立地与R1或R2相同；R5是氢，甲基，或羟甲基。R1和R2之间，和/或R3和R4之间，可以形成一个环结构。
B是一个含有甲酰基(CHO)的结构，即甲酸，甲醛，乙二醛，甲酸酯，甲酰胺，甲酸铵，甲酸碱金属或碱土金属盐，C1-C24脂肪型醛，或C6-C24芳香型醛；即R6可以是羟基，氢，CHO，R1，OR1，NHR1，NR1R2，OM(M是金属或碱土金属阳离子)。当R6取值为氢，即B为甲醛时，B可以是自由甲醛或者甲醛的聚合体形式，包括固态的甲醛聚合物或液态的甲醛聚合物(相应的产物D是R1R2NCH2OH)。
优选的，R6取值为羟基，即B为甲酸。甲酸可以为市售的甲酸，或为在反应过程中原位生成的甲酸，例如甲酸的碱金属或碱土金属盐HCO2M和质子酸反应原位生成的甲酸或其化学等价物。如下式(II)所示，上述反应的结果除了产物外，唯一副产物是水，具有突出的环境友好型和经济竞争力。
Conditions是指有机碱，无机碱，催化剂或促进剂，阻聚剂，热，微波，超声波，真空或压力，溶剂等条件中的任意一种，或是上述任意两种或两种以上因素的联合使用，并无特别限定。有机碱是脂肪或芳香叔胺型化合物，包括含有C＝N双键的叔胺；无机碱是碱金属，碱土金属，或过渡金属的氢氧化物，氧化物，硫化物，碳酸盐，羧酸盐，或磺酸盐；催化剂或促进剂是指路易斯酸性或碱性化合物；反应中优选地使用到阻聚剂，常用的阻聚剂是苯酚，苯酚类衍生物(包括但不限于对苯二酚，邻苯二酚，间苯二酚，对甲基苯酚，对甲氧基苯酚，2，6-二叔丁基-4-甲基苯酚，焦性没食子酸等)，三(N-亚硝基-N-苯基羟胺)铝盐，或CuCl，吩噻嗪，亚磷酸酯，亚磷酸三哌啶氮氧自由基酯，N，N-二烷基二硫代氨基甲酸铜，或上述阻聚剂的混合体系，阻聚剂的用量按照原料的摩尔百分比计为0.01-5％，优选的是0.01-3％；热是指反应体系在加热条件下进行，反应温度是-25-400摄氏度，优选的是0-200摄氏度，更优选的是10-150摄氏度；微波或超声波是指使用微波或超声波发生器辐射反应体系；压力是指反应体系在加压或一定真空度条件下进行，反应工艺的压力可以是0.001-50个大气压，优选的是0.001-20个大气压，更优选的是0.001-10个大气压。溶剂可以是芳香性或脂肪性烃，卤代芳香性或脂肪性烃，或各类酯，醇，醚，腈，酮，酰胺，砜，碳酸酯，或水，或新兴的“离子液(Ionic Liquids)型”或超临界二氧化碳(Supercritical CO2)等所谓绿色溶剂；或上述任意二者或二者以上的混合溶剂体系。溶剂的使用是优选但非必需的，在某些条件下，可以不使用溶剂，反应原料直接混合后在加热或气相条件下进行反应。
结构式A所示的取代丙酰胺原料通常是已知的化合物，如下式(III)所示，可以直接商业采购和/或经由文献已知方法自下述所示的胺E和G与丙烯酸(酯)F直接缩合方便地加以制备(一个示例性文献是Tetrahedron Lett.2008，49，5147)；这里R7和R1的定义相同。
有鉴于此，目标化合物C和/或D的制备也可以考虑在不分离中间体A的条件下，由相应的原材料E和G依次与F先行反应制备A，A再和B在Conditions下反应制备产物。即将反应(III)和(I)耦合，以“一锅煮”的方式进行，本发明披露的工艺因此具有很强的实用性和经济竞争力。
一个示例性的合成是制备代表性化合物丙烯酰吗啉(ACMO)。如下所示，自文献已知的方法(日本专利JP09-279395或JP2006182676)可方便制备的3-吗啉基丙酰吗啉和甲酸在合适的条件下直接作用，即可生成丙烯酰吗啉和甲酰吗啉两个目标产物。另一个示例性的合成是制备代表性化合物N，N-二乙基丙烯酰胺(DEAA)。如下所示，3-二乙胺基丙酰二乙胺和甲酸在合适的条件下直接作用，即可生成N，N-二乙基丙烯酰胺和N，N-二乙基甲酰胺两个目标产物。这种原子经济性的合成拥有无与伦比的经济竞争力和绿色化学工艺优势。
可以经由本申请披露技术制备的丙烯酰吗啉类化合物的示例性而非限定性化合物例如如下结构：
上面所描述的丙烯酰胺型化合物是重要的含烯不饱和辐射聚合单体材料。
在实施例中我们将进一步说明。
【具体实施方式】
下面结合具体实施例进一步说明本发明要旨：
实施例一：
在氩气保护下，将50.0克3-吗啉基丙酰吗啉，11.1克甲酸，0.5克阻聚剂吩噻嗪和200毫升二甲苯加入反应瓶中，升温到140摄氏度反应2小时，补加11.0克甲酸，继续搅拌反应过夜后脱除溶剂，残留混合物减压蒸馏得到产品45.5克，气相色谱GC检测主要为两个产品峰，分别为甲酰吗啉和丙烯酰吗啉，含量分别为48.7％和51.8％。该产品精馏分馏后即得到单一纯品产品。
实施例二：
在氩气保护下，将40.0克3-二乙胺基丙酰二乙胺，9.2克甲酸，0.4克阻聚剂吩噻嗪和170毫升二甲苯加入反应瓶中，升温到140摄氏度反应2小时，补加9.2克甲酸，继续搅拌反应8小时后脱除溶剂，残留混合物减压蒸馏得到产品52.6克，气相色谱GC检测主要为两个产品峰，分别为甲酰二乙胺和丙烯酰吗啉，含量分别为46.7％和49.2％。该产品精馏分馏后即得到单一纯品产品。
实施例三：
在氩气保护下，将50.0克3-吗啉基丙酰吗啉，7.2克多聚甲醛，0.5克阻聚剂吩噻嗪和200毫升二甲苯加入反应瓶中，升温到110摄氏度反应4小时，补加7.2克多聚甲醛，继续搅拌反应8小时后脱除溶剂，残留混合物减压蒸馏得到产品42.5克，气相色谱GC检测主要为两个产品峰，分别为羟甲基吗啉和丙烯酰吗啉，含量分别为48.9％和52.1％。该产品精馏分馏后即得到单一纯品产品。
实施例四：以丙烯酸为原料“一锅煮”法合成
在氩气保护下，室温下烧瓶中加入322克吗啉和66.3克丙烯酸，升温至50℃搅拌半小时。升温至135℃后保温反应8小时，100℃减压蒸馏除去吗啉和生成的水份，再加入147.4克新鲜无水吗啉，升温至135℃，继续回流反应3小时，观察到吗啉基丙酰吗啉生成完全，在100℃减压蒸馏回收大部分吗啉后，在高真空蒸馏10分钟去除残留吗啉，得到的203克3-吗啉基丙酰吗啉中间体直接和45.2克甲酸，1.9克阻聚剂吩噻嗪和1升二甲苯加入反应瓶中，升温到140摄氏度反应4小时，补加46.2克甲酸，继续搅拌反应过夜后脱除溶剂，残留混合物减压蒸馏得到产品198.4克，气相色谱GC检测主要为两个产品峰，分别为甲酰吗啉和丙烯酰吗啉，含量分别为45.4％和50.6％。该产品精馏分馏后即得到单一纯品产品。
实施例五：以丙烯酸酯为原料“一锅煮”法合成
在氩气保护下，室温下于烧瓶中加入92.5克吗啉和0.22克阻聚剂BHT，于1小时内缓慢滴加37克丙烯酸甲酯，加毕再补加18.5克吗啉，体系于55℃保温反应2小时。在该温度下于1小时内缓慢滴加7.8克的30％的甲醇钠和40克甲醇的混合液，加完升温至75℃保温反应约5小时，反应完后缓慢滴加2.3克浓硫酸，常压蒸馏回收甲醇，减压蒸馏回收吗啉。得到的93.4克3-吗啉基丙酰吗啉中间体直接和18.8克甲酸，0.84克阻聚剂吩噻嗪和450毫升二甲苯加入反应瓶中，升温到140摄氏度反应2小时，补加18.1克甲酸，继续搅拌反应过夜后脱除溶剂，残留混合物减压蒸馏得到产品95.6克，气相色谱GC检测主要为两个产品峰，分别为甲酰吗啉和丙烯酰吗啉，含量分别为46.1％和51.7％。该产品精馏分馏后即得到单一纯品产品。
实施例六：
在氩气保护下，将5.2克预先制备的3-N，N-二乙胺基丙酰吗啉，1.3克甲酸，58毫克阻聚剂吩噻嗪和25毫升二甲苯加入反应瓶中，升温到140摄氏度反应45分钟，补加1.2克甲酸，继续搅拌反应5小时后脱除溶剂，残留混合物减压蒸馏得到产品5.1克，气相色谱GC检测主要为两个产品峰，分别为N，N-二乙基甲酰胺和丙烯酰吗啉，含量分别为44.8％和50.3％。该产品精馏分馏后即得到单一纯品产品。
需要强调的是，上述实施例仅仅为示例性而非限定性说明，基于本项申请披露，任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨，本专利的保护范围应以相关的权利书记载条目为准。

Claims (13)

1.方程式(I)描述的反应工艺技术，结构式A所示的取代丙酰胺原料和试剂B在适当的反应条件Conditions作用，同时制备一系列结构式C和/或D所示的目标产物；
在上述方程式(I)中，R1和R2分别独立的是氢，含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团，该基团可以为1-6个非连续的氧原子，氮原子，硫原子，氟原子，硅原子，羰基，羟基，胺基，羧基，双键，三键，硅氧基，或C6-C24芳环取代；或者，R1和R2分别独立的是C6-C24芳基，该芳基可以含有0-4个C1-C24烷基，OC1-C24烷氧基，SC1-C24烷硫基，NHC1-C24烷胺基，N(C1-C24)2烷胺基，或卤素取代基；R1和R2之间也可以形成一个C3-C12环结构，该环结构可以为1-4个非连续的氧原子，氮原子，硫原子，双键，或羰基间断。
R3或R4的定义彼此独立地与R1或R2相同；R5是氢，甲基，或羟甲基。R1和R2之间，和/或R3和R4之间，可以形成一个环结构。
B是一个含有甲酰基(CHO)的结构，即甲酸，甲醛，乙二醛，甲酸酯，甲酰胺，甲酸铵，甲酸碱金属或碱土金属盐，C1-C24脂肪型醛，或C6-C24芳香型醛；即R6是OH，H，CHO，R1，OR1，NHR1，NR1R2，或OM(M是金属或碱土金属阳离子)。
Conditions是指有机碱，无机碱，催化剂或促进剂，阻聚剂，热，微波，超声波，真空或压力，溶剂等条件中的任意一种，或是上述任意两种或两种以上因素的联合使用。
2.方程式(III和I)描述的“一锅煮”反应工艺技术，由相应的原材料E和G依次与F先行反应制备A，A再和B在Conditions下反应制备一系列结构式C和/或D所示的目标产物；
在上述反应式III和I中，各基团，物质，和Conditions的定义与权利要求(1)中相应项相同，R7和R1的定义相同。
3.根据权利要求(1-2)描述的工艺方法，B为甲酸，如下式所示，反应的结果除了产物外，唯一副产物是水；
在上述反应式中，各基团和Conditions的定义与权利要求(1)中相应项相同。
4.根据权利要求(1-2)描述的工艺方法，B为甲醛，如下式所示，反应的结果除了产物外，半缩醛R1R2NCH2OH可以用于回收R1R2NH；
在上述反应式中，各基团和Conditions的定义与权利要求(1)中相应项相同，B可以是自由甲醛或者甲醛的聚合体形式，包括固态的甲醛聚合物或液态的甲醛聚合物。
5.根据权利要求(1-2)描述的工艺方法，有机碱是脂肪或芳香叔胺型化合物，包括含有C＝N双键的叔胺；无机碱是碱金属，碱土金属，或过渡金属的氢氧化物，氧化物，硫化物，碳酸盐，羧酸盐，或磺酸盐；催化剂或促进剂是指路易斯酸性或碱性化合物。
6.根据权利要求(1-2)描述的工艺方法，阻聚剂是苯酚，苯酚类衍生物(包括但不限于对苯二酚，邻苯二酚，间苯二酚，对甲基苯酚，对甲氧基苯酚，2，6-二叔丁基-4-甲基苯酚，焦性没食子酸等)，三(N-亚硝基-N-苯基羟胺)铝盐，或CuCl，吩噻嗪，亚磷酸酯，亚磷酸三哌啶氮氧自由基酯，N，N-二烷基二硫代氨基甲酸铜，或上述阻聚剂的混合体系；阻聚剂的用量按照原料的摩尔百分比计为0.01-5％，优选的是0.01-3％。
7.根据权利要求(1-2)描述的工艺方法，反应温度是-25-400摄氏度，优选的是0-200摄氏度，更优选的是10-150摄氏度。微波或超声波是指使用微波或超声波发生器辐射反应体系。
8.根据权利要求(1-2)描述的工艺方法，反应压力可以是0.001-50个大气压，优选的是0.001-20个大气压，更优选的是0.001-10个大气压。
9.根据权利要求(1-2)描述的工艺方法，溶剂可以是芳香性或脂肪性烃，卤代芳香性或脂肪性烃，或各类酯，醇，醚，腈，酮，酰胺，砜，碳酸酯，或水，或“离子液型”或超临界二氧化碳绿色溶剂；或上述任意二者或二者以上的混合溶剂体系。溶剂的使用是优选但非必需的，在某些条件下，可以不使用溶剂，反应原料直接混合后在加热或气相条件下进行反应。
10.根据权利要求(1，2，和3)描述的工艺方法，由单独制备或者原位制备的3-吗啉基丙酰吗啉和甲酸在合适的Conditions下作用，制备丙烯酰吗啉(ACMO)和N-甲酰吗啉；
Conditions的定义与权利要求(1)中相应项相同。
11.根据权利要求(1，2，和3)描述的工艺方法，由单独制备或者原位制备的3-二乙胺基丙酰二乙胺和甲酸在合适的Conditions下作用，制备N，N-二乙基丙烯酰胺和N，N-二乙基甲酰胺；
Conditions的定义与权利要求(1)中相应项相同。
12.根据权利要求(1-2)描述的工艺方法，制备下述丙烯酰吗啉类化合物：
13.根据权利要求(1-2)描述的工艺方法所制备得到的丙烯酰胺化合物C和甲酰胺化合物D分别在辐射聚合过程中作为含烯不饱和单体，或在精细化工生产中作为原料或溶剂，的用途；
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