CN102020673B - Method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid under normal pressure - Google Patents
Method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid under normal pressure Download PDFInfo
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- CN102020673B CN102020673B CN2010105916389A CN201010591638A CN102020673B CN 102020673 B CN102020673 B CN 102020673B CN 2010105916389 A CN2010105916389 A CN 2010105916389A CN 201010591638 A CN201010591638 A CN 201010591638A CN 102020673 B CN102020673 B CN 102020673B
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- trimethylpentyl
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- 238000000034 method Methods 0.000 title claims abstract description 32
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 15
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 230000020477 pH reduction Effects 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000002825 nitriles Chemical class 0.000 claims abstract 2
- 239000003999 initiator Substances 0.000 claims description 8
- HZEFDBCGAGWRPF-UHFFFAOYSA-N OP(=O)CC(C)CC(C)(C)C Chemical compound OP(=O)CC(C)CC(C)(C)C HZEFDBCGAGWRPF-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 Mono-substituted 2,4,4-trimethylpentylphosphonous acid Chemical class 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
一种常压合成二(2，4，4-三甲基戊基)次膦酸的方法，是将次亚磷酸钠溶解于乙酸中，然后加入二异丁烯，常压室温条件下，在上述溶液中滴加偶氮二异丁腈，滴加完毕后加热至回流，回流条件下反应2h后，滴加一次偶氮二异丁腈，以后每间隔1-3小时补加一次偶氮二异丁腈，最后通过碱洗，酸化，脱水和真空旋蒸后得目标产物二(2，4，4-三甲基戊基)次膦酸。本发明与传统方法相比，常压下即可顺利反应，反应时间大大缩短、反应条件温和以及二(2，4，4-三甲基戊基)次膦酸收率高，工艺过程简单等优点，合成路线只需一步完成，减少了多步合成造成的原料和能源的消耗，降低了成本。A method for synthesizing di(2,4,4-trimethylpentyl)phosphinic acid under normal pressure is to dissolve sodium hypophosphite in acetic acid, then add diisobutene, under normal pressure and room temperature, in the above solution Add azobisisobutyronitrile dropwise, after the dropwise addition, heat to reflux, react under reflux for 2 hours, add azobisisobutyronitrile dropwise, and then add azobisisobutyronitrile every 1-3 hours Nitrile, and finally the target product bis(2,4,4-trimethylpentyl)phosphinic acid was obtained after alkali washing, acidification, dehydration and vacuum rotary evaporation. Compared with the traditional method, the present invention can react smoothly under normal pressure, the reaction time is greatly shortened, the reaction conditions are mild, the yield of di(2,4,4-trimethylpentyl)phosphinic acid is high, and the process is simple, etc. Advantages, the synthetic route only needs to be completed in one step, which reduces the consumption of raw materials and energy caused by multi-step synthesis, and reduces the cost.
Description
技术领域technical field
本发明涉及一种常压合成二(2，4，4-三甲基戊基)次膦酸的方法。The invention relates to a method for synthesizing di(2,4,4-trimethylpentyl)phosphinic acid under normal pressure.
技术背景technical background
二(2，4，4-三甲基戊基)次膦酸，是一种新型的酸性稀有金属的萃取剂，在钴镍萃取方面表现优异，是一种重要的化工产品。结构如下：Bis(2,4,4-trimethylpentyl)phosphinic acid is a new type of extraction agent for acidic rare metals. It has excellent performance in the extraction of cobalt and nickel, and is an important chemical product. The structure is as follows:
现有文献报导的合成二(2，4，4-三甲基戊基)次膦酸的方法主要有：①RORBERTSON A J.在名称为“Di-2，4，4’-trimethylpentyl phosphinic acidand its preparation.”的专利号为US4374780，申请日为1983/02/03的专利中介绍了以二异丁烯、磷化氢和过氧化氢为原料，在催化剂和压力条件下经自由基加成、氧化两步反应合成二(2，4，4-三甲基戊基)次膦酸的方法。The methods for the synthesis of di(2,4,4-trimethylpentyl)phosphinic acid reported in existing literature mainly contain: 1. RORBERTSON A J. The patent No. of "is US4374780, and the patent application date is 1983/02/03. In the patent, diisobutene, phosphine and hydrogen peroxide are used as raw materials, and two steps of free radical addition and oxidation are carried out under catalyst and pressure conditions. Reaction method for synthesizing two (2,4,4-trimethylpentyl) phosphinic acid.
另外，Shiming Wo和Floryan De Campo在名为“Process for thePreparation of Highly Purified，Dialkyl Phosphinic Acids”，专利号为US20060089508A1，申请日为2004/10/25以及Leo Zhaoqing Liu和GaryWoodward在名为“Process for the Preparation of Highly Purified，Dialkydithiophosphinic Compounds”，专利号为US20080103330A1，申请日为2006/10/25的专利中介绍了以次亚磷酸钠和二异丁烯为原料、以二叔丁基过氧化物为引发剂，在高温和压力条件下合成二(2，4，4-三甲基戊基)次膦酸的方法。文献和公开专利所述合成方法和制备工艺均要求在高压釜内进行，并且反应时间长，反应条件苛刻(压力、惰性环境、高温等)，对设备要求很高。In addition, Shiming Wo and Floryan De Campo in the titled "Process for the Preparation of Highly Purified, Dialkyl Phosphinic Acids", the patent number is US20060089508A1, the application date is 2004/10/25 and Leo Zhaoqing Liu and Gary Woodward in the titled "Process for the Preparation of Highly Purified, Dialkydithiophosphinic Compounds", the patent number is US20080103330A1, and the patent application date is 2006/10/25, which introduces sodium hypophosphite and diisobutylene as raw materials and di-tert-butyl peroxide as the initiator. A method for synthesizing bis(2,4,4-trimethylpentyl)phosphinic acid under conditions of high temperature and pressure. The synthesis method and preparation process described in the literature and published patents are all required to be carried out in an autoclave, and the reaction time is long, the reaction conditions are harsh (pressure, inert environment, high temperature, etc.), and the requirements for equipment are very high.
发明内容Contents of the invention
本发明的目的就是提供一种生产成本低、产品收率高的常压合成二(2，4，4-三甲基戊基)次膦酸的方法。The purpose of the present invention is to provide a method for synthesizing di(2,4,4-trimethylpentyl)phosphinic acid at normal pressure with low production cost and high product yield.
本发明的常压合成二(2，4，4-三甲基戊基)次膦酸的方法，包括以下步骤：Normal pressure synthesis of the present invention two (2,4, the method for 4-trimethylpentyl) phosphinic acid, comprises the following steps:
将次亚磷酸钠溶解于乙酸中，然后加入二异丁烯，常压室温条件下，在上述溶液中滴加次亚磷酸钠摩尔数4％的偶氮二异丁腈，滴加完毕后加热至回流，回流条件下反应2h后，滴加一次偶氮二异丁腈，以后每间隔1-3小时补加一次偶氮二异丁腈，补加量为次亚磷酸钠摩尔数的2％，总反应时间为8-12h，最后通过碱洗，酸化，脱水和真空旋蒸后得目标产物二(2，4，4-三甲基戊基)次膦酸。Dissolve sodium hypophosphite in acetic acid, then add diisobutylene, under normal pressure and room temperature, add dropwise azobisisobutyronitrile with 4% sodium hypophosphite molar number to the above solution, and heat to reflux after dropping , after reacting for 2 hours under reflux conditions, add azobisisobutyronitrile dropwise once, and then add azobisisobutyronitrile once every 1-3 hours. The reaction time is 8-12 hours. Finally, the target product di(2,4,4-trimethylpentyl)phosphinic acid is obtained after alkali washing, acidification, dehydration and vacuum rotary evaporation.
上述过程中，次亚磷酸钠与偶氮二异丁腈的摩尔比为5-10∶1。In the above process, the molar ratio of sodium hypophosphite to azobisisobutyronitrile is 5-10:1.
上述过程中，次亚磷酸钠与二异丁烯的摩尔比为1∶3-5。In the above process, the molar ratio of sodium hypophosphite to diisobutylene is 1:3-5.
上述过程中，次亚磷酸钠与乙酸的摩尔比为1∶1.5-2.0。In the above process, the molar ratio of sodium hypophosphite to acetic acid is 1: 1.5-2.0.
由于引发剂偶氮二异丁腈的10小时半衰期温度为65℃，因此保持反应体系处于回流状态可确保链引发反应的顺利发生。另外，在反应过程中，每隔一段时间即补加一定量的偶氮二异丁腈，可确保反应体系中维持一定浓度的自由基，使得链引发和链增长反应顺利进行。以上过程可示意如下：Since the 10-hour half-life temperature of the initiator azobisisobutyronitrile is 65° C., keeping the reaction system in a reflux state can ensure the smooth occurrence of the chain initiation reaction. In addition, during the reaction process, a certain amount of azobisisobutyronitrile is added at intervals to ensure that a certain concentration of free radicals is maintained in the reaction system, so that the chain initiation and chain growth reactions proceed smoothly. The above process can be illustrated as follows:
其反应机理如下：Its reaction mechanism is as follows:
链引发：chain triggers:
链增长：Chain growth:
本发明的常压合成二(2，4，4-三甲基戊基)次膦酸的方法，与传统方法相比，具有不需要加压、常压下即可顺利反应，反应时间大大缩短、反应条件温和以及二(2，4，4-三甲基戊基)次膦酸收率高，工艺过程简单等优点；合成路线只需一步完成，减少了多步合成造成的原料和能源的消耗，降低了成本。Compared with the traditional method, the method for synthesizing di(2,4,4-trimethylpentyl)phosphinic acid under normal pressure of the present invention has the advantages of being able to react smoothly without pressurization and under normal pressure, and the reaction time is greatly shortened , mild reaction conditions and high yield of di(2,4,4-trimethylpentyl)phosphinic acid, simple process and other advantages; the synthetic route only needs to be completed in one step, which reduces the cost of raw materials and energy caused by multi-step synthesis consumption, reducing costs.
具体实施方法Specific implementation method
实施例1：Example 1:
在装有机械搅拌、温度计、冷凝管和滴液漏斗的1000mL四口瓶中依次加入50.0g(471mmol)次亚磷酸钠、50.0g(833mmol)乙酸和211.40g(1413mmol)二异丁烯(75％)，搅拌，室温下从滴液漏斗中滴加3.09g(18.84mmol)偶氮二异丁腈的苯溶液，滴加完毕后，加热至回流，搅拌反应2小时后，在回流条件下滴加1.55g(9.42mmol)偶氮二异丁腈的苯溶液，每间隔2小时即补加一次引发剂。反应10小时后，降温至50℃，碱洗，酸化，干燥和真空旋蒸后得产物二(2，4，4-三甲基戊基)次膦酸。产物组成如下：Add 50.0g (471mmol) of sodium hypophosphite, 50.0g (833mmol) of acetic acid and 211.40g (1413mmol) of diisobutylene (75%) in a 1000mL four-necked flask equipped with a mechanical stirrer, a thermometer, a condenser and a dropping funnel. , stirred, and dropwise added 3.09g (18.84mmol) of benzene solution of azobisisobutyronitrile from the dropping funnel at room temperature. The benzene solution of g (9.42mmol) azobisisobutyronitrile was added with an initiator every 2 hours. After reacting for 10 hours, the temperature was lowered to 50° C., washed with alkali, acidified, dried and vacuum rotary evaporated to obtain the product di(2,4,4-trimethylpentyl)phosphinic acid. The composition of the product is as follows:
31P-NMR分析： 31P -NMR analysis:
目标产物二(2，4，4-三甲基戊基)次膦酸 78％Target product di(2,4,4-trimethylpentyl)phosphinic acid 78%
单取代物2，4，4-三甲基戊基亚膦酸 13.8％Mono-substituted 2,4,4-trimethylpentylphosphonous acid 13.8%
其它组分 8.2％。Other components 8.2%.
实施例2：Example 2:
按实施例1的方法，引发剂补加时间间隔改为1小时，其它方法不变。产物组成如下：According to the method of Example 1, the time interval for adding the initiator was changed to 1 hour, and the other methods were unchanged. The composition of the product is as follows:
31P-NMR分析： 31P -NMR analysis:
目标产物二(2，4，4-三甲基戊基)次膦酸 88.9％Target product di(2,4,4-trimethylpentyl)phosphinic acid 88.9%
单取代物2，4，4-三甲基戊基亚膦酸 6.4％Mono-substituted 2,4,4-trimethylpentylphosphonous acid 6.4%
其它组分 4.7％。Other components 4.7%.
实施例3：Example 3:
按实施例1的方法，引发剂补加时间间隔改为3小时，其它方法不变。产物组成如下：According to the method of Example 1, the time interval for adding the initiator was changed to 3 hours, and the other methods were unchanged. The composition of the product is as follows:
31P-NMR分析： 31P -NMR analysis:
目标产物二(2，4，4-三甲基戊基)次膦酸 71.4％Target product di(2,4,4-trimethylpentyl)phosphinic acid 71.4%
单取代物2，4，4-三甲基戊基亚膦酸 17.5％Mono-substituted 2,4,4-trimethylpentylphosphonous acid 17.5%
其它组分 11.1％。Other components 11.1%.
实施例4：Example 4:
按实施例1的方法，反应时间改为8小时，其它方法不变。产物组成如下：By the method of embodiment 1, the reaction time was changed into 8 hours, and other methods were unchanged. The composition of the product is as follows:
31P-NMR分析： 31P -NMR analysis:
目标产物二(2，4，4-三甲基戊基)次膦酸 71.4％Target product di(2,4,4-trimethylpentyl)phosphinic acid 71.4%
单取代物2，4，4-三甲基戊基亚膦酸 17.5％Mono-substituted 2,4,4-trimethylpentylphosphonous acid 17.5%
其它组分 11.1％。Other components 11.1%.
实施例5：Example 5:
按实施例1的方法，反应时间改为12小时，其它方法不变。产物组成如下：By the method of embodiment 1, the reaction time was changed into 12 hours, and other methods were unchanged. The composition of the product is as follows:
31P-NMR分析： 31P -NMR analysis:
目标产物二(2，4，4-三甲基戊基)次膦酸 80.3％Target product di(2,4,4-trimethylpentyl)phosphinic acid 80.3%
单取代物2，4，4-三甲基戊基亚膦酸 10.6％Mono-substituted 2,4,4-trimethylpentylphosphonous acid 10.6%
其它组分 9.1％。Other components 9.1%.
Claims (4)
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| CN102268038A (en) * | 2011-06-21 | 2011-12-07 | 江西科技师范学院 | Method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid with double initiators |
| CN102321117A (en) * | 2011-07-26 | 2012-01-18 | 江西科技师范学院 | Method for synthesizing di(2,4,4-trimethylamyl) hypophosphorous acid by using double initiators |
| CN102321118A (en) * | 2011-07-26 | 2012-01-18 | 江西科技师范学院 | Preparation method of dicyclohexyl-methyl-phosphinic acid |
| CN102372740A (en) * | 2011-12-06 | 2012-03-14 | 南开大学 | Preparation method for di(2,4,4-trimethyl pentyl) hypophosphorous acid |
| CN110746455A (en) * | 2019-11-25 | 2020-02-04 | 岳阳富和科技有限公司 | Preparation method of aluminum bis (2, 4, 4-trimethylpentyl) phosphinate |
| CN113956285A (en) * | 2021-08-26 | 2022-01-21 | 东南大学 | Method for synthesizing dialkyl aluminum phosphinate under normal pressure condition |
| CN116606317A (en) * | 2023-05-26 | 2023-08-18 | 天津崇研科技有限公司 | Preparation method and preparation equipment of dialkyl hypophosphorous acid |
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| CN1280582A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acid |
| US6300516B1 (en) * | 1997-11-28 | 2001-10-09 | Clariant Gmbh | Process for preparing dialkylphosphinic acids |
| CN101048344A (en) * | 2004-10-25 | 2007-10-03 | 罗迪亚公司 | Process for the preparation of highly purified, dialkyl phosphinic acids |
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