CN102167708A - Preparation method of tri-n-butylmyristylphosphonium chloride - Google Patents
Preparation method of tri-n-butylmyristylphosphonium chloride Download PDFInfo
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- CN102167708A CN102167708A CN2011100579612A CN201110057961A CN102167708A CN 102167708 A CN102167708 A CN 102167708A CN 2011100579612 A CN2011100579612 A CN 2011100579612A CN 201110057961 A CN201110057961 A CN 201110057961A CN 102167708 A CN102167708 A CN 102167708A
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Abstract
The invention relates to a preparation method of tri-n-butylmyristylphosphonium chloride. The method comprises the following steps: (1) preparing tri-n-butyl-phosphine; (2) adding tri-n-butyl-phosphine, heating to 120 DEG C; adding 1-chlorotetradecane, keeping the temperature to 120-130 DEG C; after adding 1-chlorotetradecane, keeping the temperature to 120-130 DEG to react for 10 hours, reducing the temperature to 90 DEG C, refilling deionized water; washing to separate out water layer, distilling the water layer under reduced pressure to remove water and other light components, and adding deionized water in material to adjust the product content to 50+/-1%. The method is simple; the reaction is easy to perform and can be performed thoroughly; the yield is more than 95%; and the method is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of three normal-butyl tetradecyl phosphorus chloride, particularly relate to the preparation method of a kind of three positive fourth phosphines and three normal-butyl tetradecyl phosphorus chloride.
Background technology
Tri-n-butyl phosphine is important organic phosphine compound, is the tensio-active agent of excellent property by tri-n-butyl phosphine synthetic season phosphonium salt, has characteristics such as wide, the low bubble of pH value subject range, also be simultaneously a class efficiently, wide spectrum, low toxicity sterilant.The title complex that tri-n-butyl phosphine and many transition metals form is a very important class catalyzer, and in polyurethane industrial, tri-n-butyl phosphine is the good catalyzer of synthetic isocyanate trimerization reaction.In addition, tri-n-butyl phosphine can also be used as extraction agent, fuel dope and organic synthesis reagent etc.The tri-n-butyl phosphine of China main dependence on import of originating, and the report that domestic industry production is arranged is not seen in costing an arm and a leg of tri-n-butyl phosphine.
At present the synthetic method of tri-n-butyl phosphine has multiplely, and classical synthetic method is the grignard reagent synthesis method, early than nineteen twenty-nine by foundation such as WC Davies, this method is carried out in ether, remove reagent dosage big, owing to the ether boiling point is low, processing safety is also poor.
Adopt phosphuret-(t)ed hydrogen and alkene free radical addition prepared in reaction tri-n-butyl phosphine, domestic existing bibliographical information is as Wang Xiaokang. the synthetic and application [master thesis] of tributylphosphine. and Nanjing University of Chemical Technology, 1999; This document has synthesized tributylphosphine with the grignard reagent method.Yan Xianglan, Xia Chungu, Li Dagang etc. the technological process of preparation organic phosphine compound: China, 91105352.2[P] .1993-02-17.
At present use alkyl chloride, bromoalkane and tributylphosphine to synthesize tetradecyl tributyl phosphorus chloride, dodecyl tributyl phosphorus chloride, hexadecyl tributyl phosphorus chloride respectively as raw material, domestic existing bibliographical information, become as Yao, Bu Hongzhong, Jin Tang etc. the synthetic and performance study [C] of novel quaternary alkylphosphonium salt tensio-active agent. the 8th industrial surface activity agent Technological Economy in the whole nation and application and development meeting paper selected works, 19990800:174-177; Wang Ying, Fu Jiajun, Yan Lianhe. synthetic and the performance study [J] of alkyl tributyl phosphorus chloride. use chemical industry, 2005, (8): 478481.Wherein, Yao Cheng etc. are raw material with 1 monobromination dodecane, the 1 one bromo tetradecanes and tributylphosphine, synthetic two kinds of novel quaternary alkylphosphonium salt dodecyl tributyl bromo-phosphoniums and tetradecyl tributyl bromo-phosphonium, and in tributylphosphine, yield is respectively 98.5% and 98%; Wang Ying etc. are raw material with alkyl chloride and tributylphosphine, prepare alkane base quaternary phosphine salt biocide by bimolecular nucleophilic substitution (SN2).
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of tri-n-butyl phosphine, and this method is simple, and cost is low, and productive rate is suitable for suitability for industrialized production greater than 93.5%; Adopt high pressure (5.0-8.0MPa) reaction, butylene and phosphuret-(t)ed hydrogen all are liquid under this condition, make that reaction is easier to be carried out, further utilize tri-n-butyl phosphine that a kind of preparation method of three normal-butyl tetradecyl phosphorus chloride is provided, this method is simple, and reaction is carried out easily, and reaction thoroughly, yield is suitable for suitability for industrialized production greater than 95%.
Reaction formula of the present invention is as follows:
The preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride of the present invention comprises:
(1) reaction
Raw material hybrid reactor and entire reaction system fully replace with nitrogen, add n-butene and initiator in the raw material hybrid reactor, fully stir make dissolve fully compound; Add described compound by fresh feed pump to reactive system, reactive system is warming up to 80 ℃, add phosphine gas by compressor to reactive system simultaneously, material adds 80～85 ℃ of back valve-off control reaction temperature, reaction pressure 5.0～8.0Mpa continues heat-insulation pressure keeping reaction 2 hours, is cooled to＜50 ℃, the reactive system pressure release is transferred to intermediate storage tank to 0.5Mpa with reaction solution;
(2) rectifying
Distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in the rectifying still, regulates vacuum tightness 200mbar, slowly is warming up to 80 ℃, collects light constituent; Slowly improve vacuum again to 5mbar, temperature rises to 150 ℃, collects cut, promptly gets tri-n-butyl phosphine;
(3) reaction
Fully replace and use nitrogen protection with nitrogen in the reactor, add tri-n-butyl phosphine, be warming up to 120 ℃; Slowly add the 1-chlorine tetradecane, keep 120～130 ℃ of temperature; Be incubated 120～130 ℃ of reactions 10 hours after the 1-chlorine tetradecane all adds again, be cooled to 90 ℃, add deionized water; Use toluene wash, divide water-yielding stratum, moisture and other light constituent are removed in the water layer underpressure distillation, in material, add deionized water and be adjusted to content 50 ± 1%.
The n-butene of described step (1) and the mass ratio of initiator are 25: 1, and the mass ratio of phosphuret-(t)ed hydrogen and n-butene is 1: 4.2
Initiator in the described step (1) is a benzoyl peroxide.
Phosphuret-(t)ed hydrogen in the described step (1) is generally produces the tail gas that produces in the sodium hypophosphite process.
The concrete steps of collecting cut in the described step (2) be to collect the part front-end volatiles earlier, treat that product content begins to collect product after qualified, and product content drops to and stops to collect after defective, lowers the temperature to system, obtains qualified product tri-n-butyl phosphine.
Tri-n-butyl phosphine in the described step (3), the 1-chlorine tetradecane and deionized mass ratio are 1: 1.25: 1.25.
Three normal-butyl tetradecyl phosphorus chloride are that a new generation is efficient, wide spectrum, low toxicity sterilant, not only sterilizing ability is strong, and having the characteristics such as the pH value scope of application that foam is low, the foundry loam stripping ability is strong and very wide, this product is widely used in the breeding of controlled chilling water microorganism, the processing of industrial cleaning water, oil-field water processing, paper industry water and other Treatment of Industrial Water as sterilant and uses.
Beneficial effect
(1) preparation method of the present invention is simple, and cost is low, and productive rate is suitable for suitability for industrialized production greater than 93.5%;
(2) the present invention adopts high pressure (5.0-8.0MPa) reaction, and butylene and phosphuret-(t)ed hydrogen all are liquid under this condition, makes that reaction is easier to be carried out;
(3) preparation method of the present invention is simple, nitrogen protection and 120～130 ℃ reaction is carried out easily, reaction thoroughly, yield is suitable for suitability for industrialized production greater than 95%.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
A kind of preparation method of three normal-butyl tetradecyl phosphorus chloride comprises:
(1) reaction
Raw material hybrid reactor and entire reaction system fully replace with nitrogen, add 500kg n-butene and 20kg benzoyl peroxide in the raw material hybrid reactor, fully stir and make consoluet compound; Add described compound by fresh feed pump to reactive system, reactive system is warming up to 80 ℃, add phosphine gas (quality 80%) by compressor to reactive system simultaneously, material adds 80～85 ℃ of back valve-off control reaction temperature, reaction pressure 5.0～8.0Mpa; Continue heat-insulation pressure keeping reaction 2 hours, be cooled to 50 ℃, the reactive system pressure release is transferred to intermediate storage tank to 0.5Mpa with reaction solution, the tail gas that described phosphuret-(t)ed hydrogen is made a living and produced in the parity sodium phosphate process;
(2) rectifying
Distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in the rectifying still, regulates vacuum tightness 200mbar, slowly is warming up to 80 ℃, collects light constituent; Slowly improve vacuum again to 5mbar, temperature rises to 150 ℃, collects earlier the part front-end volatiles, treats that product content begins to collect product after qualified, and product content drops to and stops to collect after defective, to system's cooling, obtains qualified product tri-n-butyl phosphine;
(3) reaction
Fully replace and use nitrogen protection with nitrogen in the reactor, add the 400kg tri-n-butyl phosphine, be warming up to 120 ℃; Slowly add the 500kg 1-chlorine tetradecane, keep 120～130 ℃ of temperature; Be incubated 120～130 ℃ of reactions 10 hours after the 1-chlorine tetradecane all adds again, be cooled to 90 ℃, add the 500kg deionized water; Use the 300kg toluene wash, divide water-yielding stratum, moisture and other light constituent are removed in the water layer underpressure distillation, add deionized water and be adjusted to content 50 ± 1% in material, the productive rate of gained three normal-butyl tetradecyl phosphorus chloride is 95%.
Claims (5)
1. the preparation method of a normal-butyl tetradecyl phosphorus chloride comprises:
(1) raw material hybrid reactor and entire reaction system fully replace with nitrogen, add n-butene and initiator in the raw material hybrid reactor, fully stir make dissolve fully compound; Add described compound by fresh feed pump to reactive system, reactive system is warming up to 80 ℃, add phosphine gas by compressor to reactive system simultaneously, material adds 80～85 ℃ of back valve-off control reaction temperature, reaction pressure 5.0～8.0Mpa continues heat-insulation pressure keeping reaction 2 hours, is cooled to＜50 ℃, the reactive system pressure release is transferred to intermediate storage tank to 0.5Mpa with reaction solution;
(2) distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in the rectifying still, regulates vacuum tightness 200mbar, slowly is warming up to 80 ℃, collects light constituent; Slowly improve vacuum again to 5mbar, temperature rises to 150 ℃, collects cut, promptly gets tri-n-butyl phosphine;
(3) fully replace and use nitrogen protection with nitrogen in the reactor, add above-mentioned tri-n-butyl phosphine, be warming up to 120 ℃; Slowly add the 1-chlorine tetradecane, keep 120～130 ℃ of temperature; Be incubated 120～130 ℃ of reactions 10 hours after the 1-chlorine tetradecane all adds again, be cooled to 90 ℃, add deionized water; Use toluene wash, divide water-yielding stratum, moisture and other light constituent are removed in the water layer underpressure distillation, in material, add deionized water and be adjusted to content 50 ± 1%.
2. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1 is characterized in that: the n-butene in the described step (1) and the mass ratio of initiator are 25: 1, and the mass ratio of phosphuret-(t)ed hydrogen and n-butene is 1: 4.2.
3. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1 is characterized in that: the initiator in the described step (1) is a benzoyl peroxide.
4. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1, it is characterized in that: the concrete steps of collecting cut in the described step (2) are for collecting the part front-end volatiles earlier, treat that product content begins to collect product after qualified, product content drops to and stops after defective collecting.
5. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1 is characterized in that: the mass ratio of the tri-n-butyl phosphine in the described step (3), the 1-chlorine tetradecane and deionized water is 1: 1.25: 1.25.
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| CN201110057961.2A CN102167708B (en) | 2011-03-10 | 2011-03-10 | Preparation method of tri-n-butylmyristylphosphonium chloride |
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| CN201110057961.2A CN102167708B (en) | 2011-03-10 | 2011-03-10 | Preparation method of tri-n-butylmyristylphosphonium chloride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315305A (en) * | 2014-07-28 | 2016-02-10 | 中国石油化工股份有限公司 | Synthetic method for alkyl phosphine |
| CN106518921A (en) * | 2015-09-15 | 2017-03-22 | 中国石油化工股份有限公司 | Preparation method of tertiary phosphine and application thereof as well as preparation method of tertiary phosphine |
| CN111892626A (en) * | 2020-08-28 | 2020-11-06 | 山东卓俊实业有限公司 | Method for producing alkyl phosphine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324919A (en) * | 1979-09-07 | 1982-04-13 | Hoechst Aktiengesellschaft | Production of tertiary phosphines |
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2011
- 2011-03-10 CN CN201110057961.2A patent/CN102167708B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324919A (en) * | 1979-09-07 | 1982-04-13 | Hoechst Aktiengesellschaft | Production of tertiary phosphines |
Non-Patent Citations (3)
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| 姚成，等: "杀菌剂DTPC和TTPC的合成及应用研究", 《工业水处理》 * |
| 王勃: "三聚催化剂三正丁基膦的合成方法", 《聚氨酯工业》 * |
| 王瑛，等: "烷基三丁基氯化鏻的合成与性能研究", 《应用化工》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315305A (en) * | 2014-07-28 | 2016-02-10 | 中国石油化工股份有限公司 | Synthetic method for alkyl phosphine |
| CN105315305B (en) * | 2014-07-28 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of method of synthesis of alkyl phosphine |
| CN106518921A (en) * | 2015-09-15 | 2017-03-22 | 中国石油化工股份有限公司 | Preparation method of tertiary phosphine and application thereof as well as preparation method of tertiary phosphine |
| CN106518921B (en) * | 2015-09-15 | 2018-08-28 | 中国石油化工股份有限公司 | The preparation method and applications and a kind of preparation method of quaternary alkylphosphonium salt of a kind of three-level phosphine |
| CN111892626A (en) * | 2020-08-28 | 2020-11-06 | 山东卓俊实业有限公司 | Method for producing alkyl phosphine |
| CN111892626B (en) * | 2020-08-28 | 2022-12-20 | 江西永通科技股份有限公司 | Method for producing alkyl phosphine |
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Denomination of invention: A preparation method of tri-n-butyl tetradecyl phosphorus chloride Effective date of registration: 20211216 Granted publication date: 20140625 Pledgee: Jiangsu Changshu Rural Commercial Bank Co.,Ltd. Fushan sub branch Pledgor: CHANGSHU NEW-TECH CHEMICALS Co.,Ltd. Registration number: Y2021320010566 |
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