CN102167708B - Preparation method of tri-n-butylmyristylphosphonium chloride - Google Patents
Preparation method of tri-n-butylmyristylphosphonium chloride Download PDFInfo
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- CN102167708B CN102167708B CN201110057961.2A CN201110057961A CN102167708B CN 102167708 B CN102167708 B CN 102167708B CN 201110057961 A CN201110057961 A CN 201110057961A CN 102167708 B CN102167708 B CN 102167708B
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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, and the season phosphonium salt being synthesized by tri-n-butyl phosphine is the tensio-active agent of excellent property, has the features such as pH value subject range is wide, low bubble, is also simultaneously that a class is efficient, 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 tri-n-butyl phosphine is expensive, the report of producing there are no domestic industryization.
At present the synthetic method of tri-n-butyl phosphine has multiplely, and classical synthetic method is grignard reagent synthesis method, early than nineteen twenty-nine by foundation such as WC Davies, the method is carried out in ether, except reagent dosage greatly, because ether boiling point is low, processing safety is also poor.
Adopt phosphuret-(t)ed hydrogen and alkene Radical Addition to prepare tri-n-butyl phosphine, domestic existing bibliographical information, as Wang little Kang. the synthetic and application [master thesis] of tributylphosphine. and Nanjing University of Chemical Technology, 1999; This document has synthesized tributylphosphine with grignard reagent method.Yan Xianglan, Xia Chungu, Li Dagang etc. prepare the technological process of organic phosphine compound: China, 91105352.2[P] .1993-02-17.
Use at present alkyl chloride, bromoalkane and tributylphosphine to synthesize respectively tetradecyl tributyl phosphorus chloride, dodecyl tributyl phosphorus chloride, hexadecyl tributyl phosphorus chloride for raw material, domestic existing bibliographical information, as Yao becomes, Bu Hongzhong, Jin Tang etc. the synthetic and performance study [C] of novel quaternary alkylphosphonium salt tensio-active agent. the 8th time, whole nation industrial surface activity agent Technological Economy 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. application chemical industry, 2005, (8): 478481.Wherein, Yao Cheng etc., taking 1 monobromination dodecane, 1 one bromotetradecanes and tributylphosphine as raw material, synthesize 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., taking alkyl chloride and tributylphosphine as raw material, prepare alkane base quaternary phosphine salt biocide by bimolecular nucleophilic substitution (SN2).
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of tri-n-butyl phosphine, and the method is simple, and cost is low, and productive rate is greater than 93.5%, is suitable for suitability for industrialized production; Adopt high pressure (5.0-8.0MPa) reaction, under this condition, butylene and phosphuret-(t)ed hydrogen are all liquid, reaction is more easily carried out, further utilize tri-n-butyl phosphine that a kind of preparation method of three normal-butyl tetradecyl phosphorus chloride is provided, the method is simple, and reaction is easily carried out, and reaction thoroughly, yield is greater than 95%, is suitable for suitability for industrialized production.
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, comprising:
(1) reaction
Raw material hybrid reactor and whole reactive system are fully replaced with nitrogen, in raw material hybrid reactor, add n-butene and initiator, fully stir and make to dissolve completely to obtain compound; Add described compound by fresh feed pump to reactive system, reactive system is warming up to 80 DEG C, add phosphine gas by compressor to reactive system simultaneously, material adds 80～85 DEG C of rear valve-off control temperature of reaction, reaction pressure 5.0～8.0Mpa, continues heat-insulation pressure keeping reaction 2 hours, is cooled to 50 DEG C of <, reactive system pressure release, to 0.5Mpa, is transferred to intermediate storage tank by reaction solution;
(2) rectifying
Distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in rectifying still, regulates vacuum tightness 200mbar, is slowly warming up to 80 DEG C, collects light constituent; Slowly improve vacuum to 5mbar, temperature rises to 150 DEG C again, collects cut, obtains tri-n-butyl phosphine;
(3) reaction
In reactor, fully replace and use nitrogen protection with nitrogen, add tri-n-butyl phosphine, be warming up to 120 DEG C; Slowly add the 1-chlorine tetradecane, keep 120～130 DEG C of temperature; After the 1-chlorine tetradecane all adds, be incubated again 120～130 DEG C of reactions 10 hours, be cooled to 90 DEG C, add deionized water; Use toluene wash, point water-yielding stratum, removes moisture and other light constituent by water layer underpressure distillation, is adjusted to content 50 ± 1% to adding deionized water in material.
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 described step (1) is benzoyl peroxide.
Phosphuret-(t)ed hydrogen in described step (1) is generally produces the tail gas producing in sodium hypophosphite process.
The concrete steps of collecting cut in described step (2), for first collecting part front-end volatiles, start to collect product after product content is qualified, and product content drops to after defective and stops collecting, and lowers the temperature to system, obtains qualified product tri-n-butyl phosphine.
Tri-n-butyl phosphine, the 1-chlorine tetradecane and deionized mass ratio in described step (3) 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 thering is the features such as foam is low, foundry loam stripping ability the is strong and very wide pH value scope of application, this product is widely used in controlling water coolant microbial reproduction, industrial cleaning water processing, oil-field water processing, paper industry water and the application of other Treatment of Industrial Water as sterilant.
beneficial effect
(1) preparation method of the present invention is simple, and cost is low, and productive rate is greater than 93.5%, is suitable for suitability for industrialized production;
(2) the present invention adopts high pressure (5.0-8.0MPa) reaction, and under this condition, butylene and phosphuret-(t)ed hydrogen are all liquid, and reaction is more easily carried out;
(3) preparation method of the present invention is simple, nitrogen protection and 120～130 DEG C, reaction is easily carried out, and thoroughly, yield is greater than 95%, is suitable for suitability for industrialized production in reaction.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
A preparation method for three normal-butyl tetradecyl phosphorus chloride, comprising:
(1) reaction
Raw material hybrid reactor and whole reactive system are fully replaced with nitrogen, in raw material hybrid reactor, add 500kg n-butene and 20kg benzoyl peroxide, fully stir and make consoluet compound; Add described compound by fresh feed pump to reactive system, reactive system is warming up to 80 DEG C, add phosphine gas (quality 80%) by compressor to reactive system, material adds 80～85 DEG C of rear valve-off control temperature of reaction, reaction pressure 5.0～8.0Mpa simultaneously; Continue heat-insulation pressure keeping reaction 2 hours, be cooled to 50 DEG C, reactive system pressure release, to 0.5Mpa, is transferred to intermediate storage tank by reaction solution, the described phosphuret-(t)ed hydrogen tail gas producing in parity sodium phosphate process of making a living;
(2) rectifying
Distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in rectifying still, regulates vacuum tightness 200mbar, is slowly warming up to 80 DEG C, collects light constituent; Slowly improve vacuum to 5mbar, temperature rises to 150 DEG C, first collects part front-end volatiles again, starts to collect product after product content is qualified, and product content drops to after defective and stops collecting, and to system cooling, obtains qualified product tri-n-butyl phosphine;
(3) reaction
In reactor, fully replace and use nitrogen protection with nitrogen, add 400kg tri-n-butyl phosphine, be warming up to 120 DEG C; Slowly add the 500kg 1-chlorine tetradecane, keep 120～130 DEG C of temperature; After the 1-chlorine tetradecane all adds, be incubated again 120～130 DEG C of reactions 10 hours, be cooled to 90 DEG C, add 500kg deionized water; Use 300kg toluene wash, point water-yielding stratum, removes moisture and other light constituent by water layer underpressure distillation, is adjusted to content 50 ± 1% to adding deionized water in material, and the productive rate of gained three normal-butyl tetradecyl phosphorus chloride is 95%.
Claims (3)
1. a preparation method for three normal-butyl tetradecyl phosphorus chloride, comprising:
(1) raw material hybrid reactor and whole reactive system are fully replaced with nitrogen, in raw material hybrid reactor, add n-butene and initiator, fully stir and make to dissolve completely to obtain compound; Add described compound by fresh feed pump to reactive system, reactive system rises to 80 DEG C, add phosphine gas by compressor to reactive system simultaneously, material adds 80～85 DEG C of rear valve-off control temperature of reaction, reaction pressure 5.0～8.0Mpa, continues heat-insulation pressure keeping reaction 2 hours, is cooled to 50 DEG C of <, reactive system pressure release, to 0.5Mpa, is transferred to intermediate storage tank by reaction solution; Wherein, the mass ratio of n-butene and initiator is 25:1, and the mass ratio of phosphuret-(t)ed hydrogen and n-butene is 1:4.2;
(2) distillation system is fully replaced with nitrogen, and step (1) reaction solution is joined in rectifying still, regulates vacuum tightness 200mbar, is slowly warming up to 80 DEG C, collects light constituent; Slowly improve vacuum to 5mbar, temperature rises to 150 DEG C again, collects cut, obtains tri-n-butyl phosphine;
(3) in reactor, fully replace and use nitrogen protection with nitrogen, add above-mentioned tri-n-butyl phosphine, be warming up to 120 DEG C; Slowly add the 1-chlorine tetradecane, keep 120～130 DEG C of temperature; After the 1-chlorine tetradecane all adds, be incubated again 120～130 DEG C of reactions 10 hours, be cooled to 90 DEG C, add deionized water; Use toluene wash, point water-yielding stratum, removes moisture and other light constituent by water layer underpressure distillation, is adjusted to content 50 ± 1% to adding deionized water in material; Wherein, the mass ratio of tri-n-butyl phosphine, the 1-chlorine tetradecane and deionized water is 1:1.25:1.25.
2. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1, is characterized in that: the initiator in described step (1) is benzoyl peroxide.
3. the preparation method of a kind of three normal-butyl tetradecyl phosphorus chloride according to claim 1, it is characterized in that: in described step (2), collect the concrete steps of cut for first collecting part front-end volatiles, after product content is qualified, start to collect product, product content drops to after defective and stops collecting.
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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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| CN102167708B true CN102167708B (en) | 2014-06-25 |
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| 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 |
| 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 |
| 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 |
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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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 (4)
| Title |
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| 三聚催化剂三正丁基膦的合成方法;王勃;《聚氨酯工业》;20041231;第19卷(第3期);15-17 * |
| 姚成,等.杀菌剂DTPC和TTPC的合成及应用研究.《工业水处理》.1999,第19卷(第3期),16-18. * |
| 王勃.三聚催化剂三正丁基膦的合成方法.《聚氨酯工业》.2004,第19卷(第3期),15-17. |
| 王瑛，等.烷基三丁基氯化鏻的合成与性能研究.《应用化工》.2005,第34卷(第8期),478-481. * |
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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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