CN101891762A - Preparation method and application of diethyl phosphinates - Google Patents
Preparation method and application of diethyl phosphinates Download PDFInfo
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- CN101891762A CN101891762A CN2010102135166A CN201010213516A CN101891762A CN 101891762 A CN101891762 A CN 101891762A CN 2010102135166 A CN2010102135166 A CN 2010102135166A CN 201010213516 A CN201010213516 A CN 201010213516A CN 101891762 A CN101891762 A CN 101891762A
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Abstract
The invention discloses a preparation method and application of diethyl phosphinates, belonging to the field of green flame retardants. The preparation method of the diethyl phosphinates comprises the following steps of: making hypophosphorous acid and/or an alkali metal salt thereof react with ethylene under the irradiation of ultraviolet light in the presence of a photoinitiator in a solvent system to obtain diethyl phosphinic acid and/or an alkali metal salt thereof; and making the obtained diethyl phosphinic acid and/or the alkali metal salt thereof react with metallic compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Ce, Sn and/or Fe to obtain corresponding diethyl phosphinates. In the invention, the photoinitiator is decomposed into free radicals under the irradiation of the ultraviolet light to initiate an additive reaction so that the reaction rate can be improved, the energy consumption required in the reaction can be reduced and the production cost of products can be lowered.
Description
Technical field:
The invention belongs to environment-friendly flame retardant agent field, relate to a kind of preparation method and its usage of diethyl phosphinates.
Background technology:
At present, organo phosphorous compounds demonstrates its importance day by day in industrial production.They can be used to prepare sterilant, extraction agent and fire retardant etc., and wherein, the salt of organic phospho acid is as fire retardant, uses more extensively, and the method kind of its preparation is more.
For example, US 6011172 and CN1280581 have described the method that is prepared phostonic acid and dialkylphosphinic salts by element yellow phosphorus and alkylogen, be reflected under the existence of the alkali metal hydroxide aqueous solution or the alkaline earth metal hydroxides aqueous solution and carry out, also use organic solvent system in the reaction, and the product that obtains belongs to the mixed system that phostonic acid accounts for main component.It is the phosphorus source that the shortcoming of this method is to use yellow phosphorus, obtains mixture systems such as monoalkyl-phosphinous acid, dialkyl phosphinic acid, Hypophosporous Acid, 50, makes the purity of product reduce greatly, and in addition, the productive rate of this method two alkyl phosphinic acid is low, only is 16%.
US 6300516 and US 6329544 have described in the presence of peroxide radical initiator, the method for alkene and hypophosphite prepared in reaction dialkylphosphinic salts.But in this technology, the temperature of reaction of reaction system is initiator by the decomposition temperature decision of thermal initiator with the organic or inorganic superoxide, and the decomposition temperature of its most peroxide catalyst is above 100 ℃., therefore, reaction system is temperature required higher, and its energy consumption is bigger, has increased the synthetic cost of product.In addition, reaction solvent commonly used mostly is low-boiling point material greatly, and the decomposition temperature of peroxide catalyst is above 100 ℃.For successful reaction is carried out, then generally take pressuring method to improve the boiling point of solvent system, greatly reduce the security of reaction system with this.
In view of the above problems, the present invention proposes a kind of less energy-consumption, easy and simple to handle, and the synthetic method of manageable diethyl phosphinates.
Summary of the invention:
The objective of the invention is to improve the synthesis technique of diethyl phosphinates, improve the transformation efficiency and the product purity of product, cut down the consumption of energy, simplify technical process, save cost.To achieve these goals, the technical solution used in the present invention is:
The synthetic method of diethyl phosphinates may further comprise the steps:
(1) Hypophosporous Acid, 50 and/or its an alkali metal salt are dissolved in the solvent system, move to then in the withstand voltage reactor, feed ethylene gas then, make its still internal pressure remain on 1～20atm; Described solvent system is water and/or organic solvent;
(2) slowly splash into light trigger in the reaction system; When splashing into light trigger, to stir, ultraviolet lamp is opened in heating, reacts 2～30 hours down at 0～200 ℃;
(3) treat that light trigger drips off, reaction is closed ultraviolet lamp after finishing, reactor cooling, pressure release, and obtaining with diethyl phospho acid and/or its basic metal is the main solution of forming;
(4) reaction in (3) is obtained the solution immigration and be equipped with in the stillpot of stirring, dropper, and be heated to 0～150 ℃, slowly splash into metal salt solution, obtain corresponding diethyl phosphinates precipitation;
(5) (4) described mixed solution is filtered, washing is with the solid heating, vacuum drying that obtains.
Described solvent system is one or more in water, the organic solvent.
Preferred acetate of described organic solvent or ethanol.
The mol ratio of described ethene and Hypophosporous Acid, 50 and/or its an alkali metal salt sum is 2.1～3.0.
Described light trigger is one or more in ketone or the aldehydes.
The mol ratio of light trigger total amount and Hypophosporous Acid, 50 and/or its an alkali metal salt is 1: 10～100 in the step (2).
Wherein the preferred 20-130 of temperature of reaction in the step (2) ℃.
The described metal salt solution of step (4), its metal is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Ce, Sn and Fe, one or more in the aforementioned metal.
Wherein step (4) is middle the preferred 20-130 of temperature of reaction ℃.
The application method of described diethyl phosphinates is as the application of fire retardant.
The present invention has following advantage:
(1) the inventive method can shorten the reaction times.The fracture of P-H key needs the existence of abundant free radical in the Hypophosporous Acid, 50 root, and light trigger is responsive to UV-light, is decomposed into free radical immediately after the absorption UV-light, in the whole process of reaction, can obtain velocity of initiation faster,, shorten the needed reaction times of complete reaction with this.
(2) the inventive method can reduce energy consumption of reaction.Adopt light trigger to cause addition reaction in the reaction, the characteristics of its light trigger are the UV-light sensitivity, under lower temperature, can absorb UV-light, and be decomposed into free radical.Free radical in the reaction can provide at a lower temperature, therefore, can reduce the temperature of whole reaction system, cuts down the consumption of energy with this.
(3) the inventive method is carried out the synthetic of diethyl phosphinates at a lower temperature, and its ethene is difficult for polymerization reaction take place at low temperatures, has improved the utilization ratio of ethylene gas.Because temperature of reaction is lower, can suppress the generation of by product among the present invention, and the no strong oxidizing property of the light trigger that adopts among the present invention itself, can avoid the Hypophosporous Acid, 50 root of initiator and reductibility to react, improve degree of purity of production with this.
Embodiment:
Following examples further describe the present invention.
Embodiment 1
106g (1mol) hydration sodium hypophosphite is dissolved in the 750ml water, then its solution is moved to 2L strap clamp cover and be equipped with in the withstand voltage reactor of ultraviolet lamp, allow reacting liquid temperature maintain room temperature, feed ethylene gas then, make its still internal pressure maintain 5atm, and reach capacity, ultraviolet lamp energising then, the UV-irradiation reaction solution, simultaneously in 6 hours, evenly and slowly splash into 1.45g (2.5mol%) acetone, treat that light trigger splashes into fully after, reacted again 1 hour, with the reactor decompression, then gained solution is heated to 90 ℃.Slowly splash into liquor alumini chloridi (42.5g (0.35mol) is dissolved in the 100g water), in 60min, add.The suspension liquid of gained is filtered, obtain white solid, use the 1L hot wash, then 130 ℃ of following vacuum-dryings.The gained solid is analyzed.
31PNMR
Diethyl phospho acid aluminium: 87%
Single ethyl phospho acid aluminium: 3.3%
Unidentified compound: 9.7%.
Embodiment 2
106g (1mol) hydration sodium hypophosphite is dissolved in the 400ml acetate, then its solution is moved to 2L strap clamp cover and be equipped with in the withstand voltage reactor of ultraviolet lamp, right reacting liquid temperature maintains room temperature, feed ethylene gas then, make its still internal pressure maintain 6atm, and reach capacity, ultraviolet lamp energising then, the UV-irradiation reaction solution, simultaneously in 8 hours, evenly and slowly splash into 2.2g (5mol%) acetaldehyde, treat that it splashes into fully after, reacted again 1 hour, with the reactor decompression, then gained solution is heated to 85 ℃.Slowly splash into aluminum acetate solution (81.9g (0.35mol) is dissolved in the 150g water), in 60min, add.The suspension liquid of gained is filtered, obtain white solid, use the 1L hot wash, then 130 ℃ of following vacuum-dryings.The gained solid is analyzed.
31PNMR
Diethyl phospho acid aluminium: 90.8%
Single ethyl phospho acid aluminium: 2.5%
Unidentified compound: 6.7%.
Embodiment 3
Obtain diethyl phospho acid sodium solution with embodiment 1, then its solution is heated to 85 ℃.Slowly splash into alum liquor (233.1gAl
2(SO
4) 318H
2O (0.35mol) is dissolved in the 150g water), the suspension liquid that adds in 60min gained filters, and obtains white solid, uses the 1L hot wash, then 130 ℃ of following vacuum-dryings.The gained solid is analyzed.
31P?NMR
Diethyl phospho acid aluminium: 84.7%
Single ethyl phospho acid aluminium: 4.1%
Unidentified compound: 11.2%.
Claims (10)
1. the preparation method of a diethyl phosphinates is characterized in that, this synthetic method may further comprise the steps:
(1) Hypophosporous Acid, 50 and/or its an alkali metal salt are dissolved in the solvent system, move to then in the withstand voltage reactor, feed ethylene gas then, make its still internal pressure remain on 1～20atm; Described solvent system is water and/or organic solvent;
(2) slowly splash into light trigger in the reaction system; When splashing into light trigger, to stir, ultraviolet lamp is opened in heating, reacts 2～30 hours down at 0～200 ℃;
(3) treat that light trigger drips off, reaction is closed ultraviolet lamp after finishing, reactor cooling, pressure release, and obtaining with diethyl phospho acid and/or its basic metal is the main solution of forming;
(4) reaction in (3) is obtained the solution immigration and be equipped with in the stillpot of stirring, dropper, and be heated to 0～150 ℃, slowly splash into metal salt solution, obtain corresponding diethyl phosphinates precipitation;
(5) (4) described mixed solution is filtered, washing is with the solid heating, vacuum drying that obtains.
2. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that described solvent system is one or more in water, the organic solvent.
3. according to the synthetic method of a kind of diethyl phosphinates described in claim 1 and 2, it is characterized in that preferred acetate of described organic solvent or ethanol.
4. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that the mol ratio of described ethene and Hypophosporous Acid, 50 and/or its an alkali metal salt sum is 2.1～3.0.
5. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that described light trigger is one or more in ketone or the aldehydes.
6. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that the mol ratio of light trigger total amount and Hypophosporous Acid, 50 and/or its an alkali metal salt is 1: 10～100 in the step (2).
7. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that wherein the preferred 20-130 of temperature of reaction in the step (2) ℃.
8. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that, the described metal salt solution of step (4), its metal is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Ce, Sn and Fe, one or more in the aforementioned metal.
9. according to the synthetic method of a kind of diethyl phosphinates described in the claim 1, it is characterized in that wherein step (4) is middle the preferred 20-130 of temperature of reaction ℃.
10. the application method of the described diethyl phosphinates of claim 1 is as the application of fire retardant.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372740A (en) * | 2011-12-06 | 2012-03-14 | 南开大学 | Preparation method for di(2,4,4-trimethyl pentyl) hypophosphorous acid |
| CN102746512A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of polymerization alkyl aluminum hypophosphite |
| CN102746334A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of diisobutyl phosphinic acid aluminum |
| CN102924508A (en) * | 2012-09-19 | 2013-02-13 | 浙江新化化工股份有限公司 | Preparation method for dialkyl phosphinates |
| CN103073576A (en) * | 2012-09-19 | 2013-05-01 | 广州金凯新材料有限公司 | Preparation method of dialkyl phosphinic acid and salt thereof |
| CN103319525A (en) * | 2013-06-18 | 2013-09-25 | 浙江新化化工股份有限公司 | Preparation method of dialkyl phosphinate |
| CN103319524A (en) * | 2013-04-15 | 2013-09-25 | 泰州百力化学股份有限公司 | Diethyl phosphinate fire retardation agent preparation method |
| CN104402923A (en) * | 2014-11-14 | 2015-03-11 | 南开大学 | One-step synthesis method of dialkylphosphinic acid mixture |
| CN104478923A (en) * | 2014-12-19 | 2015-04-01 | 西华大学 | Preparation method of diethyl phosphinic acid and salts thereof without monoethyl phosphinic acid group |
| WO2015149265A1 (en) * | 2014-04-01 | 2015-10-08 | 中国科学院宁波材料技术与工程研究所 | Preparation process and product of dialkyl phosphinate |
| CN106925104A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of wet desulphurization synergist |
| CN108864182A (en) * | 2018-07-24 | 2018-11-23 | 济南泰星精细化工有限公司 | The synthetic method of alkyl phosphinic acid and its aluminium salt under a kind of normal pressure, temperate condition |
| CN109608491A (en) * | 2018-12-14 | 2019-04-12 | 湖北宏嘉化工股份有限公司 | A kind of preparation method of diethyl hypophosphites |
| CN110407869A (en) * | 2019-07-11 | 2019-11-05 | 兰州大学 | A kind of preparation method and application of list trifluoro propyl phosphinic acids aluminium fire retardant |
| CN114685856A (en) * | 2022-04-21 | 2022-07-01 | 兰州瑞朴科技有限公司 | Preparation method of aluminum diethylphosphinate |
| WO2023138015A1 (en) * | 2022-01-22 | 2023-07-27 | 兰州瑞朴科技有限公司 | Aluminum diethylphosphinate flame retardant and preparation method therefor |
| CN117534702A (en) * | 2024-01-10 | 2024-02-09 | 太仓维龙化工有限公司 | Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof |
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| WO2013083047A1 (en) * | 2011-12-06 | 2013-06-13 | 南开大学 | Method for preparing bis(2,4,4-trimethyl pentyl) 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 |
| CN102746512A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of polymerization alkyl aluminum hypophosphite |
| CN102746334A (en) * | 2012-07-13 | 2012-10-24 | 南开大学 | Preparation method of diisobutyl phosphinic acid aluminum |
| CN102746512B (en) * | 2012-07-13 | 2014-02-26 | 南开大学 | Preparation method of polymerization alkyl aluminum hypophosphite |
| CN103073576B (en) * | 2012-09-19 | 2015-09-23 | 广州金凯新材料有限公司 | The preparation method of a kind of dialkyl phosphinic acid and salt thereof |
| CN102924508A (en) * | 2012-09-19 | 2013-02-13 | 浙江新化化工股份有限公司 | Preparation method for dialkyl phosphinates |
| CN103073576A (en) * | 2012-09-19 | 2013-05-01 | 广州金凯新材料有限公司 | Preparation method of dialkyl phosphinic acid and salt thereof |
| CN102924508B (en) * | 2012-09-19 | 2016-03-02 | 浙江新化化工股份有限公司 | A kind of preparation method of dialkylphosphinic salts |
| CN103319524B (en) * | 2013-04-15 | 2015-12-02 | 泰州百力化学股份有限公司 | A kind of preparation method of Diethyl phosphinate fire retardation agent |
| CN103319524A (en) * | 2013-04-15 | 2013-09-25 | 泰州百力化学股份有限公司 | Diethyl phosphinate fire retardation agent preparation method |
| CN103319525B (en) * | 2013-06-18 | 2015-10-28 | 浙江新化化工股份有限公司 | A kind of preparation method of dialkylphosphinic salts |
| CN103319525A (en) * | 2013-06-18 | 2013-09-25 | 浙江新化化工股份有限公司 | Preparation method of dialkyl phosphinate |
| US9802970B2 (en) | 2014-04-01 | 2017-10-31 | Ningbo Inst. Of Materials Tech. & Eng., Chinese Acad. Of Sciences | Process for preparing dialkylphosphinate and a product thereof |
| WO2015149265A1 (en) * | 2014-04-01 | 2015-10-08 | 中国科学院宁波材料技术与工程研究所 | Preparation process and product of dialkyl phosphinate |
| JP2017513817A (en) * | 2014-04-01 | 2017-06-01 | 中国科学院寧波材料技術与工程研究所 | Production method and product of dialkylphosphinate |
| CN104402923A (en) * | 2014-11-14 | 2015-03-11 | 南开大学 | One-step synthesis method of dialkylphosphinic acid mixture |
| CN104478923A (en) * | 2014-12-19 | 2015-04-01 | 西华大学 | Preparation method of diethyl phosphinic acid and salts thereof without monoethyl phosphinic acid group |
| CN106925104A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of wet desulphurization synergist |
| CN108864182A (en) * | 2018-07-24 | 2018-11-23 | 济南泰星精细化工有限公司 | The synthetic method of alkyl phosphinic acid and its aluminium salt under a kind of normal pressure, temperate condition |
| CN109608491A (en) * | 2018-12-14 | 2019-04-12 | 湖北宏嘉化工股份有限公司 | A kind of preparation method of diethyl hypophosphites |
| CN109608491B (en) * | 2018-12-14 | 2023-12-05 | 湖北宏嘉化工股份有限公司 | Preparation method of diethyl phosphinate |
| CN110407869A (en) * | 2019-07-11 | 2019-11-05 | 兰州大学 | A kind of preparation method and application of list trifluoro propyl phosphinic acids aluminium fire retardant |
| WO2023138015A1 (en) * | 2022-01-22 | 2023-07-27 | 兰州瑞朴科技有限公司 | Aluminum diethylphosphinate flame retardant and preparation method therefor |
| CN114685856A (en) * | 2022-04-21 | 2022-07-01 | 兰州瑞朴科技有限公司 | Preparation method of aluminum diethylphosphinate |
| CN114685856B (en) * | 2022-04-21 | 2024-02-20 | 兰州瑞朴科技有限公司 | Preparation method of diethyl aluminum phosphinate |
| CN117534702A (en) * | 2024-01-10 | 2024-02-09 | 太仓维龙化工有限公司 | Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof |
| CN117534702B (en) * | 2024-01-10 | 2024-04-05 | 太仓维龙化工有限公司 | Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof |
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Application publication date: 20101124 |