CN112661790B - Preparation method of dialkyl phosphinate - Google Patents

Preparation method of dialkyl phosphinate Download PDF

Info

Publication number
CN112661790B
CN112661790B CN202110008008.2A CN202110008008A CN112661790B CN 112661790 B CN112661790 B CN 112661790B CN 202110008008 A CN202110008008 A CN 202110008008A CN 112661790 B CN112661790 B CN 112661790B
Authority
CN
China
Prior art keywords
reaction
catalyst
dialkyl phosphinate
halogenated
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110008008.2A
Other languages
Chinese (zh)
Other versions
CN112661790A (en
Inventor
陈章明
李金忠
雷华
杨建伟
王家凯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Liside New Materials Co ltd
Original Assignee
Jiangsu Liside New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Liside New Material Co ltd filed Critical Jiangsu Liside New Material Co ltd
Priority to CN202110008008.2A priority Critical patent/CN112661790B/en
Publication of CN112661790A publication Critical patent/CN112661790A/en
Priority to PCT/CN2021/094487 priority patent/WO2022147941A1/en
Application granted granted Critical
Publication of CN112661790B publication Critical patent/CN112661790B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a preparation method of dialkyl phosphinate, which comprises the steps of taking dialkyl phosphinate and halogenated compounds as raw materials, and reacting under the action of a catalyst to obtain the dialkyl phosphinate; the catalyst is one or more of phase transfer catalyst or amphoteric compound, and comprises at least one of cation polyalkyl quaternary ammonium salt compound, cation halogenated polyalkyl quaternary ammonium salt compound, alkyl ammonium chloride, alkyl ammonium bromide, anion alkyl sulfate compound, alkyl sulfonate, alkyl benzene sulfonate, nonionic surfactant, and quaternary phosphonium salt. Compared with the traditional synthesis method, the method for synthesizing the dialkyl phosphinate by the one-step method has the advantages of higher yield, less byproducts, easy separation, simple steps, short time consumption, safe and environment-friendly process, lower cost and easier implementation.

Description

Preparation method of dialkyl phosphinate
Technical Field
The invention relates to the technical field of preparation of dialkyl phosphinate, and particularly relates to a preparation method of dialkyl phosphinate.
Background
Phosphate is a multipurpose chemical product, wherein phosphite ester and alkyl phosphate are main varieties of organic phosphorus flame retardants, and the phosphate has the advantages of lasting flame retardant effect, good compatibility with polymer base materials, water resistance, weather resistance and the like, so that the phosphate is widely applied to high polymer materials such as polyurethane, epoxy resin, polycarbonate, unsaturated resin and the like.
Phosphites include dimethyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and the like, and are usually obtained by reacting phosphorus trichloride with a corresponding alcohol or phenol.
Phosphite esters with monoalkyl C-P structures comprise dimethyl methylphosphonate (DMMP), diethyl ethylphosphate (DEEP) and the like, and are obtained by taking trimethyl phosphite and triethyl phosphite as raw materials through a rearrangement reaction. Meanwhile, the monoalkyl flame retardant is a chemical which is mainly monitored by the International organization for chemical industry inhibition, and the production, the use and the circulation of the monoalkyl flame retardant are all strictly controlled.
The dialkyl phosphinate has a hypophosphorous acid structure in a molecular structure, so that the dialkyl phosphinate also has good flame retardant performance, and the hypophosphorous acid structure is contained in the molecular structure of hypophosphite and organic derivative salt flame retardants which are widely applied at present. And the dialkyl phosphinate does not belong to monitoring chemicals of the International banning mart organization because the dialkyl phosphinate does not contain a monoalkyl structure, and has wide prospects in subsequent development. However, the development and application of the compound at home and abroad are late, the compound is just started, the published and reported chemical structures are few, the synthesis method mainly comprises the reaction of phosphorus oxychloride and alcohol or epoxy compound (such as the patent technology with the publication number of CN 112028932A) or other methods (such as the patent technology with the publication number of CN 103965511A) and the like, the synthesis process is long, the process is complicated, the reaction pressure is high, the requirement on equipment is high, the used monomer is expensive, the cost is high, a large amount of highly-polluted halogen acid and flammable and explosive organic matters are by-produced, and the process is not environment-friendly and unsafe. Therefore, there is a need to develop a novel synthesis process to solve the problems faced by the prior art.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides the preparation method of the dialkyl phosphinate, the dialkyl phosphinate is synthesized by adopting the dialkyl phosphinate and the halogenated compound as raw materials through a one-step method, and compared with the traditional synthesis method, the method has the advantages of higher yield, fewer byproducts, easiness in separation, simple steps, short consumed time, safe and environment-friendly process, lower cost and easiness in implementation.
A preparation method of dialkyl phosphinate ester comprises the steps of taking dialkyl phosphinate and halogenated compounds as raw materials, and reacting under the action of a catalyst to obtain the dialkyl phosphinate ester;
the reaction process is as follows:
Figure BDA0002884244920000021
wherein R is1、R2Are each independently selected from C1-C24Alkyl (including alkanyl, cycloalkyl, etc.), aryl or alkenyl of (A), R3Selected from alkane group, aromatic group, olefin group, epoxy group, alcohol group, phenol group or halogenated group, M is metal element, X is halogen, M is valence number of metal element M, and n is an integer of 1-3.
The catalyst is one or more of a phase transfer catalyst or an amphoteric compound, and comprises at least one of a cation polyalkyl quaternary ammonium salt compound, a cation halogenated polyalkyl quaternary ammonium salt compound, alkyl ammonium chloride, alkyl ammonium bromide, an anion alkyl sulfate compound, alkyl sulfonate, alkyl benzene sulfonate, a nonionic surfactant and quaternary phosphonium salt.
In the preparation method of the invention, the reactant dialkyl hypophosphite is solid, the halogenated compound is usually liquid, the liquid-solid reaction under the action of the catalyst is realized, the target product is prepared by the one-step method, the conversion rate is high, the by-product except the target compound is inorganic halogenated metal salt, the dialkyl hypophosphite is liquid, the by-product metal salt is insoluble in the halogenated compound and the dialkyl hypophosphite, exists in the reaction system in a solid form and is easy to separate from the target product, the halogenated metal salt has small harm to the environment, the combustion and explosion can not occur, the process is environment-friendly and safe, and the defects of the traditional synthesis process are overcome. In addition, the halogenated compound can be extracted from the product through a simple mode such as negative pressure evaporation and the like, on one hand, the halogenated compound can be recycled, and on the other hand, the purity of the target product dialkyl phosphinate is ensured.
The dialkylphosphinic salts can be selected in particular from: dimethyl phosphinate, diethyl phosphinate, methylethylphosphinate, di-n-propyl phosphinate, diisopropyl phosphinate, methylpropyl phosphinate, ethylpropyl phosphinate, di-n-butyl phosphinate, di-sec-butyl phosphinate, diisobutyl phosphinate, di-tert-butyl phosphinate, methylbutyl phosphinate, ethylbutyl phosphinate, di-n-octyl phosphinate, diisooctyl phosphinate, and phosphinates of other alkane groups within 24 carbons, and the like.
M is preferably at least one selected from sodium, potassium, calcium, aluminum, magnesium, zinc and barium.
The halogenated compound may be chosen in particular from: halogenated methane, halogenated ethane, halogenated propane, halogenated butane, halogenated ethylene oxide, halogenated propylene oxide, halogenated methyl propylene oxide, halogenated butylene oxide, halogenated methanol, halogenated ethanol, halogenated butanol, halogenated ethylene, halogenated propylene, halogenated benzene, halogenated toluene, halogenated phenol, halogenated methyl phenol, and other halogenated aromatic groups, olefins, epoxy groups, alcohols, phenol groups, and the like.
X is preferably selected from one or more of fluorine, chlorine, bromine and iodine.
The preparation method of the invention has extremely low conversion rate when no catalyst is added, and does not have industrialized production conditions. Preferably, the catalyst comprises at least one of polyalkyl ammonium chloride, polyalkyl ammonium bromide, alkyl sulfate, alkyl sulfonate, alkylbenzene sulfonate, fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates, alkyl phosphate and polyhydric alcohol. The polyol includes ethylene glycol and the like.
The temperature of the reaction is preferably 40 to 150 ℃ and more preferably 100 to 150 ℃.
The pressure of the reaction may be negative pressure, normal pressure or pressure greater than one atmosphere, preferably 0 to 5MPa, and more preferably greater than one atmosphere and not greater than 5 MPa.
The reaction time can be selected by the person skilled in the art according to the actual need. Alternatively, the reaction time may be adjusted depending on the catalyst, the reaction temperature, the desired degree of reaction, and the like. In general, the reaction can be completed within 0.5 to 20 hours at a higher reaction speed; alternatively, the reaction time is from 1 to 10 hours.
The molar ratio of the dialkylphosphinic salt to the halogenated compound is preferably 1:0.1-10, more preferably 1: 1.01-5.
Preferably, the catalyst is used in an amount of 0.001 wt% to 10 wt% of the amount of the dialkylphosphinic salt. Further preferably, the amount of the catalyst is 0.1 wt% to 5.0 wt% of the amount of the dialkylphosphinic salt.
The preparation method can adopt batch reaction or continuous reaction.
The continuous process may be carried out using a series of reaction apparatus, such as a pipe reactor. And separating the product from the raw material after the reaction is finished, and returning the excessive halogenated compound to the raw material tank to realize continuous reaction.
The batch reaction may be carried out by using a series of reaction apparatuses such as reaction vessels. And separating the product from the raw material after the reaction is finished, and returning the excessive halogenated compound to the raw material tank to realize continuous reaction.
In the present invention, C1-C24Etc. refer to the number of carbon atoms contained in the group.
In the present invention, the "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of the alkane compound. The alkane compound includes straight-chain alkane, branched-chain alkane, cycloalkane and the like.
According to the preparation method, after the dialkyl phosphinate is obtained through reaction, a finished product can be obtained through further purification.
The purification comprises the methods of adding auxiliary agent for reaction, filtering or distilling and the like. Optionally, after the reaction is finished, the product is filtered and distilled to obtain the product. The distillation described herein may be distillation, evaporation; such as reduced pressure distillation, atmospheric distillation, falling film evaporation and the like.
Compared with the prior art, the invention has the main advantages that: the invention adopts dialkyl phosphinate and halogenated compound as raw materials to synthesize the compound by a one-step method. The reaction process has the advantages of convenient operation, high reaction yield, little by-product pollution and low preparation cost.
Drawings
FIG. 1 is a nuclear magnetic resonance phosphorus spectrum of the product obtained in example 1 (A)31P NMR chart);
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product obtained in example 1 (1H NMR chart);
FIG. 3 is a schematic representation of the NMR spectrum of the product obtained in example 2;
FIG. 4 is a schematic nuclear magnetic resonance hydrogen spectrum of the product obtained in example 2;
FIG. 5 is a schematic representation of the NMR spectrum of the product obtained in example 3;
FIG. 6 is a schematic nuclear magnetic resonance hydrogen spectrum of the product obtained in example 3.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Unless otherwise specified, the starting materials were all purchased commercially.
Nuclear Magnetic Resonance (NMR) testing: the model used was AVANCE DMX 400MHz, Bruker, Switzerland; the test method comprises the following steps:
1h NMR in CDCl3As a solvent, tetramethylsilane as an internal standard;
31p NMR, using deuterated halogenated chloroform as a solvent, using 85% phosphoric acid as an external standard, and scanning for 64 times;
by passing31P NMR and1h NMR can determine the molecular structure of the target product obtained.
In the following examples and comparative examples, the yield was calculated as follows: (product weight/product theoretical weight). times.100%.
EXAMPLE 1 preparation of Compounds having the Structure of formula (I)
Figure BDA0002884244920000051
Directional dress288g (2mol) of sodium diethylphosphinate and 6.0g of tetrabutylammonium bromide catalyst are added into a pressure kettle with a stirrer and a thermometer, the stirring is started, nitrogen is introduced for three times for replacement, 500g of chloroethane is introduced, the temperature is increased to 110-140 ℃, the temperature is reduced after the stirring is carried out for 10 hours, the evacuation is carried out, the vacuum is started, and the unreacted chloroethane is removed. And filtering and distilling the product to obtain 270g of a finished product, wherein the conversion rate is 90 percent, and the product of the compound shown in the formula (I) is obtained. It is composed of31P NMR and1h NMR is shown in figures 1 and 2 respectively, and the obtained compound has the structure shown in the formula (I) through spectrogram analysis.
Example 2 preparation of a Compound having the Structure of formula (II)
Figure BDA0002884244920000052
288g (2mol) of sodium diethylphosphinate and 6.0g of tetrabutylammonium bromide catalyst are added into a pressure kettle provided with a stirrer and a thermometer, the stirring is started, nitrogen is introduced for three times for replacement, 550g of chloroethanol is introduced, the temperature is increased to 110-140 ℃, the vacuum is started after the stirring is carried out for 10 hours under the condition of heat preservation, the unreacted chloroethanol is removed, and the temperature is reduced. And filtering and distilling the product to obtain 305g of a finished product, wherein the conversion rate is 92 percent, and the product of the compound shown in the formula (II) is obtained. It is composed of31P NMR and1h NMR is shown in FIGS. 3 and 4, respectively, and the obtained compound can be analyzed from the spectra to have the structure shown in formula (II).
Example 3 preparation of a Compound having the Structure of formula (III)
Figure BDA0002884244920000061
288g (2mol) of sodium diethylphosphinate, 6.0g of tetrabutylammonium bromide as a catalyst and 600g of epoxy chloropropane are added into a pressure kettle provided with a stirrer and a thermometer, the stirring is started, nitrogen is introduced for replacement for three times, the temperature is increased to 110-. The product is filtered, distilled and purified to obtain 338g of finished product, and the conversion rate is 95 percent to obtain the product shown in the formula (III). It is composed of31P NMR and1h NMR is shown in FIGS. 5 and 6, respectively, and the obtained compound was analyzed to have the structure shown in formula (III).
Comparative example 1
The difference from the example 3 is that no catalyst is added, the rest steps and conditions are the same, the product is filtered and distilled to obtain 10g of finished product, and the conversion rate is 3 percent, thus obtaining the product of the formula (III). It can be seen that if no catalyst is added, the conversion rate of the reaction is very low, and the conditions for industrial production are not met.
Comparative example 2
The traditional process for preparing diethyl ethyl hypophosphite (structural formula (I)) takes diethyl sodium hypophosphite as a raw material, and the preparation process comprises 3 steps:
(1) preparation of diethylhypophosphorous acid
600g of a 30 wt% diethylhypophosphite solution was passed through a cation exchange resin to obtain a diethylhypophosphite solution, which was allowed to stand for stratification, and the oil phase liquid was taken and evaporated to remove water to obtain 140g of diethylhypophosphite in a yield of 91.8%.
(2) Preparation of diethylphosphinic acid chloride
122g of diethyl hypophosphorous acid is heated to 80-90 ℃, 125g of thionyl chloride is added dropwise, and sodium hydroxide solution is used for absorbing the by-product sulfur dioxide and hydrogen chloride to form mixed by-product solution of sodium sulfite and sodium chloride. Dropwise adding for 5 hours, and keeping the temperature for 1 hour. The mixture was purified by distillation under reduced pressure to obtain 121g of diethylphosphinate acid chloride in a yield of 86.1%.
(3) Preparation of ethyl diethylphosphinate
Heating 70g of diethyl phosphoryl chloride to 50-60 ℃, gradually dropwise adding 70g of absolute ethyl alcohol, adding 45g of pyridine dropwise for 4 hours, and keeping the temperature for 1 hour. And filtering out pyridine hydrochloride serving as a byproduct, and carrying out reduced pressure distillation and purification to obtain 64g of finished diethyl phosphinic acid ethyl ester, wherein the yield is 85.4%.
Compared with the example 1, the same target product is prepared from the same raw material, the preparation step of the comparative example 2 is overlong, the yield is 67.5 percent, the yield is far lower than that of the one-step process, and the method has the advantages of more byproducts, larger pollution of the byproducts and no environmental protection.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (7)

1. The preparation method of dialkyl phosphinate is characterized in that dialkyl phosphinate and halogenated compound X are usednR3The dialkyl phosphinate is used as a raw material and is obtained by reaction under the action of a catalyst;
the reaction process is as follows:
Figure FDA0003594251330000011
wherein R is1、R2Are all ethyl, XnR3Selected from chloroethane, chlorohydrin and epichlorohydrin, wherein M is a metal element, X is chlorine, M is the valence number of the metal element M, and n is 1;
the catalyst is tetrabutylammonium bromide.
2. The method according to claim 1, wherein M is at least one selected from the group consisting of sodium, potassium, calcium, aluminum, magnesium, zinc, and barium.
3. The process according to claim 1, wherein the reaction is carried out at a temperature of 40 to 150 ℃ under a pressure of 0 to 5MPa for a period of 0.5 to 20 hours.
4. The method of claim 1, wherein the molar ratio of dialkylphosphinic salt to halogenated compound is from 1:0.1 to 10.
5. The method of claim 1, wherein the catalyst is used in an amount of 0.001 wt% to 10 wt% based on the amount of the dialkylphosphinic salt.
6. The method according to claim 1, wherein a batch-type or continuous-type reaction is used.
7. The method according to claim 1, wherein after the reaction to obtain the dialkylphosphinic ester, further purification is performed to obtain a finished product;
the purification comprises the steps of adding an auxiliary agent for reaction, filtering or distilling.
CN202110008008.2A 2021-01-05 2021-01-05 Preparation method of dialkyl phosphinate Active CN112661790B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202110008008.2A CN112661790B (en) 2021-01-05 2021-01-05 Preparation method of dialkyl phosphinate
PCT/CN2021/094487 WO2022147941A1 (en) 2021-01-05 2021-05-19 Dialkyl phosphinate preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110008008.2A CN112661790B (en) 2021-01-05 2021-01-05 Preparation method of dialkyl phosphinate

Publications (2)

Publication Number Publication Date
CN112661790A CN112661790A (en) 2021-04-16
CN112661790B true CN112661790B (en) 2022-07-01

Family

ID=75412959

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110008008.2A Active CN112661790B (en) 2021-01-05 2021-01-05 Preparation method of dialkyl phosphinate

Country Status (2)

Country Link
CN (1) CN112661790B (en)
WO (1) WO2022147941A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112661790B (en) * 2021-01-05 2022-07-01 江苏利思德新材料有限公司 Preparation method of dialkyl phosphinate
CN112778368B (en) * 2021-01-05 2022-08-23 江苏利思德新材料有限公司 Dialkyl phosphinate containing active epoxy group and preparation and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980306A (en) * 2014-04-28 2014-08-13 湖南大学 Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds
CN106117394A (en) * 2016-04-22 2016-11-16 中山大学 A kind of phosphonic acid ester light trigger containing fluorocarbon chain and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103951700B (en) * 2014-05-15 2016-06-29 江苏利思德新材料有限公司 Preparation method of a kind of dimethyl hypophosphites and products thereof and application
CN112661790B (en) * 2021-01-05 2022-07-01 江苏利思德新材料有限公司 Preparation method of dialkyl phosphinate
CN112778368B (en) * 2021-01-05 2022-08-23 江苏利思德新材料有限公司 Dialkyl phosphinate containing active epoxy group and preparation and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980306A (en) * 2014-04-28 2014-08-13 湖南大学 Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds
CN106117394A (en) * 2016-04-22 2016-11-16 中山大学 A kind of phosphonic acid ester light trigger containing fluorocarbon chain and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Alkylation of phosphinic acid salts in the presence of crown ethers;Golubski, Zbigniew E. et al;《Synthesis》;19801231;第8卷;第632-4页 *
ALKYLATION OF POTASSIUM 1-(N-BENZYLOXYCARBONYL-AMIN0)ALKYLPHOSPHONATES AND PHOSPHINATES IN THE PRESENCE OF 18-CROWN-6;Mariusz Skwarczynski et al;《SYNTHETIC COMMUNICATIONS》;19951231;第25卷;第3565-3571页 *
Ultrasound Promoted Synthesis of Biologically Active α- Hydroxyphosphonates/Hydroxyphosphinates using 1,4- Dimethylpiperazine as a Catalyst;S. Rasheed Et al;《Phosphorus, Sulfur, and Silicon and the Related Elements》;20141231;第189卷;第606-614页 *

Also Published As

Publication number Publication date
CN112661790A (en) 2021-04-16
WO2022147941A1 (en) 2022-07-14

Similar Documents

Publication Publication Date Title
CN112661790B (en) Preparation method of dialkyl phosphinate
CN112778368B (en) Dialkyl phosphinate containing active epoxy group and preparation and application thereof
JP4695080B2 (en) Flame retardant phosphonate additives for thermoplastics
CN105061503A (en) Diaryl alkylphosphonates and methods for preparing same
CN111363157A (en) Preparation method of oligomeric phosphonate flame retardant
US9120833B2 (en) Polyfluoroalkylphosphonic acid ester and process for producing the same
CN112142779B (en) Rapid preparation method of bisphenol A bis (diaryl phosphate)
US7683199B2 (en) Fluorine-containing polyether phosphonic acid ester compound and process for producing the same
CN111763351B (en) Reactive phosphaphenanthrene/phosphite ester biradical flame retardant, preparation method and application thereof
CN107445985A (en) A kind of preparation method and applications of polyhydroxy phosphate
CN110885344B (en) Preparation method of DOPO vinylidene bridge chain derivative, flame retardant and flame-retardant high polymer material
KR101965572B1 (en) Synthesis method of flame retarding diol, flame retarding diol for the production of thermoplastic polyurethane, and thermoplastic polyurethane having the same
JP2000038399A (en) Production of phosphonous ester
CN102675371A (en) Cyclic phenyl phosphonate compound and method for preparing same
CA2766277C (en) Polyfluoroalkylphosphonic acid ester and process for producing the same
CN114524843A (en) Hydroxyl-terminated reactive flame retardant and preparation method thereof
KR101864260B1 (en) Phosphoric acid ester production method
CN114106038A (en) Preparation method of hydroxyl phosphonate
US10759818B2 (en) Simple preparation method for dialkoxypropyl methylphosphonate
CN112028932B (en) Dialkyl phosphinate flame retardant and preparation method and application thereof
KR101852521B1 (en) A producing method of non-halogen phosphorus-based flame retardant
US3450798A (en) Phosphate esters of hydroxy-carboranes
CN102448971A (en) Method for the manufacture of dialkylphosphites
CN1583768A (en) Preparation of N,N-di(2-ethoxyl) aminomethyl diethyl phosphoric acid
JP4128279B2 (en) An improved method for the preparation of phosphites.

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: No. 88, Zhonghua East Road, Guanzhuang, Houbao Community, Tianmushan Street, Jiangyan District, Taizhou City, Jiangsu Province 225529

Patentee after: Jiangsu LISIDE New Materials Co.,Ltd.

Address before: 225529 Houbao village, Tianmushan street, Jiangyan District, Taizhou City, Jiangsu Province

Patentee before: Jiangsu Liside New Material Co.,Ltd.