CN116874522A - Organophosphorus alkoxide and preparation method thereof - Google Patents

Organophosphorus alkoxide and preparation method thereof Download PDF

Info

Publication number
CN116874522A
CN116874522A CN202210362168.1A CN202210362168A CN116874522A CN 116874522 A CN116874522 A CN 116874522A CN 202210362168 A CN202210362168 A CN 202210362168A CN 116874522 A CN116874522 A CN 116874522A
Authority
CN
China
Prior art keywords
alkoxide
organic phosphorus
general formula
organophosphorus
preparing
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.)
Pending
Application number
CN202210362168.1A
Other languages
Chinese (zh)
Inventor
涂建军
张�浩
李鹏
顾仁发
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.)
Changhua Chemical Technology Co ltd
Original Assignee
Changhua Chemical Technology 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 Changhua Chemical Technology Co ltd filed Critical Changhua Chemical Technology Co ltd
Priority to CN202210362168.1A priority Critical patent/CN116874522A/en
Publication of CN116874522A publication Critical patent/CN116874522A/en
Pending legal-status Critical Current

Links

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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds thereof

Abstract

The invention relates to an organic phosphorus alkoxide and a preparation method thereof, which mainly solve the problem that an alkali catalyst used in the production of the existing polyether polyol cannot simultaneously meet the requirements of low unsaturation degree, high molecular weight and high activity. The invention adopts an organic phosphorus alkoxide, and the structural general formula (1) is as follows:

Description

Organophosphorus alkoxide and preparation method thereof
Technical Field
The invention relates to an organic phosphorus alkoxide and a preparation method thereof.
Background
Polyether polyol is one of the main raw materials for synthesizing polyurethane materials, and the preparation methods of the polyether polyol are numerous and mainly comprise anionic polymerization, cationic polymerization, coordination polymerization and the like. CN201410061357.0 relates to a process for preparing polyether polyols, based on primer compounds which are solid at room temperature, without solvent. The anionic polymerization uses inorganic strong base (such as KOH) as a catalyst, and the inorganic strong base has the advantages of low cost, easy removal in polyether polyol and the like, and is widely used in the preparation of low molecular weight polyether polyolHowever, inorganic strong alkali easily isomerizes propylene oxide to produce monohydroxy polyether with unsaturated double bond at the end, so that the functionality and relative molecular weight of polyether polyol become smaller, especially when preparing high molecular weight products, the content of monohydroxy polyether is very high, for example, when preparing polyether triol with trifunctional relative molecular weight of 5000, the unsaturation degree is more than 0.05 mol/kg; cationic polymerization utilizes strong lewis acids (e.g., BF 3. Diethyl ether) is used as a catalyst, and by-products with dioxane structures can be formed when olefin oxide polymerization is carried out, so that the performance of the prepared polyurethane product is adversely affected, the impurities are required to be removed by using a complicated process, and basically no use is made in industrial production; although double metal cyanide complex catalysts are very active in propylene oxide homopolymerization and ethylene oxide/propylene oxide random copolymerization, polyether polyols with high molecular weight can be prepared, but small-molecular polyols (such as glycerol) cannot be directly used as an initiator, and particularly when the double metal cyanide complex catalysts are used for ethylene oxide homopolymerization, the double metal cyanide complex catalysts can cause ethylene oxide to undergo self-polymerization reaction to generate byproducts of polyethylene oxide, so that the performance of the polyether polyol is affected.
Chinese patent CN102171272B provides a catalyst comprising a salt of a phosphazenium cation and an active hydrogen compound anion, and a method for producing the catalyst, wherein the catalyst for producing a polyalkylene glycol is produced by mixing a phosphazenium salt with an active hydrogen compound, heating the mixture, and then adding an alkylene oxide to ring-open polymerize the alkylene oxide; the polyalkylene oxide in the present invention is an important polymer that is used as a raw material for polyurethane foam, elastomer, or the like, or as a surfactant, or the like, by reacting with an isocyanate compound.
Chinese patent CN101547929B provides a phosphonium salt compound which is easy to synthesize and useful as a base catalyst, wherein the phosphonium salt is used as a polymerization catalyst for an alkylene oxide compound, wherein the phosphonium salt is derived from a phosphine compound and the above-mentioned active hydrogen, and the phosphonium salt in the present invention is also useful as a raw material for polyurethane foam and elastomer, a polyalkylene oxide useful as a surfactant, or the like, and a salt of an anion and a counter cation of an active hydrogen compound obtained by removing protons from an active hydrogen compound is widely known, and there are problems in that a large number of steps are required in the production method, the operation is complicated, and the economical aspect is problematic.
The high activity polyether polyol is a polyether polyol with primary hydroxyl (-CH) 2 OH) structure, the most widely used polyether triol with the number average molecular weight of 4500-6000 is mainly applied to preparing high-resilience polyurethane foam plastic; the preparation of high resilience polyurethane foams generally employs two methods, one is the reaction of a high activity polyether polyol with Toluene Diisocyanate (TDI), the number average molecular weight of such high activity polyether polyol is generally between 4500 and 5000; the other is to react with diphenylmethane diisocyanate (MDI) using a high activity polyether polyol having a higher number average molecular weight, typically above 6000.
However, the catalysts described in the above documents are insufficient in polymerization activity and do not satisfy the characteristics of low unsaturation, high molecular weight and high activity (ethylene oxide end-capping) at the same time when used for producing polyether polyols.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the alkali catalyst used in the production of polyether polyol in the prior art cannot simultaneously meet the problems of low unsaturation degree, high molecular weight and high activity, and a novel organophosphorus alkoxide which has higher reactivity and can meet the advantages of low unsaturation degree, high molecular weight and high activity when being used for producing polyether polyol is provided.
The second technical problem to be solved by the invention is a preparation method of organic phosphorus alkoxide corresponding to one of the technical problems.
In order to solve one of the problems, the invention adopts the following technical scheme: an organic phosphorus alkoxide has a structural general formula (1) as follows:
wherein Ph is aryl or heteroatom group substituted aryl, and R is alkyl of 1-4 carbon atoms.
In the above technical scheme, preferably, the aryl or heteroatom group substituted aryl is selected from phenyl, p-methylphenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl; r is methyl.
In the above technical scheme, preferably, the aryl or heteroatom group substituted aryl is selected from phenyl.
In order to solve the second problem, the technical scheme adopted by the invention is as follows: a method for preparing an organophosphorus alkoxide, comprising the steps of: a) Reacting phosphorus trichloride with imine compound corresponding to the general formula (2) in aromatic hydrocarbon solvent under the protection of gas inert to the reactant to obtain organic phosphorus salt of the general formula (3),
wherein Ph is aryl or heteroatom group substituted aryl, n is an integer of 1-3, A is the anion of inorganic salt;
b) Reacting the organic phosphorus salt of the general formula (3) with inorganic alcohol base in a polar solvent to obtain organic phosphorus alkoxide of the general formula (1); wherein the inorganic alcohol base has the structure of the general formula (4):
M + RO-(4)
wherein M is + Is an alkali metal ion; r is an alkyl group of 1 to 4 carbon atoms.
In the above technical solution, preferably, the gas inert to the reactant is nitrogen; in the step a), the molar ratio of the phosphorus trichloride to the imine compound corresponding to the general formula (2) is 1:5-12; the anion of the inorganic salt in step a) is X - Or BF 4 -wherein X-is halogen; the reaction temperature in the step a) is between-5 ℃ and 50 ℃, and the reaction pressure is between normal pressure and 1.0MPa; the aromatic hydrocarbon solvent in step a) is selected from at least one of o-dichlorobenzene, chlorobenzene, benzene, toluene or xylene.
In the above technical scheme, preferably, the reaction temperature in the step a) is 0-30 ℃, and the reaction pressure is normal pressure; the aromatic hydrocarbon solvent in step a) is o-dichlorobenzene.
In the above technical scheme, preferably, the reaction pressure in the step a) is 0-0.3MPa.
In the above technical scheme, preferably, in the step b), the polar solvent is an aliphatic alcohol having 1 to 4 carbon atoms; the inorganic alcohol base in step b) is selected from sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide or sodium butoxide; the reaction temperature in the step b) is 0-50 ℃ and the reaction pressure is normal pressure.
In the above-described embodiment, it is preferable that the molar ratio of the organic phosphorus salt of the general formula (3) and the inorganic alcohol base in the step b) is the amount required for calculation of the stoichiometric equivalent.
In the above technical solution, preferably, the polar solvent in step b) is methanol; the inorganic alcohol alkali in the step b) is at least one of potassium methoxide or sodium methoxide; the reaction temperature in step b) is ambient.
The specific implementation process is as follows:
the organophosphorus alkoxide represented by the general formula (1) is synthesized first, ph can be the same or different aryl or heteroatom substituted aryl, specifically Ph can be phenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl, most preferably phenyl, R is alkyl of 1-4 carbon atoms, preferably methyl.
Reacting an imine compound having the general formula (2) with phosphorus trichloride in the presence of an aromatic hydrocarbon solvent at a low temperature to produce an organic phosphorus salt having the general structural formula (3), wherein the organic phosphorus salt is selected from the following compounds, for example: tris (benzophenone-imino) phosphonium chloride and tris [ bis (4-chloro) benzophenone-imino]Phosphonium chloride, tris [ di (4-bromo) benzophenone imino]Phosphonium chloride, tris [ di (4-iodo) benzophenone imino group]Phosphonium chloride and tris [ di (4-nitro) benzophenone imino]Phosphonium chloride and the like; the anions of these salts can also be converted to NO 3 - 、SO 4 2- 、PO 4 2- 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - The method comprises the steps of carrying out a first treatment on the surface of the Then the organic phosphorus salt is reacted with inorganic alcohol alkali selected from alkali metal or alkaline earth metal to generate the general purpose catalystAn organophosphorus alkoxide of formula (1); the inorganic alcohol base is selected from potassium methoxide, sodium methoxide, potassium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide, sodium butoxide, etc.; the organic phosphorus salt is prepared by reacting imine compounds with a general formula (4) with phosphorus trihalide; the inorganic alkoxide has a structure of the general formula (4), wherein M + Is an alkali metal or alkaline earth metal ion; r is an alkyl group of 1 to 4 carbon atoms.
The preparation of the polyether polyol with low unsaturation degree, high molecular weight and high activity adopts organophosphorus alkoxide as a catalyst, and the polyether polyol is prepared by polymerization reaction of active hydrogen-containing compound and alkylene oxide at a certain temperature and pressure; in the present invention, the active hydrogen-containing compound means an organic compound containing a hydroxyl group, and is selected from the group consisting of: hydroxy alcohols having 2 to 20 carbon atoms and 1 to 8 hydroxyl groups, saccharides or derivatives thereof, for example: ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, glycerol, trimethylolpropane, diglycerol, trimethylol melamine, pentaerythritol, glucose, sorbitol, fructose, sucrose, etc., polyether polyols having a molecular weight of 200-5000 having a hydroxyl number of 2-8; in the present invention, the alkylene oxide includes ethylene oxide, propylene oxide, 1, 2-butylene oxide, styrene oxide or a mixture thereof, and the alkylene oxide is added in stages, and the latter stage must be ethylene oxide.
In the present invention, the amount of the organophosphorous alkoxide is not particularly limited, but the amount is usually 1X 10 -6 —5×10 -3 g/mol alkylene oxide, preferably 5X 10 -5 —2×10 -3 g/mol alkylene oxide.
In the present invention, the temperature of the polymerization reaction is selected to be in the range of 50 to 160 ℃, preferably 70 to 130 ℃, more preferably 70 to 90 ℃; the polymerization pressure is selected to be in the range of-0.05 to 3.0MPa, preferably 0.01 to 1MPa, more preferably 0.05 to 0.5 MPa; the polymerization time is selected to be within 50 hours, preferably within 1 to 30 hours, more preferably within 2 to 24 hours.
The polyether polyol prepared in the present invention may be used after removing the organophosphorus alkoxide catalyst by a conventional refining method, for example, an adsorption method or an acid type ion exchange resin treatment.
In the invention, as the novel organophosphorus alkoxide is adopted as the catalyst for preparing polyether polyol, the organophosphorus alkoxide catalyst can be used for preparing polyether polyol at a lower temperature, and has the characteristics of low unsaturation degree, high molecular weight and high activity, for example, when the molecular weight of polyether triol reaches 7500, the unsaturation degree is less than 0.03mol/kg; the polyether polyol is more suitable for an MDI foam system, and achieves better technical effects.
The present invention is further illustrated by, but not limited to, the following examples.
Detailed Description
[ example 1 ]
137.5g of phosphorus trichloride and 1000ml of o-dichlorobenzene are added into a 3000ml three-neck flask provided with a stirrer, a thermometer and a dropping funnel, 918g of benzophenone imine is slowly added dropwise under the protection of nitrogen, the reaction temperature is controlled at 18 ℃, the temperature is slowly raised to normal temperature after the dropwise addition is finished, the mixture is stirred for 4 hours at normal temperature, the precipitate is removed by filtration, 75g of sodium methoxide and 400ml of methanol are added into the obtained solution, the mixture is reacted for 5 hours at 50 ℃, the methanol is removed by reduced pressure distillation, the precipitate is removed by filtration, and the catalyst A with the mass of 461.3g is obtained.
[ example 2 ]
Adding 68.75g phosphorus trichloride and 1000ml o-dichlorobenzene into a 3000ml three-neck flask equipped with a stirrer, a thermometer and a dropping funnel, slowly dropwise adding 454g benzophenone imine under the protection of nitrogen, controlling the reaction temperature at 18 ℃, slowly raising the temperature to normal temperature after the dropwise addition is finished, stirring for 2.5 hours at normal temperature, filtering to remove precipitate, decompressing the obtained solution to remove o-dichlorobenzene, and adding 10% wtNaBF 4 The mixture was reacted at 45℃for 2.5 hours, cooled to 10℃or lower to give a white solid, 35.0g of potassium methoxide and 200ml of methanol were added to the obtained solid, reacted at room temperature for 5 hours, and after centrifuging the solid, methanol was distilled off under reduced pressure at 50℃to give 256.2g of catalyst B.
[ example 3 ]
According to the conditions and procedure described in example 2, 10% by weight of Na 2 CO 3 Is an aqueous solution 5 of (2)30g instead of NaBF 4 Catalyst C was obtained in a mass of 244.0g.
[ example 4 ]
Catalyst D, having a mass of 457.7g, was obtained by substituting bis (4-bromo) benzophenone imine for benzophenone imine according to the conditions and procedures described in example 2.
[ example 5 ]
Catalyst E, 371.0g in mass, was obtained by substituting bis (4-nitro) benzophenone imine for benzophenone imine according to the conditions and procedures described in example 2.
[ example 6 ]
Adding 1.98g of catalyst A and 16.8g of glycerin into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, vacuumizing until the pressure of the reaction kettle is reduced to 0.09MPa, slowly adding 1160g of propylene oxide when the temperature is increased to 90 ℃, controlling the reaction pressure to be less than 0.4MPa, continuously stirring until the pressure of the reaction kettle is not changed after the propylene oxide is added, slowly adding 230g of ethylene oxide, and obtaining 1401g of light yellow crude polyether triol after the reaction is finished. And neutralizing the obtained crude polyether triol by phosphoric acid, dehydrating and adsorbing by magnesium silicate to obtain the refined polyether triol. The hydroxyl value is 22.9mgKOH/g, the unsaturation degree is 0.027mol/Kg, the primary hydroxyl content is 90.6 percent, the theoretical functionality is 3.00, and the actual functionality is 2.64.
[ example 7 ]
1.87g of catalyst B and 16.8g of glycerin are added into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, after oxygen is removed by vacuumizing and nitrogen replacement, 1160g of propylene oxide is slowly added at the temperature of 85 ℃ after the oxygen content is less than 150ppm, and the reaction pressure is controlled to be less than 0.4Mpa. After the reaction of propylene oxide is finished, 230g of ethylene oxide is slowly added, 1396.0g of light yellow crude polyether triol is obtained after the reaction is finished, the hydroxyl value is 23.1mgKOH/g, the unsaturation degree is 0.025mol/Kg, the primary hydroxyl content is 91.0%, the theoretical functionality is 3.00, and the actual functionality is 2.73.
[ example 8 ]
Catalyst C was used instead of catalyst B according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 23.5mgKOH/g, a degree of unsaturation of 0.028mol/Kg, a primary hydroxyl content of 88.7%, a theoretical functionality of 3.00 and an actual functionality of 2.62.
[ example 9 ]
Catalyst B was replaced with 2.6g of catalyst D according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 23.5mgKOH/g, a degree of unsaturation of 0.031mol/Kg, a primary hydroxyl content of 89.3%, a theoretical functionality of 3.00 and an actual functionality of 2.60.
[ example 10 ]
Catalyst B was replaced with 3.1g of catalyst E according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 24.1mgKOH/g, a degree of unsaturation of 0.033mol/Kg, a primary hydroxyl content of 88.0%, a theoretical functionality of 3.00 and an actual functionality of 2.52.
[ example 11 ]
Adding 1.62g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, vacuumizing until the pressure of the reaction kettle is reduced to 0.09MPa, slowly adding 1160g of propylene oxide when the temperature is raised to 88 ℃, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g of ethylene oxide after the propylene oxide is added, obtaining 1390.0g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 23.1mgKOH/g, the unsaturation degree is 0.028mol/kg, the primary hydroxyl content is 91.1%, the theoretical functionality is 3.00, and the actual functionality is 2.64.
[ example 12 ]
According to the conditions and procedures described in example 11, 16.8g of glycerin was replaced with 24.5g of trimethylolpropane, and after the completion of the reaction, a purified polyether triol was obtained having a hydroxyl value of 22.9mgKOH/g, a degree of unsaturation of 0.027mol/kg, a primary hydroxyl group content of 91.3%, a theoretical functionality of 3.00 and an actual functionality of 2.71.
[ example 13 ]
Adding 1.8g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, slowly adding 1160g of propylene oxide at the temperature of 125 ℃ after the oxygen content is less than 150ppm, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g of ethylene oxide after the reaction of the propylene oxide is finished, obtaining 1392.8g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 23.5mgKOH/g, the unsaturation degree is 0.029mol/kg, the primary hydroxyl content is 89.8%, the theoretical functionality is 3.00 and the actual functionality is 2.64 after the refining.
[ example 14 ]
Adding 1.2g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, slowly adding 759g of propylene oxide at the temperature of 90 ℃ after the oxygen content is less than 150ppm, controlling the reaction pressure to be less than 0.4MPa, slowly adding 137g of ethylene oxide after the reaction of the propylene oxide is finished, obtaining 912.0g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 34.2mgKOH/g after refining, the unsaturation degree is 0.017mol/kg, the primary hydroxyl content is 84.5%, the theoretical functionality is 3.00 and the actual functionality is 2.83.
[ comparative example 1 ]
Adding 4.2g KOH and 16.8g glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, heating to 120 ℃, vacuumizing and dehydrating for 1h, slowly adding 1160g propylene oxide, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g ethylene oxide after the propylene oxide is added, obtaining 1389g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 25.0mgKOH/g, the unsaturation degree is 0.088mol/kg, the primary hydroxyl content is 87.2%, the theoretical functionality is 3.00, and the actual functionality is 2.15 after the refining.
[ comparative example 2 ]
According to the conditions and procedure described in example 14, using 2.74g KOH instead of 1.2g catalyst B, vacuum dehydration was carried out at 120℃for 1 hour to give a purified polyether triol having a hydroxyl number of 36.2mgKOH/g, an unsaturation degree of 0.068mol/kg, a primary hydroxyl group content of 76.4%, a theoretical functionality of 3.00 and an actual functionality of 2.49.

Claims (9)

1. An organic phosphorus alkoxide, the structural general formula (1) is:
wherein Ph is aryl or heteroatom group substituted aryl, and R is alkyl of 1-4 carbon atoms.
2. The organophosphorus alkoxide of claim 1, wherein the aryl or heteroatom group substituted aryl is selected from phenyl, p-methylphenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl, or p-nitrophenyl; r is methyl.
3. The organophosphorus alkoxide of claim 2, wherein the aryl or heteroatom group substituted aryl is selected from phenyl.
4. A process for preparing the organophosphorus alkoxide as defined in claim 1, comprising the steps of:
a) Reacting phosphorus trichloride with imine compound corresponding to the general formula (2) in aromatic hydrocarbon solvent under the protection of gas inert to the reactant to obtain organic phosphorus salt of the general formula (3),
wherein Ph is aryl or heteroatom group substituted aryl, n is an integer of 1-3, A is the anion of inorganic salt;
b) Reacting the organic phosphorus salt of the general formula (3) with inorganic alcohol base in a polar solvent to obtain organic phosphorus alkoxide of the general formula (1); wherein the inorganic alcohol base has the structure of the general formula (4):
M + RO - (4)
wherein M is + Is an alkali metal ion; r is an alkyl group of 1 to 4 carbon atoms.
5. The method for preparing an organic phosphorus alkoxide according to claim 4, wherein the molar ratio of phosphorus trichloride to the imine compound corresponding to the general formula (2) in the step a) is 1:5-12; the anion of the inorganic salt in step a) is X - Or BF 4 - Wherein X is - Is halogen; the reaction temperature in the step a) is between-5 ℃ and 50 ℃, and the reaction pressure is between normal pressure and 1.0MPa; the aromatic hydrocarbon solvent in step a) is selected from at least one of o-dichlorobenzene, chlorobenzene, benzene, toluene or xylene.
6. The process for preparing an organic phosphorus alkoxide according to claim 5, wherein the reaction temperature in step a) is 0 to 30℃and the reaction pressure is normal pressure; the aromatic hydrocarbon solvent in step a) is o-dichlorobenzene.
7. The process for preparing an organophosphorus alkoxide according to claim 4, wherein the polar solvent in step b) is a fatty alcohol having 1 to 4 carbon atoms; the inorganic alcohol base in step b) is selected from sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide or sodium butoxide; the reaction temperature in the step b) is 0-50 ℃ and the reaction pressure is normal pressure.
8. The process for preparing an organic phosphorus alkoxide as claimed in claim 4, wherein the molar ratio of the organic phosphorus salt of the formula (3) to the inorganic alcohol base in step b) is calculated as the stoichiometric equivalent.
9. The process for preparing an organophosphorus alkoxide according to claim 7, wherein the polar solvent in step b) is methanol; the inorganic alcohol alkali in the step b) is at least one of potassium methoxide or sodium methoxide; the reaction temperature in step b) is ambient.
CN202210362168.1A 2022-04-07 2022-04-07 Organophosphorus alkoxide and preparation method thereof Pending CN116874522A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210362168.1A CN116874522A (en) 2022-04-07 2022-04-07 Organophosphorus alkoxide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210362168.1A CN116874522A (en) 2022-04-07 2022-04-07 Organophosphorus alkoxide and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116874522A true CN116874522A (en) 2023-10-13

Family

ID=88270433

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210362168.1A Pending CN116874522A (en) 2022-04-07 2022-04-07 Organophosphorus alkoxide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116874522A (en)

Similar Documents

Publication Publication Date Title
US20200369829A1 (en) Method for preparing polyols
KR101611590B1 (en) Polyalkylene glycol producing catalyst, and method for producing polyalkylene glycol using same
CN106536047B (en) Catalyst and process for preparing same
KR102480802B1 (en) Dual catalyst system for high primary hydroxyl polyols
KR102391669B1 (en) Alkylene oxide polymerization catalyst and method for producing polyalkylene oxides using same
KR100323125B1 (en) Process for preparing poly(alkylene oxide)
KR20160125400A (en) Catalyst
WO2013004694A1 (en) Continuous method for the synthesis of polyols
KR20130064754A (en) Methods for producing polyetherols
US5003111A (en) Isobutylene oxide polyols
CN104497298B (en) Method for preparing polyether polyol with low degree of unsaturation, high molecular weight and high activity
CN115141368B (en) Organophosphorus alkoxide catalyst and preparation method thereof
CN116874522A (en) Organophosphorus alkoxide and preparation method thereof
CN116874761A (en) Process for preparing low unsaturation, high activity polyether polyols
CN104497046B (en) Organic alkoxide and preparation method thereof
CN104558583A (en) Preparation method of polyether polyol
CN116874762A (en) Process for preparing low unsaturation, high molecular weight polyether polyols
JPH10158388A (en) Modified polyetherpolyol and production of polyurethane resin
WO2019081931A1 (en) Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates
JP6350103B2 (en) Polyalkylene glycol production catalyst
EP1448663B1 (en) Process for the alkoxylation of organic compounds
US5055496A (en) Polymer product containing isobutylene oxide polyols
KR101796304B1 (en) Biodegradable copolymeric resin and molded product of the same
KR20230101863A (en) (Poly) all block copolymers
KR20210074618A (en) A method for manufacturing polyethercarbonate polyol using carbon dioxide and a method for manufacturing catalyst for manufacturing the same

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