CN115141368B - Organophosphorus alkoxide catalyst and preparation method thereof - Google Patents
Organophosphorus alkoxide catalyst and preparation method thereof Download PDFInfo
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- CN115141368B CN115141368B CN202211067980.8A CN202211067980A CN115141368B CN 115141368 B CN115141368 B CN 115141368B CN 202211067980 A CN202211067980 A CN 202211067980A CN 115141368 B CN115141368 B CN 115141368B
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- 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
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
Abstract
The invention relates to an organic phosphorus alkoxide catalyst and a preparation method thereof, and mainly solves the problems that an alkali catalyst used in the production of the existing polyether polyol cannot simultaneously meet the requirements of low unsaturation degree and high activity, and the cost of raw materials of the organic catalyst meeting the requirements is high. The invention adopts the organic phosphorus alkoxide catalyst, the catalyst has higher reaction activity when being used for producing polyether polyol, can simultaneously meet the advantages of low unsaturation degree, high molecular weight and high activity, and has low cost of raw materials of the catalyst, and the technical scheme of the preparation method of the catalyst is provided to better solve the problems, and the catalyst can be used for producing and preparing the polyether polyol.
Description
Technical Field
The invention relates to an organic phosphorus alkoxide catalyst and a preparation method thereof.
Background
Polyether polyol is one of main raw materials for synthesizing polyurethane materials, and the preparation methods of the polyether polyol mainly comprise anionic polymerization, cationic polymerization, coordination polymerization and the like. Anionic polymerization utilizes inorganic strong base (such as KOH) as a catalyst, the inorganic strong base has the advantages of low price, easy removal in polyether polyol and the like, and is widely applied to industrial production when preparing polyether polyol with low molecular weight, however, the inorganic strong base easily isomerizes propylene oxide to generate monohydroxy polyether with unsaturated double bonds at the tail end, so that the functionality and the relative molecular weight of the polyether polyol are reduced, and particularly, when preparing a product with high molecular weight, the content of the monohydroxy polyether is very high, for example, when preparing polyether triol with three functionality and relative molecular weight of 5000, the unsaturation degree is more than 0.05 mol/kg; cationic polymerization using strong Lewis acids (e.g., BF) 3. Ether) is used as a catalyst, a by-product of a dioxane structure is formed during olefin oxide polymerization, the performance of a prepared polyurethane product is adversely affected, impurities need to be removed by a complicated process, and the catalyst is basically not used in industrial production; the activity of the double metal cyanide complex catalyst is very high when the double metal cyanide complex catalyst is used for homopolymerization of propylene oxide and random copolymerization of ethylene oxide and propylene oxide, and polyether polyol with high molecular weight can be prepared, but small molecular polyol (such as glycerol) cannot be directly used as an initiator, and especially when the double metal cyanide complex catalyst is used for homopolymerization of ethylene oxide, the ethylene oxide can generate self-polymerization reaction to generate a polyethylene oxide by-product, so that the performance of the polyether polyol is influenced.
Chinese patent CN102171272B provides a catalyst containing a salt of a phosphazenium cation and an anion of an active hydrogen compound and a method for producing the catalyst, in the invention, a catalyst for producing polyalkylene glycol is used, the catalyst is prepared by mixing a phosphazenium salt and an active hydrogen compound, heating the mixture, adding alkylene oxide, and ring-opening polymerizing the alkylene oxide to obtain a catalyst for producing polyalkylene glycol; the polyalkylene oxide in the present invention is an important polymer used as a raw material for polyurethane foam, elastomer or the like or a surfactant or the like by reacting with an isocyanate compound.
Chinese patent CN101547929B provides a phosphonium salt compound which is easily synthesized and useful as a base catalyst, and which is used as a polymerization catalyst for an alkylene oxide compound, and which is derived from a phosphine compound and the above active hydrogen, and a salt of an anion and a counter cation of an active hydrogen compound obtained by deprotonating a proton from the active hydrogen compound is widely known, and the production process requires many steps, and is complicated in operation, and has a problem in economical efficiency, because the phosphonium salt in the present invention can be used as a polyalkylene oxide useful as a raw material for polyurethane foams and elastomers, or as a surfactant.
By high-activity polyether polyol is meant a polyether polyol having a primary hydroxyl group (-CH) 2 OH) structure, the most widely used is polyether triol with the number average molecular weight of 4500-6000, and the preparation method is mainly applied to the preparation of high-resilience polyurethane foam plastics; the preparation of high resilience polyurethane foam is generally carried out by two methods, one is to react high activity polyether polyol with Toluene Diisocyanate (TDI), and the number average molecular weight of the high activity polyether polyol is generally 4500-5000; another is to use highly reactive polyether polyols, which have a number average molecular weight of more than 6000, to react with diphenylmethane diisocyanate (MDI).
However, when the catalysts described in the above documents are used, the polymerization activity is insufficient, and when the catalysts are used for producing polyether polyols, they do not satisfy the characteristics of low unsaturation degree, high molecular weight and high activity (ethylene oxide capping) at the same time; chinese patent CN104497046B provides an organic alkoxide and its preparation method, although the catalyst has the advantages of low unsaturation degree, high molecular weight and high activity when used for producing polyether polyol, the guanidine substance used in the raw material of the catalyst has high cost and high industrial production cost.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a novel organic phosphorus alkoxide catalyst, which can not only satisfy the requirements of low unsaturation degree and high activity, but also satisfy the requirement of high cost of raw materials of organic catalysts, when used for producing polyether polyol, the organic phosphorus alkoxide catalyst has high reaction activity, and can satisfy the advantages of low unsaturation degree, high molecular weight and high activity, and the cost of raw materials of the catalyst is low.
The second technical problem to be solved by the present invention is a method for preparing an organophosphorous alkoxide catalyst corresponding to the first technical problem.
In order to solve one of the problems, the technical scheme adopted by the invention is as follows: an organophosphorus alkoxide catalyst having the general structural formula (1):
wherein Ph is aryl or heteroatom substituted aryl, and R is alkyl of 1-4 carbon atoms.
In the above technical solution, preferably, the aryl or the aryl substituted by the heteroatom group is selected from phenyl, p-methylphenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl; r is methyl.
In the above technical solution, preferably, the aryl or the heteroatom substituted aryl is selected from phenyl.
In order to solve the second problem, the invention adopts the following technical scheme: a preparation method of an organophosphorus alkoxide catalyst comprises the following steps: a) Reacting phosphorus pentahalide with an imine compound corresponding to a general formula (2) in an aromatic hydrocarbon solvent under the protection of gas inert to reactants to obtain an organic phosphorus salt of a general formula (3),
wherein Ph is aryl or heteroatom substituted aryl, n is an integer from 1 to 3, and A is an anion of an inorganic salt;
b) Reacting the organic phosphorus salt with the general formula (3) with inorganic alcohol alkali in a polar solvent to obtain the organic phosphorus alkoxide catalyst with the general formula (1); wherein the inorganic alcohol base has the structure of formula (4):
M + RO ‐ （4）
wherein M is + Is an alkali metal ion; r is alkyl of 1-4 carbon atoms.
In the above technical solution, preferably, the gas inert to the reactant is nitrogen; the molar ratio of phosphorus pentahalide to corresponding imine compound of general formula (2) in step a) is 1:5-11; the anion of the inorganic salt in step a) is X - Or BF 4 - Wherein X - Is halogen; in the step a), the reaction temperature is 60-120 ℃, and the reaction pressure is from normal pressure to 0.5MPa; in the step a), the aromatic hydrocarbon solvent is at least one selected from o-dichlorobenzene, chlorobenzene, benzene, toluene or xylene.
In the above technical scheme, preferably, the reaction temperature in the step a) is 90-110 ℃, and the reaction pressure is normal pressure; in the step a), the aromatic hydrocarbon solvent is o-dichlorobenzene.
In the above technical solution, preferably, the reaction pressure in the step a) is 0-0.3MPa.
In the above technical solution, preferably, the polar solvent in step b) is an aliphatic alcohol with 1-4 carbon atoms; in step b), the inorganic alcohol alkali is selected from sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide or sodium butoxide; in the step b), the reaction temperature is 0-50 ℃, and the reaction pressure is normal pressure.
In the above technical solution, preferably, the molar ratio of the organophosphate of the general formula (3) and the inorganic alcohol base in step b) is required for calculating the stoichiometric amount.
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 normal temperature.
The specific implementation process is as follows:
first, an organophosphorous alkoxide catalyst represented by the general formula (1) is synthesized, ph may be selected from the same or different aryl groups or hetero atom-substituted aryl groups, specifically Ph may be selected from a phenyl group, a p-chlorophenyl group, a p-bromophenyl group, a p-iodophenyl group or a p-nitrophenyl group, most preferably a phenyl group, and R is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
Reacting imine compounds with general formula (2) with phosphorus pentachloride in the presence of aromatic hydrocarbon solvent at a certain temperature to generate organic phosphorus salt with general formula (3), wherein the organic phosphorus salt is selected from the following compounds, for example: tetrakis (benzophenoneimido) phosphonium chloride, tetrakis [ bis (4-chloro) benzophenoneimido ] phosphonium chloride, tetrakis [ bis (4-bromo) benzophenoneimido ] phosphonium chloride, tetrakis [ bis (4-iodo) benzophenoneimido ] phosphonium chloride, tetrakis [ bis (4-nitro) benzophenoneimido ] phosphonium chloride, etc.; the anions of these salts can also be converted into NO 3 - 、SO 4 2- 、PO 4 2- 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - (ii) a Then, reacting the organic phosphorus salt with inorganic alcohol alkali selected from alkali metal or alkaline earth metal to generate an organic phosphorus alkoxide catalyst with a general 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 (2) with phosphorus pentahalide; the inorganic alcohol base has the structure of formula (4), wherein M + Is an alkali metal or alkaline earth metal ion; r is alkyl of 1-4 carbon atoms.
The preparation of polyether polyol with low unsaturation degree, high molecular weight and high activity adopts organophosphorus alkoxide catalyst, and the polyether polyol is prepared by polymerization reaction of active hydrogen-containing compound and olefin oxide under certain temperature and pressure; the active hydrogen-containing compound in the present invention refers to an organic compound containing a hydroxyl group, and is selected from: hydroxyl alcohols, sugars or derivatives thereof having 2 to 20 carbon atoms and 1 to 8 hydroxyl groups, such as: ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, glycerin, trimethylolpropane, diglycerin, trimethylolmelamine, pentaerythritol, glucose, sorbitol, fructose, sucrose, etc., polyether polyols having a molecular weight of 200 to 5000 having a hydroxyl number of 2 to 8; in the present invention, the alkylene oxide includes ethylene oxide, propylene oxide, 1, 2-butylene oxide, styrene oxide or their mixture, and the alkylene oxide is added in a stepwise manner, and ethylene oxide is necessary in the latter stage.
In the present invention, the amount of the organic phosphorus alkoxide catalyst to be used is not particularly limited, but is usually 1X 10 -6 —5×10 -3 g/mol of alkylene oxide, preferably 5X 10 -5 —2×10 -3 g/mol of alkylene oxide.
In the present invention, the polymerization temperature is selected in the range of 50 to 160 ℃, preferably 70 to 130 ℃, more preferably 80 to 100 ℃; the polymerization pressure is selected in the range of-0.05 to 3.0MPa, preferably 0.01 to 1MPa, more preferably 0.05 to 0.5MPa; the polymerization time is selected within 50 hours, preferably from 1 to 30 hours, more preferably from 5 to 24 hours.
The polyether polyol prepared in the present invention can be used after removing the organic phosphorus alkoxide catalyst by a common purification method such as an adsorption method or an acid type ion exchange resin treatment.
In the invention, because the novel organophosphorus alkoxide catalyst is adopted to prepare the polyether polyol, the organophosphorus alkoxide catalyst is surprisingly found to be capable of preparing the polyether polyol at a lower temperature and has the characteristics of low unsaturation degree, high molecular weight and high activity, and the raw material used for synthesizing the catalyst is an imine compound, so that the cost is lower than that of guanidine substances, and a better technical effect is achieved.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
A3000 ml three-neck flask provided with a stirrer, a thermometer and a dropping funnel is added with 208.2g of phosphorus pentachloride and 1000ml of o-dichlorobenzene, 1450g of benzophenone imine is slowly dropped under the protection of nitrogen, the reaction temperature is controlled at 90 ℃, after dropping, the mixture is slowly cooled to the normal temperature, the mixture is stirred for 4 hours at the normal temperature, precipitates are removed by filtration, 81g of sodium methoxide and 400ml of methanol are added into the obtained solution, the mixture is reacted for 5 hours at the temperature of 50 ℃, the methanol is removed by reduced pressure distillation, and then the precipitates are removed by filtration, so that the catalyst A with the mass of 626.2g is obtained.
[ example 2 ]
Adding 104.1g of phosphorus pentachloride and 1000ml of o-dichlorobenzene into a 3000ml three-neck flask provided with a stirrer, a thermometer and a dropping funnel, slowly dripping 724.8g of benzophenone imine under the protection of nitrogen, controlling the reaction temperature at 90 ℃, after finishing dripping, slowly cooling to normal temperature, stirring for 2.5 hours at normal temperature, filtering to remove precipitates, decompressing the obtained solution to remove the o-dichlorobenzene, and adding 10 percent of wtNaBF 4 824g of the aqueous solution (A) was reacted at 45 ℃ for 2.5 hours, and the temperature was lowered to 10 ℃ or lower to obtain a white solid, 52.6g of potassium methoxide and 200ml of methanol were added to the obtained solid to react at room temperature for 5 hours, and after the solid was separated by centrifugation, methanol was distilled off under reduced pressure at 50 ℃ to obtain 328.8g of a catalyst B.
[ example 3 ]
According to the conditions and procedures described in example 2, using 10% wt Na 2 CO 3 795g of aqueous solution of (A) in place of NaBF 4 Thus, catalyst C was obtained, which had a mass of 320.9g.
[ example 4 ] A method for producing a polycarbonate
Catalyst D was obtained with a mass of 576.2g using the conditions and procedures described in example 2, substituting benzophenone imine with bis (4-bromo) benzophenone imine.
[ example 5 ] A method for producing a polycarbonate
Following the conditions and procedures described in example 2, bis (4-nitro) benzophenone imine was substituted for benzophenone imine to give catalyst E having a mass of 477.1g.
[ example 6 ] A method for producing a polycarbonate
Adding 7.5g of catalyst A and 120g of 700 molecular weight crude polyether polyol into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing nitrogen to remove oxygen, vacuumizing until the pressure of the reaction kettle is reduced to-0.09 MPa after the oxygen content is less than 150ppm, slowly adding 1130g of propylene oxide when the temperature is increased to 95 ℃, controlling the reaction pressure to be less than 0.4MPa, continuously stirring until the pressure of the reaction kettle is not changed any more after the propylene oxide is added, slowly adding 250g of ethylene oxide, and obtaining 1460g of faint 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. It was determined by analysis to have a hydroxyl number of 22.5mgKOH/g, an unsaturation of 0.027mol/Kg, a primary hydroxyl content of 90.6%, a theoretical functionality of 3.00, and an actual functionality of 2.64.
[ example 7 ] A method for producing a polycarbonate
6g of catalyst B and 120g of crude polyether polyol having 700 molecular weight trifunctional were charged into a 2L autoclave equipped with a thermometer, a pressure gauge and a stirrer, and after removing oxygen by evacuation and nitrogen substitution, 1130g of propylene oxide was slowly charged at a temperature of 95 ℃ after the oxygen content was less than 150ppm, and the reaction pressure was controlled to be less than 0.4MPa. After the reaction of propylene oxide, 250g of ethylene oxide was slowly added to obtain 1482.0g of pale yellow crude polyether triol, which was refined to have a hydroxyl value of 22.6mgKOH/g, an unsaturation of 0.025mol/Kg, a primary hydroxyl content of 91.0%, a theoretical functionality of 3.00, and an actual functionality of 2.67.
[ example 8 ]
The conditions and procedure described in example 7 were followed, replacing catalyst B with catalyst C. A refined polyether triol was obtained which had a hydroxyl value of 22.9mgKOH/g, an unsaturation of 0.028mol/Kg, a primary hydroxyl content of 88.7%, a theoretical functionality of 3.00 and an actual functionality of 2.64.
[ example 9 ] A method for producing a polycarbonate
The conditions and procedure described in example 7 were followed, replacing catalyst B by 6g of catalyst D. The refined polyether triol is obtained, and has a hydroxyl value of 22.8mgKOH/g, an unsaturation degree of 0.026mol/Kg, a primary hydroxyl group content of 89.3%, a theoretical functionality of 3.00 and an actual functionality of 2.60.
[ example 10 ]
The conditions and procedure described in example 7 were followed, replacing catalyst B by 6g of catalyst E. A purified polyether triol was obtained which had a hydroxyl value of 23.0mgKOH/g, an unsaturation of 0.027mol/Kg, a primary hydroxyl content of 88.0%, a theoretical functionality of 3.00 and an actual functionality of 2.58.
[ example 11 ] A method for producing a polycarbonate
4.5g of catalyst B and 120g of crude polyether polyol with 700 molecular weight and three functions are added into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, the oxygen is removed by vacuumizing and nitrogen replacement, after the oxygen content is less than 150ppm, the vacuum is pumped until the pressure of the reaction kettle is reduced to 0.09MPa, when the temperature is increased to 95 ℃, 1130g of propylene oxide is slowly added, the reaction pressure is controlled to be less than 0.4MPa, after the propylene oxide is added, 250g of ethylene oxide is slowly added, 1475g of light yellow crude polyether triol is obtained after the reaction is finished, the hydroxyl value is 23.1mgKOH/g after refining, 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 2.81.
[ example 12 ] A method for producing a polycarbonate
According to the conditions and procedure described in example 11, instead of using 120g of the 700 molecular weight crude polyether polyol, there was obtained a purified polyether triol in which the hydroxyl value was 25.8mgKOH/g, the unsaturation degree was 0.027mol/kg, the primary hydroxyl group content was 91.3%, the theoretical functionality was 3.00 and the actual functionality was 2.68, by replacing 102g of the 600 molecular weight crude polyether polyol with 102g of the crude trifunctional polyether polyol.
[ example 13 ] to prepare a suspension
6g of catalyst B and 120g of 700 molecular weight trifunctional crude polyether polyol are added into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, after vacuum pumping and nitrogen replacement are carried out to remove oxygen, when the oxygen content is less than 150ppm, 1130g of propylene oxide is slowly added at the temperature of 125 ℃, the reaction pressure is controlled to be less than 0.4MPa, 250g of ethylene oxide is slowly added after the reaction of the propylene oxide is finished, 1492g of light yellow crude polyether triol is obtained after the reaction is finished, the hydroxyl value is 23.4mgKOH/g after refining, the unsaturation degree is 0.029mol/kg, the primary hydroxyl group content is 89.8%, the theoretical functionality is 3.00, and the actual functionality is 2.63.
[ example 14 ]
Adding 3g of catalyst B and 120g of 700-molecular-weight trifunctional crude polyether polyol 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 739g of propylene oxide at the temperature of 95 ℃ after the oxygen content is less than 150ppm, controlling the reaction pressure to be less than 0.4MPa, slowly adding 149g of ethylene oxide after the propylene oxide reaction is finished, obtaining 998g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 33.5mgKOH/g after the purification, 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 2.58.
[ COMPARATIVE EXAMPLE 1 ]
Adding 4.5g of KOH and 120g of 700-molecular-weight trifunctional crude polyether polyol 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, raising the temperature to 120 ℃ after the oxygen content is less than 150ppm, vacuumizing and dehydrating for 1h, slowly adding 1130g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, slowly adding 250g of ethylene oxide after the propylene oxide is added, obtaining 1389g of light yellow crude polyether triol after the reaction is finished, and refining to obtain the crude polyether triol with the hydroxyl value of 25.0mgKOH/g, the unsaturation degree of 0.088mol/kg, the primary hydroxyl group content of 87.2%, the theoretical functionality of 3.00 and the actual functionality of 2.84.
[ COMPARATIVE EXAMPLE 2 ]
By following the conditions and procedures described in example 14, using 3g of KOH instead of catalyst B, and dehydrating under vacuum at 120 ℃ for 1 hour, a purified polyether triol having a hydroxyl value of 32.6mgKOH/g, an unsaturation degree of 0.098mol/kg, a primary hydroxyl group content of 76.4%, a theoretical functionality of 3.00 and an actual functionality of 2.24 was obtained.
Claims (9)
1. An organophosphorus alkoxide catalyst, having a general structural formula (1):
wherein Ph is aryl or heteroatom substituted aryl, and R is alkyl of 1-4 carbon atoms.
2. An organophosphorus alkoxide catalyst according to claim 1, wherein the aryl or heteroaryl group substituted aryl is selected from phenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl; r is methyl.
3. An organophosphorus alkoxide catalyst according to claim 2, wherein the aryl or heteroaryl group substituted aryl group is selected from phenyl.
4. A process for the preparation of an organophosphorus alkoxide catalyst according to claim 1, comprising the steps of:
a) Reacting phosphorus pentahalide with corresponding imine compounds of general formula (2) in at least one solvent selected from o-dichlorobenzene, chlorobenzene, benzene, toluene or xylene under the protection of inert gases with reactants to obtain organophosphorus salt of general formula (3),
wherein Ph is aryl or aryl substituted by heteroatom group, n is 1, A is halide;
b) Reacting an organophosphate of general formula (3) with an alkali metal alkoxide in a polar solvent to obtain an organophosphate alkoxide catalyst of general formula (1); wherein the alkali metal alkoxide has a structure of formula (4):
M + RO ‐ (4)
wherein M is + Is a baseA metal ion; r is alkyl of 1-4 carbon atoms.
5. The process for producing an organophosphorus alkoxide catalyst according to claim 4, wherein the molar ratio of the phosphorus pentahalide to the corresponding imine compound of the general formula (2) in step a) is 1:5-11; in the step a), the reaction temperature is 60-120 ℃, and the reaction pressure is from normal pressure to 0.5MPa.
6. The process for preparing an organophosphorus alkoxide catalyst according to claim 5, wherein the phosphorus pentahalide in the step a) is selected from phosphorus pentachloride, the reaction temperature is 90 to 110 ℃, and the reaction pressure is normal pressure; the solvent in the step a) is ortho-dichlorobenzene.
7. The process for preparing an organophosphorus alkoxide catalyst according to claim 4, wherein the polar solvent in step b) is an aliphatic alcohol having 1 to 4 carbon atoms; the alkali metal alkoxide in the step b) is selected from sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide or sodium butoxide; in the step b), the reaction temperature is 0-50 ℃, and the reaction pressure is from normal pressure to 0.03MPa.
8. A process for the preparation of an organophosphorus alkoxide catalyst according to claim 4, wherein in step a), after the reaction of phosphorus pentahalide with the imine compound, the organophosphorus salt of general formula (3) is obtained by anion substitution with an inorganic salt solution, where n is 1 or 2, A is selected from NO 3 - 、SO 4 2- 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - An anion of the inorganic salt of (1); the molar ratio of organophosphorous salt and alkali metal alkoxide of the general formula (3) in step b) is the amount required for the stoichiometric reaction.
9. The process for producing an organophosphorus alkoxide catalyst according to claim 7, wherein the polar solvent in step b) is methanol; the alkali metal alkoxide in the step b) is at least one of potassium methoxide or sodium methoxide; the reaction temperature in step b) is normal temperature.
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