CN115141368A - Organophosphorus alkoxide catalyst and preparation method thereof - Google Patents
Organophosphorus alkoxide catalyst and preparation method thereof Download PDFInfo
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- 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 organophosphorus 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 polyether polyol mainly comprise anionic polymerization, cationic polymerization, coordination polymerization and the like. Anionic polymerization utilizes strong inorganic bases (such as KOH) as a catalyst, which are inexpensive and easy to remove from polyether polyols, and is widely used in industrial production for the preparation of polyether polyols having low molecular weights, however, strong inorganic bases readily isomerize propylene oxide to produce monohydroxy polyethers having unsaturated double bonds at the ends, reducing the functionality and relative molecular weight of polyether polyols, especially for the preparation of high molecular weightsWhen the product is a product, the content of monohydroxy polyether is very high, for example, when polyether triol with three functionality relative molecular weight of 5000 is prepared, the unsaturation degree is more than 0.05 mol/kg; cationic polymerization utilizing 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 comprising a salt of a phosphazenium cation and an active hydrogen compound anion 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 with an active hydrogen compound, heating the mixture, adding alkylene oxide, and performing ring-opening polymerization on 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 No. CN101547929B provides a phosphonium salt compound which is easily synthesized and useful as a base catalyst, which is useful as a polymerization catalyst for an alkylene oxide compound, and which is derived from a phosphine compound and the above active hydrogen, and which is also useful as a polyalkylene oxide useful as a raw material for polyurethane foam and elastomer, or as a surfactant, and a salt of an anion and a counter cation of an active hydrogen compound obtained by removing a proton from the active hydrogen compound is widely known, and there are many steps required in the production method, complicated operation, and problems in economy.
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 usually adopts two methods, one is to use high activity polyether polyol to react with Toluene Diisocyanate (TDI), the number average molecular weight of the high activity polyether polyol is usually 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 a preparation method thereof, and although the catalyst has the advantages of low unsaturation degree, high molecular weight and high activity when used for producing polyether polyol, the guanidine substances adopted in the raw materials of the catalyst have 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 corresponding imine compounds of a general formula (2) in an aromatic hydrocarbon solvent under the protection of gas which is inert to reactants to obtain organic phosphorus salts of a general formula (3),
wherein Ph is aryl or aryl substituted by heteroatom group, n is an integer of 1-3, and A is anion of 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; step (ii) ofa) The anion of the medium inorganic salt 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 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 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; the inorganic alcohol alkali 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 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 the amount required for stoichiometric calculation.
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 to 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 polyether polyol with low unsaturation degree, high molecular weight and high activity is prepared by adopting an organic phosphorus alkoxide catalyst and carrying out polymerization reaction on a compound containing active hydrogen and olefin oxide at 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 1 to 30 hours, more preferably 5 to 24 hours.
The polyether polyol prepared in the present invention can be used after removing the organic phosphorus alkoxide catalyst by a conventional 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 ]
Adding 208.2g 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 dropwise adding 1450g of benzophenone imine under the protection of nitrogen, controlling the reaction temperature at 90 ℃, after dropwise adding, slowly cooling to the normal temperature, stirring for 4 hours at the normal temperature, filtering to remove precipitates, adding 81g of sodium methoxide and 400ml of methanol into the obtained solution, reacting for 5 hours at 50 ℃, distilling under reduced pressure to remove the methanol, filtering to remove the precipitates, and obtaining the catalyst A with the mass of 626.2g.
[ 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 ℃, slowly cooling to normal temperature after dripping is finished, 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 (2), and reacting at 45 DEG C2.5 hours, cooling to below 10 ℃ to obtain white solid, adding 52.6g potassium methoxide and 200ml methanol into the obtained solid, reacting for 5 hours at normal temperature, centrifugally separating the solid, and distilling at 50 ℃ under reduced pressure to remove methanol to obtain catalyst B with the mass of 328.8g.
[ example 3 ]
According to the conditions and procedures described in example 2, by 10% wt Na 2 CO 3 795g of aqueous solution of (A) in place of NaBF 4 The mass of the obtained catalyst C is 320.9g.
[ example 4 ]
Following the conditions and procedures described in example 2, bis (4-bromo) benzophenone imine was substituted for benzophenone imine to give catalyst D having a mass of 576.2g.
[ example 5 ] A method for producing a polycarbonate
Catalyst E, having a mass of 477.1g, was prepared according to the conditions and procedures described in example 2 substituting benzophenone imine with bis (4-nitro) benzophenone imine.
[ example 6 ] A method for producing a polycarbonate
Adding 7.5g of catalyst A 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, 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 ]
A2L autoclave equipped with a thermometer, a pressure gauge and a stirrer was charged with 6g of catalyst B and 120g of a 700 molecular weight trifunctional crude polyether polyol, and after evacuation and nitrogen substitution to remove oxygen, 1130g of propylene oxide was slowly added at a temperature of 95 ℃ after the oxygen content was less than 150ppm, with the reaction pressure being controlled at < 0.4MPa. After the reaction of propylene oxide, 250g of ethylene oxide is slowly added, and light yellow crude polyether triol 1482.0g is obtained after the reaction is finished, the hydroxyl value is 22.6mgKOH/g after the purification, the unsaturation degree is 0.025mol/Kg, the primary hydroxyl content is 91.0 percent, the theoretical functionality is 3.00, and the actual functionality is 2.67.
[ example 8 ]
Catalyst B was replaced with catalyst C according to the conditions and procedures described in example 7. 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 ]
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 with 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 ]
4.5g 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, the oxygen is removed by vacuumizing and nitrogen displacement, after the oxygen content is less than 150ppm, the vacuumizing is carried out 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 ]
According to the conditions and procedures described in example 11, a refined polyether triol was obtained after the reaction was complete which had a hydroxyl value of 25.8mgKOH/g, an unsaturation value of 0.027mol/kg, a primary hydroxyl group content of 91.3%, a theoretical functionality of 3.00 and an actual functionality of 2.68, by replacing 120g of 700 molecular weight crude polyether polyol with 102g of 600 molecular weight crude polyether polyol.
[ example 13 ]
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 reaction of the propylene oxide is finished, obtaining 998g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 33.5mgKOH/g after refining, the unsaturation degree is 0.017mol/kg, the primary hydroxyl group content is 84.5%, the theoretical functionality is 3.00, and the actual functionality is 2.58.
[ COMPARATIVE EXAMPLE 1 ]
4.5g of KOH 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, the oxygen is removed by vacuum pumping and nitrogen displacement, when the oxygen content is less than 150ppm, the temperature is raised to 120 ℃, the vacuum pumping is carried out for dehydration for 1h, 1130g of propylene oxide is slowly added, the reaction pressure is controlled to be less than 0.4MPa, 250g of ethylene oxide is slowly added after the propylene oxide is added, 1389g of light yellow crude polyether triol is obtained after the reaction is finished, the hydroxyl value is 25.0mgKOH/g after the refining, the unsaturation degree is 0.088mol/kg, the primary hydroxyl group content is 87.2%, the theoretical functionality is 3.00, and the actual functionality is 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 said aryl or heteroatom-substituted aryl is selected from phenyl, p-methylphenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl; r is methyl.
3. An organophosphorus alkoxide catalyst according to claim 2, wherein said aryl or heteroatom-substituted aryl group is selected from phenyl.
4. A process for preparing an organophosphorus alkoxide catalyst according to claim 1, comprising the steps of:
a) Reacting phosphorus pentahalide with corresponding imine compounds of a general formula (2) in an aromatic hydrocarbon solvent under the protection of gas which is inert to reactants to obtain organic phosphorus salts of a general formula (3),
wherein Ph is aryl or aryl substituted by heteroatom group, n is an integer of 1-3, and A is anion of 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.
5. The process for the preparation of 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; the anion of the inorganic salt in step a) is X - Or BF 4 - Wherein X is - 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 selected from at least one of o-dichlorobenzene, chlorobenzene, benzene, toluene or xylene.
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; in the step a), the aromatic hydrocarbon solvent is o-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 inorganic alcohol alkali 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. The process for producing an organophosphorus alkoxide catalyst according to claim 4, wherein the organophosphorus salt of the general formula (3) is obtained by anion substitution with an inorganic salt solution after the reaction of phosphorus pentahalide with the imine compound in the step a); the molar ratio of the organophosphorous salt of the general formula (3) and the inorganic alcohol base in the step b) is the amount required for stoichiometric calculation.
9. The process for producing an organophosphorus alkoxide catalyst 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 normal temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228100A (en) * | 1997-05-28 | 1999-09-08 | 三井化学株式会社 | Polyoxyalkylenepolyols, derivatives thereof, and process for producing polyoxyalkylenepolyols |
| CN1287563A (en) * | 1998-10-20 | 2001-03-14 | 三井化学株式会社 | Process for producing polyoxyalkylene polyol and producing derivative thereof |
| CN111087598A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation and use method of inorganic supported phosphazene catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228100A (en) * | 1997-05-28 | 1999-09-08 | 三井化学株式会社 | Polyoxyalkylenepolyols, derivatives thereof, and process for producing polyoxyalkylenepolyols |
| CN1287563A (en) * | 1998-10-20 | 2001-03-14 | 三井化学株式会社 | Process for producing polyoxyalkylene polyol and producing derivative thereof |
| CN111087598A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation and use method of inorganic supported phosphazene catalyst |
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