CN110628010B - Catalyst composition and method for preparing polyethylene glycol with medium molecular weight by using same - Google Patents
Catalyst composition and method for preparing polyethylene glycol with medium molecular weight by using same Download PDFInfo
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- 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
- C08G65/2603—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 the other compounds containing oxygen
- C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
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- 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
- C08G65/2654—Aluminium or boron; Compounds thereof
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- 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
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The application relates to a catalyst composition and a method for preparing medium molecular weight polyethylene glycol by using the same. The catalyst composition comprises alkyl aluminum, organoborane and phosphorus salt, wherein the molar ratio of the alkyl aluminum to the organoborane to the phosphorus salt is 1-20: 1-20: 1, and the phosphorus salt comprises monohydrogen phosphate, dihydrogen phosphate and hypophosphite in a molar ratio of 1-10: 0.5-5: 1. The catalyst composition is cheap and easy to obtain, can catalyze the ring-opening polymerization of ethylene oxide at low temperature (70-90 ℃), has high polymerization reaction activity and small dosage, and can be used for preparing polyethylene glycol with the weight-average molecular weight of 2-5 ten thousand; moreover, the ring-opening polymerization of the ethylene oxide is bulk polymerization, no solvent is used in the reaction process, the post-treatment operation is simple and easy, the product is pure, separation is not needed, the method is economic and environment-friendly, and meanwhile, the yield is high and can reach 98-99%.
Description
Technical Field
The present invention relates to a catalyst composition and its application and method for preparing medium molecular weight polyethylene glycol, in particular, it relates to a catalyst composition for ring-opening polymerization of ethylene oxide, more specifically, it relates to a catalyst composition for preparing medium molecular weight polyethylene glycol by bulk polymerization and its application and method for preparing medium molecular weight polyethylene glycol by using said catalyst composition.
Background
The polyethylene glycol has good performance, can be used as a surfactant, a lubricant, a plasticizer, a dispersing agent, a solubilizer, an adhesive, a release agent, a softening agent, an antistatic agent, an emulsifying aid, a detergent and the like, and is widely applied to the fields of textiles, coatings, electronics, chemical engineering, buildings and the like. And the excellent water solubility, stability, biocompatibility, safety and anti-immunogenicity, and the preparation method has irreplaceable effect on the preparation of medicines, foods, personal care products and cosmetics.
The ethylene oxide and the compound containing active hydrogen are subjected to ring-opening polymerization under the action of a catalyst to generate polyethylene glycol. Different catalyst systems can be adopted to obtain polyethylene glycol with greatly different molecular weight levels. Common catalysts for ethylene oxide polymerization include alkali metal-based catalysts (e.g., potassium, sodium hydroxides and alkoxides), alkaline earth metal-based catalysts (e.g., strontium, barium oxides, hydroxides and calcium, strontium, barium alkoxides, carbonates, sulfates, and calcium amides), alkyl metal catalysts (e.g., aluminum alkyls, aluminum alkoxides, zinc alkyls, and magnesium alkyls), and the like. The alkali metal catalyst is a traditional alkali catalyst, is commonly used for preparing polyethylene glycol with molecular weight lower than 2 ten thousand, and has higher reaction temperature (higher than 100 ℃). The alkaline earth metal and alkyl metal catalysts are used for preparing polyethylene glycol with high molecular weight, and the two catalysts usually need to react with a plurality of compounds in advance to prepare active catalysts, the preparation process is complex, the polymerization mode adopts solution polymerization, the product needs post-treatment, and the production cost is high.
In the US 2007/0179199A 1, sodium hydroxide or potassium hydroxide is used as a catalyst, polyethylene glycol with the molecular weight of 180-40000 is synthesized, the method is a typical method for preparing polyethylene glycol by catalyzing with alkali metal hydroxide, and the preferable reaction temperature of the reaction is 120-180 ℃. Chinese patents CN 106432707B and CN 106633024B take metallic calcium as a main raw material, and carry out closed reaction at 70-100 ℃ to prepare the amino calcium catalyst. The catalyst can be used for synthesizing an ethylene oxide polymer with the molecular weight of 5-800 ten thousand at a lower temperature (10-40 ℃). Chinese patent application CN 101528809 a uses a hydrophobically modified granular inorganic oxide, an alkyl aluminum complex and a compound containing lewis base free electron pair as a catalyst composition to prepare a poly (alkylene oxide) polymer with high molecular weight (preferably 2-800 ten thousand) by solution polymerization. The Chinese patent application CN 85104956A utilizes rare earth compounds, alkyl aluminum and water to prepare a complex catalyst, and also adopts solution polymerization to prepare a series of high molecular weight (20-300 ten thousand) poly alkylene oxides including polyethylene oxide, polypropylene oxide and poly epichlorohydrin.
As described above, many documents and patents report catalysts useful for ring-opening polymerization of ethylene oxide and methods for preparing polyethylene glycol using the same, but these methods have disadvantages such as high reaction temperature, necessity of pre-synthesis of the catalyst, solution polymerization in the polymerization mode, or failure to obtain polymers having a molecular weight of 2 to 5 ten thousand.
Disclosure of Invention
It is a primary object of the present invention to overcome at least one of the above-mentioned disadvantages of the prior art by providing a catalyst composition comprising an aluminum alkyl, an organoborane and a phosphorus salt, wherein the molar ratio of the aluminum alkyl, the organoborane and the phosphorus salt is from 1 to 20:1, and the phosphorus salt comprises a monohydrogen phosphate, a dihydrogen phosphate and a hypophosphite in a molar ratio of from 1 to 10:0.5 to 5: 1.
In one embodiment, the aluminum alkyl is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, tri-n-hexylaluminum, tri-n-octylaluminum.
In one embodiment, the organoborane is one or more of triethylboron, tri-n-butylboron, triphenylboron, tris (pentafluorophenyl) boron.
In one embodiment, the monohydrogen phosphate is one or more of disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate; the dihydric phosphate is one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate; the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite.
In one embodiment, the catalyst composition is a catalyst composition for preparing an intermediate molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 ten thousand as measured by gel chromatography.
On the other hand, it is another object of the present application to provide the use of the catalyst composition of the present application for the preparation of medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 ten thousand as measured by gel chromatography.
In a third aspect, it is another object of the present application to provide a process for preparing a medium molecular weight polyethylene glycol comprising reacting an initiator and ethylene oxide in the presence of the catalyst composition of the present application to obtain said medium molecular weight polyethylene glycol, said medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 ten thousand as measured by gel chromatography.
In one embodiment, the method for preparing the medium molecular weight polyethylene glycol is a bulk polymerization method, the reaction temperature is 70-90 ℃, and the reaction pressure is 0.1-0.6 MPa.
In one embodiment, wherein the starter is selected from one or more of methanol, ethanol, n-propanol, isopropanol, butanol, t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol.
In one embodiment, the catalyst composition is used in an amount of 0.01 to 1% by mass of the sum of the mass of the initiator and the mass of the ethylene oxide.
In one embodiment, the molar ratio of ethylene oxide to the initiator is 200-1200: 1.
The catalyst composition is cheap and easy to obtain, can catalyze the ring-opening polymerization of ethylene oxide at low temperature (70-90 ℃), has high polymerization reaction activity and small dosage, and can be used for preparing polyethylene glycol with the weight-average molecular weight of 2-5 ten thousand; the catalyst composition does not need a complex treatment process, the components are simply mixed according to a molar ratio range to obtain the corresponding catalyst composition, and even the components are respectively put into a polymerization reaction system according to the molar ratio range, the catalyst composition can also play a role of the catalyst composition; moreover, the catalyst composition can catalyze the bulk polymerization of ethylene oxide, a solvent is not used in the reaction process, the post-treatment operation is simple and easy, the product is pure, separation is not needed, economy and environmental protection are realized, and meanwhile, the yield is high and can reach 98-99%.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
In one aspect, the present application provides a catalyst composition comprising an aluminum alkyl, an organoborane, and a phosphorus salt, wherein the aluminum alkyl, the organoborane, and the phosphorus salt are in a molar ratio of 1-20: 1-20: 1, and the phosphorus salt comprises a monohydrogen phosphate, a dihydrogen phosphate, and a hypophosphite in a molar ratio of 1-10: 0.5-5: 1.
For the catalyst compositions herein, the selection of the components and the ratio of the amounts therein is critical. When certain components are absent, and/or the ratio between certain components is outside the above range, the catalyst composition when used to prepare polyethylene glycol does not result in the desired medium molecular weight polyethylene glycol. Preferably, the molar ratio of the aluminium alkyl, organoborane and phosphorus salt is from 1 to 10:2 to 20:1, more preferably from 1 to 10:2 to 10:1, even more preferably from 1 to 8:2 to 8: 1.
In one embodiment herein, aluminum alkyl refers to an organoaluminum compound having at least one alkyl group, including but not limited to one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, tri-n-hexylaluminum, tri-n-octylaluminum, and the like. The aluminum alkyls may be used alone or in combination with several different aluminum alkyls so long as the total amount of aluminum alkyl satisfies the range of molar ratios for each component in the catalyst composition of the present application.
In one embodiment herein, the organoborane can be an organoborane having a substituent that can be selected from the group consisting of an alkyl group, an aryl group, and a substituted aryl group. In one embodiment, the organoborane may be selected from one or more of triethylboron, tri-n-butylboron, triphenylboron, tris (pentafluorophenyl) boron. The organoboranes can be used alone or in combination with several different organoboranes, provided that the total amount of organoboranes satisfies the range of molar ratios for the components in the catalyst compositions of the present application.
In the catalyst compositions herein, the phosphorus salts include monohydrogen phosphate, dihydrogen phosphate, and hypophosphite in a molar ratio of 1 to 10:0.5 to 5: 1. Preferably, the molar ratio of monohydrogen phosphate, dihydrogen phosphate and hypophosphite is 1-5: 0.5-5: 1. In one embodiment of the present application, the monohydrogen phosphate may be a monohydrogen phosphate of an alkali metal, alkaline earth metal, or ammonium ion, and may be selected from one or more of disodium hydrogen phosphate, dipotassium hydrogen phosphate, and diammonium hydrogen phosphate. These monohydrogen phosphate salts may be used alone or in combination with several different monohydrogen phosphate salts, as long as the total amount thereof satisfies the defined molar ratio range. The dihydrogen phosphate can be dihydrogen phosphate of alkali metal, alkaline earth metal or ammonium ion, and can be one or more selected from sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate. These dihydric phosphates may be used alone, or in combination of several different dihydric phosphates, as long as the total amount thereof satisfies the defined range of molar ratio. The hypophosphite can be alkali metal, alkaline earth metal or ammonium ion hypophosphite, and can be selected from one or more of sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite. These hypophosphite salts can likewise be used individually or in combination, as long as their total amount meets the defined molar ratio range.
The preparation process of the catalyst composition has no special requirement, and the corresponding catalyst composition can be obtained by simply mixing the components according to the molar ratio range. Even if the components are added to the polymerization reaction system in a molar ratio range, they can function as a catalyst composition.
The catalyst composition can be used for preparing medium molecular weight polyethylene glycol, and the weight average molecular weight of the medium molecular weight polyethylene glycol is in the range of 2-5 ten thousand as measured by gel chromatography. Thus, another aspect of the present application includes the use of the catalyst composition of the present application in the preparation of a medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 million as measured by gel chromatography (GPC).
In a third aspect, the present application relates to a process for preparing a medium molecular weight polyethylene glycol comprising reacting an initiator and ethylene oxide in the presence of the catalyst composition of the present application to obtain said medium molecular weight polyethylene glycol, said medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 ten thousand as measured by gel chromatography. The method for preparing the medium molecular weight polyethylene glycol adopts a bulk polymerization method, the reaction temperature is 70-90 ℃, and the reaction pressure is 0.1-0.6 MPa. The bulk polymerization method is used for preparing the medium molecular weight polyethylene glycol, and has the advantages of high utilization rate of production equipment and simple operation; the product is pure, and complex separation and purification operations are not needed; the reactor has the advantages of large effective reaction volume, large production capacity, easy serialization, low production cost and the like.
Specifically, the method may comprise the steps of:
adding an initiator and the catalyst composition into a dry reaction kettle, after nitrogen or argon is replaced for three times, heating to 70-90 ℃, slowly adding ethylene oxide, keeping the pressure at 0.1-0.6 MPa until the calculated amount of ethylene oxide is added, and continuing aging for 30 minutes to obtain the medium molecular weight polyethylene glycol.
In the process of the present application, the starter may be selected from one or more of methanol, ethanol, n-propanol, isopropanol, butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol. The dosage of the catalyst composition is 0.01-1% of the sum of the mass of the initiator and the mass of the ethylene oxide. The molar ratio of the ethylene oxide to the initiator is 200-1200: 1.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention as claimed.
Example 1
To the dried reaction vessel was added 3.0g of triethylene glycol, and the catalyst components were mixed and added (89.7 mg total of catalyst components, consisting of triethylaluminum, triethylboron, and a phosphorus salt in a molar ratio of 2:1:1 triethylaluminum to phosphorus salt, and consisting of disodium hydrogenphosphate, sodium dihydrogenphosphate, and sodium hypophosphite in a molar ratio of 2:2:1 disodium hydrogenphosphate to sodium hypophosphite). The reaction vessel was closed, nitrogen gas was purged three times, then the temperature was raised to 70 ℃ and 427g of ethylene oxide was slowly added under a pressure of 0.3MPa to carry out a reaction for 10 hours, thereby obtaining 425g of polyethylene glycol with a yield of 99% and a weight average molecular weight of 2.14 ten thousand by GPC.
Example 2
2.1g of diethylene glycol was charged into the dry reaction vessel, and the catalyst components were mixed and added (total 342.7mg of catalyst components, consisting of triisobutylaluminum, triethylboron and a phosphorus salt, wherein the molar ratio of triisobutylaluminum: triethylboron: phosphorus salt was 4:8:1, the phosphorus salt consists of dipotassium hydrogenphosphate, potassium dihydrogenphosphate and potassium hypophosphite, and the molar ratio of dipotassium hydrogenphosphate: potassium dihydrogenphosphate: potassium hypophosphite was 1:2: 1). The reaction vessel was closed, nitrogen gas was purged three times, then the temperature was raised to 80 ℃ and 568g of ethylene oxide was slowly added under a pressure of 0.4MPa to conduct a reaction for 5.5 hours, whereby 559g of polyethylene glycol was obtained in a yield of 98% and a weight average molecular weight by GPC of 2.88 ten thousand was obtained.
Example 3
0.9g of glycerin was charged into a dry reaction vessel, and the catalyst components were mixed and added (143.4 mg total of the catalyst components, consisting of triethylaluminum, triphenylboron, and a phosphorus salt, wherein the molar ratio of triethylaluminum to triphenylboron to the phosphorus salt was 1:2:1, the phosphorus salt was composed of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium hypophosphite, and the molar ratio of diammonium hydrogen phosphate to ammonium dihydrogen phosphate to ammonium hypophosphite was 3:1: 1). The reaction vessel was closed, after nitrogen substitution was carried out three times, the temperature was raised to 75 ℃, 366g of ethylene oxide was slowly added, the pressure was maintained at 0.4MPa, and reaction was carried out under these conditions for 8 hours to obtain 361g of polyethylene glycol, the yield was 98%, and the weight average molecular weight by GPC was 3.75 ten thousand.
Example 4
To the dried reaction vessel, 1.6g of triethylene glycol was added, and the catalyst components were mixed and added (total of 429.8mg of the catalyst components, consisting of triisobutylaluminum, triphenylboron, and a phosphorus salt in which the molar ratio of triisobutylaluminum to triphenylboron to phosphorus salt is 15:5:1, the phosphorus salt consists of disodium hydrogenphosphate, sodium dihydrogenphosphate, and sodium hypophosphite in which the molar ratio of disodium hydrogenphosphate to sodium dihydrogenphosphate to sodium hypophosphite is 1:3: 1). The reaction vessel was sealed, after nitrogen substitution was carried out three times, the temperature was raised to 85 ℃ and 458g of ethylene oxide was slowly added, the reaction was carried out under a pressure of 0.5MPa for 4 hours to obtain 455g of polyethylene glycol, the yield was 99%, and the weight average molecular weight by GPC was 4.31 ten thousand.
Comparative example 1
The procedure described in example 1 was repeated except that the catalyst consisted of triethylaluminum and triethylboron only and the total mass of triethylaluminum and triethylboron was unchanged (67.3mg) in a 2:1 molar ratio. After the reaction, 409g of polyethylene glycol was obtained in a yield of 95%, and a weight average molecular weight by GPC was 0.52 ten thousand.
Comparative example 2
The procedure described in example 1 was repeated except that, although the catalyst components still totaled 89.7mg, the molar ratio of the components of the catalyst was different, wherein the molar ratio of triisobutylaluminum to triphenylboron to phosphonium salt was 5:1:10, and wherein the molar ratio of disodium hydrogen phosphate to sodium dihydrogen phosphate to sodium hypophosphite in the phosphonium salt was 1:1:8, which ratio was outside the range of catalyst composition ratios defined herein. After the reaction, 413g of polyethylene glycol was obtained in a yield of 96%, and a weight average molecular weight by GPC was 1.10 ten thousand.
It has been unexpectedly discovered from the above examples and comparative examples that medium molecular weight polyethylene glycol having a weight average molecular weight of from 2 to 5 ten thousand can be obtained using the catalyst composition of the present application; while the use of catalyst compositions not defined herein only resulted in polyethylene glycols having relatively low molecular weights, all of which had a weight average molecular weight of less than 2 million. Meanwhile, in the catalytic polymerization reaction process, the dosage of the catalyst composition is very low, and is only about 0.02-0.09% of the total weight of the ethylene oxide and the initiator, so that a good catalytic effect can be achieved. The polymerization reaction using the catalyst composition can be carried out at a lower temperature (70-90 ℃), and the reaction process is simple and controllable; the polymerization reaction process can be bulk polymerization, a solvent is not used, the post-treatment operation is simple and easy to implement, the product is pure, separation is not needed, economy and environmental protection are achieved, and meanwhile, the yield is high and can reach 98-99%.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (8)
1. A catalyst composition for the preparation of medium molecular weight polyethylene glycol consisting of an aluminum alkyl, an organoborane and a phosphorus salt, wherein the molar ratio of the aluminum alkyl, the organoborane and the phosphorus salt is from 1 to 15:1 to 8:1, and the phosphorus salt comprises a monohydrogen phosphate, a dihydrogen phosphate and a hypophosphite in a molar ratio of from 1 to 3: 1;
wherein the alkyl aluminum is one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride, tri-n-hexyl aluminum and tri-n-octyl aluminum;
the organoborane is one or more of triethylboron, tri-n-butylboron, triphenylboron and tri (pentafluorophenyl) boron;
the weight average molecular weight of the medium molecular weight polyethylene glycol is in the range of 2-5 ten thousand measured by gel chromatography.
2. The catalyst composition of claim 1, wherein the monohydrogen phosphate is one or more of disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate; the dihydric phosphate is one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate; the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite.
3. Use of the catalyst composition of claim 1 or 2 in the preparation of a medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 ten thousand as measured by gel chromatography.
4. A process for preparing a medium molecular weight polyethylene glycol comprising reacting an initiator and ethylene oxide in the presence of the catalyst composition of claim 1 or 2 to obtain said medium molecular weight polyethylene glycol, said medium molecular weight polyethylene glycol having a weight average molecular weight in the range of 2 to 5 million as measured by gel chromatography.
5. The process according to claim 4, wherein the starter is selected from one or more of methanol, ethanol, n-propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol.
6. The process of claim 5, wherein the starter is tert-butanol.
7. The process according to claim 4, wherein the catalyst composition is used in an amount of 0.01 to 1% by mass of the sum of the initiator and the ethylene oxide.
8. A process according to claim 4, wherein the molar ratio of ethylene oxide to starter is from 200 to 1200: 1.
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