CN110922577B - Preparation method of polyether carbonate polyol - Google Patents
Preparation method of polyether carbonate polyol Download PDFInfo
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- CN110922577B CN110922577B CN201911258810.6A CN201911258810A CN110922577B CN 110922577 B CN110922577 B CN 110922577B CN 201911258810 A CN201911258810 A CN 201911258810A CN 110922577 B CN110922577 B CN 110922577B
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/323—General preparatory processes using carbon dioxide and alcohols
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a preparation method of polyether carbonate polyol, which mainly solves the technical problems that when the polyether carbonate polyol is prepared in the prior art, the specific surface area of a conventional amorphous bimetallic cyanide complex catalyst is larger than 10 square meters per gram, the activity of the catalyst is low, and the content of by-products in the prepared polyether carbonate polyol is high. The invention adopts the technical scheme that polyether carbonate polyol is obtained by taking polyether polyol with low molecular weight as an initiator and taking a high-activity amorphous bimetallic cyanide complex as a catalyst and carrying out copolymerization reaction of alkylene oxide and carbon dioxide under lower pressure, thereby better solving the problem and being applicable to production of the polyether carbonate polyol.
Description
Technical Field
The invention relates to a preparation method of polyether carbonate polyol.
Background
Carbon dioxide, a major greenhouse gas, is considered to have contributed to an increasingly serious environmental pollution; but from another perspective, carbon dioxide is a very abundant carbon resource. Due to the thermodynamic stability of carbon dioxide, it is necessary to select highly active reactants and highly efficient catalysts during its chemical immobilization. Alkylene oxide is a highly reactive reactant and has been widely used and used to prepare polyether polyols; the double metal cyanide complex catalyst (DMC) is a high-efficiency catalyst for preparing polyether polyol by ring-opening polymerization of alkylene oxide, and can prepare high-molecular-weight aliphatic polycarbonate when the copolymerization of the alkylene oxide and carbon dioxide is carried out under the pressure of more than 2.0 MPa. However, when polyether polyol with small molecular weight is used as an initiator and olefin oxide and carbon dioxide are copolymerized by using a common bimetallic complex catalyst to prepare polyether carbonate polyol with low molecular weight, the activity of the bimetallic cyanide complex catalyst is low, so that the reaction is incomplete, and the prepared polyether carbonate polyol contains cyclic carbonate, polycarbonate and other byproducts.
Chinese patent CN103635506B discloses a method for preparing polyether carbonate polyols, which relates to a method for preparing polyether polyols with an equivalent weight of 8000 to 20000g/mol from one or more H-functional starting compounds and one or more alkylene oxides in the presence of a double metal cyanide catalyst.
Chinese patent CN101611074B discloses a process for preparing polyether carbonate polyols by addition of alkylene oxides and carbon dioxide onto H-functional starter substances using DMC catalysts, which is characterized in that one or more starter substances are first placed in a reactor and one or more starter substances are metered continuously into the reactor during the reaction, wherein the content of propylene carbonate is up to 4.3%.
Disclosure of Invention
The invention aims to solve the technical problems that when polyether carbonate polyol is prepared in the prior art, the specific surface area of a conventional amorphous bimetallic cyanide complex catalyst is larger than 10 square meters per gram, the activity of the catalyst is low, and the content of by-products in the prepared polyether carbonate polyol is high, and provides a novel preparation method of the polyether carbonate polyol. The preparation method has the technical advantages of small specific surface area of the catalyst, high activity of the catalyst and low content of byproducts in the prepared polyether carbonate polyol.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method of preparing a polyether carbonate polyol, comprising the steps of:
a) taking polyether polyol with low molecular weight as an initiator;
b) adopting a high-activity amorphous bimetallic cyanide complex as a catalyst;
c) under lower pressure, the copolymerization reaction of the olefin oxide and the carbon dioxide is carried out to obtain the polyether carbonate polyol.
In the above technical solution, preferably, the polyether polyol with low molecular weight in step a) is selected from polyether polyols with molecular weight of 100-1500.
In the above technical solution, it is more preferable that the polyether polyol with low molecular weight in step a) is selected from polyether diol or polyether triol with molecular weight of 100-1500.
In the technical scheme, the high-activity amorphous bimetallic cyanide complex catalyst is preferably obtained by reacting soluble cyanide complex salt and soluble metal salt under the condition of common contact of tert-butyl alcohol and a nonionic surfactant, and the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-10 square meters per gram.
In the above technical solution, the soluble cyanide complex salt is more preferably one selected from potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanoferrate (iii), cobalt hexacyanocobaltate, tin hexacyanocobaltate or zinc hexacyanoferrate (iii); the soluble metal salt is selected from one of zinc chloride, zinc bromide, ferric chloride, nickel chloride, stannic chloride, lead chloride or cobalt chloride; the nonionic surfactant is selected from one of nonylphenol polyoxyethylene ether, polyethylene polyamine polyoxyethylene ether, stearyl alcohol polyoxyethylene ether or methallyl alcohol polyoxyethylene ether; the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-8 square meters per gram.
In the above technical solution, the most preferable soluble cyanide complex salt is one selected from potassium hexacyanocobaltate, sodium hexacyanocobaltate or potassium hexacyanoferrate (iii); the soluble metal salt is selected from one of zinc chloride, zinc bromide or ferric chloride; the nonionic surfactant is selected from one of nonylphenol polyoxyethylene ether, polyethylene polyamine polyoxyethylene ether or stearyl alcohol polyoxyethylene ether; the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-7 square meters per gram.
In the technical scheme, the lower pressure range is preferably-0.1-0.43 MPa; the alkylene oxide is at least one of ethylene oxide, propylene oxide or butylene oxide; the mass ratio of the carbon dioxide to the alkylene oxide is 1: 1-20; the reaction temperature is 80-140 ℃; the dosage of the high-activity amorphous bimetallic cyanide complex catalyst is 30-100 ppm; the mass ratio of the low molecular weight polyether polyol to the oxyalkylene is 1: 0.3-4.
In the above technical solution, it is more preferable that the alkylene oxide is selected from at least one of ethylene oxide or propylene oxide; the mass ratio of the carbon dioxide to the olefin oxide is 1: 4-15; the reaction temperature is 90-130 ℃; the dosage of the high-activity amorphous bimetallic cyanide complex catalyst is 50-100 ppm; the mass ratio of the low molecular weight polyether polyol to the oxyalkylene is 1: 1-3.5.
According to the invention, the polyether carbonate polyol is prepared by using the high-activity amorphous bimetallic cyanide complex catalyst, the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-10 square meters per gram, the activity of the catalyst is high, epoxy olefin and carbon dioxide are fully reacted, the content of the obtained polyether carbonate polyol is up to 99.85 percent, the content of cyclic carbonate is down to 0.15 percent, the content of polycarbonate is not detected, and a better technical effect is achieved.
Detailed Description
An initiator:
low molecular weight polyether polyol a1: a polyether polyol having a functionality of 3 and a molecular weight of 700;
low molecular weight polyether polyol a 2: a polyether polyol having a functionality of 3 and a molecular weight of 1000;
low molecular weight polyether polyol a 3: a polyether polyol having a functionality of 3 and a molecular weight of 1500;
low molecular weight polyether polyol a 4: a polyether polyol having a functionality of 2 and a molecular weight of 400;
low molecular weight polyether polyol a 5: a polyether polyol having a functionality of 2 and a molecular weight of 800;
low molecular weight polyether polyol a 6: a polyether polyol having a functionality of 2 and a molecular weight of 1000.
TABLE 1 raw material List
Example 1
Step one, preparing a high-activity amorphous bimetallic cyanide complex catalyst:
1.1 adding 100g of potassium hexacyanocobaltate aqueous solution with the mass percentage concentration of 8% into a 500ml three-neck flask, then adding 60g of tert-butyl alcohol and 20g of nonylphenol polyoxyethylene ether, adding 100g of zinc chloride aqueous solution with the mass percentage concentration of 32% under the stirring state, and obtaining a material I, wherein the reaction stirring speed is 8000rpm and the reaction time is 30 minutes;
1.2 adding 100g of water and 60g of tertiary butyl alcohol into the material I, mixing and washing for 30 minutes, then washing for 30 minutes by adopting 100g of tertiary butyl alcohol, drying for 6 hours in vacuum at 60 ℃ to obtain 12.05 g of high-activity amorphous bimetallic cyanide complex catalyst, and measuring the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst to be 6.5 square meters per gram.
Step two, preparing polyether carbonate polyol
2.1 adding 280g of initiator low molecular weight polyether polyol A1 into a 2L reaction kettle, adding the high-activity amorphous bimetallic cyanide complex catalyst prepared in the first step, heating the reaction kettle, replacing nitrogen in the kettle, charging 5g of first part of carbon dioxide gas (I) into the kettle under the stirring state until the pressure in the kettle is 0.1Mpa, adding 50g of first part of propylene oxide (I) for activating reaction, wherein the reaction temperature is 130 ℃, and the reaction time is 10-30 min; obtaining a material II;
2.2 adding 870g of second part of propylene oxide (II) into the material II continuously and flushing 120g of second part of carbon dioxide gas (II); maintaining the pressure in the reaction kettle at 0.2-0.25 Mpa, the reaction temperature at 130 ℃ and the reaction time at 6h to obtain 1320 g of polyether carbonate polyol; the quality test data of the polyether carbonate polyol obtained are shown in table 4.
Examples 2 to 5
Examples 2 to 5 and comparative examples 1 to 2 experiments were carried out according to the procedures of example 1, the only differences being the types of reaction raw materials, the ratios of raw materials, the reaction times and the temperatures, as shown in table 2; the detection data of the prepared polyether carbonate polyol are shown in table 4.
Table 2 of the raw materials of the components in examples 1 to 5 and comparative examples 1 to 2 (unit: g)
Examples 6 to 10
Examples 6 to 10 were carried out according to the procedures of example 1, with the only difference that the kinds of the reaction raw materials, the ratios of the raw materials, the reaction time and the temperature were different, as shown in table 3, and the quality test data of the polyether carbonate polyol obtained was shown in table 4.
Table 3 of the raw materials of the components in example 6 to example 10 (unit: g)
TABLE 4 quality test data for the polyether carbonate polyols obtained
Claims (3)
1. A method for preparing a polyether carbonate polyol, comprising the steps of:
a) taking polyether polyol with low molecular weight as an initiator; the low molecular weight polyether polyol is selected from polyether polyols with the molecular weight of 100-1500;
b) a high-activity amorphous double-metal cyanide complex is used as a catalyst; the high-activity amorphous bimetallic cyanide complex catalyst is obtained by reacting soluble cyanide complex salt and soluble metal salt under the condition of common contact of tert-butyl alcohol and a nonionic surfactant, and the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-8 square meters per gram; the reaction stirring rate is 8000 rpm;
c) carrying out copolymerization reaction of alkylene oxide and carbon dioxide under the lower pressure of-0.1-0.43 MPa to obtain polyether carbonate polyol;
wherein the soluble cyanide complex salt is at least one of potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanocobaltate (III), cobalt hexacyanocobaltate, tin hexacyanocobaltate or zinc hexacyano iridium (III); the soluble metal salt is selected from one of zinc chloride, zinc bromide, ferric chloride, nickel chloride, stannic chloride, lead chloride or cobalt chloride; the nonionic surfactant is selected from one of nonylphenol polyoxyethylene ether, polyethylene polyamine polyoxyethylene ether, stearyl alcohol polyoxyethylene ether or methallyl alcohol polyoxyethylene ether; the low molecular weight polyether polyol is selected from polyether diol or polyether triol with the molecular weight of 100-1500; the alkylene oxide is at least one of ethylene oxide, propylene oxide or butylene oxide; the mass ratio of the carbon dioxide to the olefin oxide is 1: 1-20; the reaction temperature is 80-140 ℃; the dosage of the high-activity amorphous bimetallic cyanide complex catalyst is 30-100 ppm; the mass ratio of the low molecular weight polyether polyol to the oxyalkylene is 1: 0.3-4.
2. The process for producing polyether carbonate polyol according to claim 1, wherein the soluble cyanide complex salt is one selected from potassium hexacyanocobaltate, sodium hexacyanocobaltate and potassium hexacyanoferrate (iii); the soluble metal salt is selected from one of zinc chloride, zinc bromide or ferric chloride; the nonionic surfactant is selected from one of nonylphenol polyoxyethylene ether, polyethylene polyamine polyoxyethylene ether or stearyl alcohol polyoxyethylene ether; the specific surface area of the high-activity amorphous bimetallic cyanide complex catalyst is 1-7 square meters per gram.
3. The process for producing the polyether carbonate polyol according to claim 1, wherein the alkylene oxide is at least one member selected from the group consisting of ethylene oxide and propylene oxide; the mass ratio of the carbon dioxide to the olefin oxide is 1: 4-15; the reaction temperature is 90-130 ℃; the dosage of the high-activity amorphous bimetallic cyanide complex catalyst is 50-100 ppm; the mass ratio of the low molecular weight polyether polyol to the oxyalkylene is 1: 1-3.5.
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| CN115838475A (en) * | 2023-02-22 | 2023-03-24 | 长华化学科技股份有限公司 | Process for preparing double metal cyanide catalysts |
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| CN102869699A (en) * | 2010-02-18 | 2013-01-09 | 拜耳知识产权有限责任公司 | Process for preparing polyether carbonate polyols with double metal cyanide catalysts and in the presence of metal salts |
| CN103097433A (en) * | 2010-05-18 | 2013-05-08 | 拜耳知识产权有限责任公司 | Method for producing polyether carbonate polyols |
| CN103781818A (en) * | 2011-07-18 | 2014-05-07 | 拜耳知识产权有限责任公司 | Method for preparing polyether carbonate polyols |
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| CN104910363B (en) * | 2015-04-14 | 2017-03-01 | 中国建筑材料科学研究总院 | Bimetal complex catalyst and its preparation method and application |
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| CN102869699A (en) * | 2010-02-18 | 2013-01-09 | 拜耳知识产权有限责任公司 | Process for preparing polyether carbonate polyols with double metal cyanide catalysts and in the presence of metal salts |
| CN103097433A (en) * | 2010-05-18 | 2013-05-08 | 拜耳知识产权有限责任公司 | Method for producing polyether carbonate polyols |
| CN103781818A (en) * | 2011-07-18 | 2014-05-07 | 拜耳知识产权有限责任公司 | Method for preparing polyether carbonate polyols |
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