CN108070082B - Method for preparing low-viscosity high-molecular-weight polyether polyol - Google Patents
Method for preparing low-viscosity high-molecular-weight polyether polyol Download PDFInfo
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- CN108070082B CN108070082B CN201611024230.7A CN201611024230A CN108070082B CN 108070082 B CN108070082 B CN 108070082B CN 201611024230 A CN201611024230 A CN 201611024230A CN 108070082 B CN108070082 B CN 108070082B
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- polyether polyol
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
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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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- 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
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of polyether polyol, in particular to a method for preparing polyether polyol. The method comprises the following steps: 1) adding an initial initiator, an unactivated multimetal cyanide complex catalyst and protonic acid into a reaction kettle, heating, and introducing inert gas for bubbling and degassing; 2) introducing inert gas into the reaction kettle again to ensure that the pressure in the reaction kettle is positive; 3) adding an epoxide to initiate the multimetal cyanide complex catalyst; 4) adding epoxide and small molecular initiator to carry out polymerization reaction; 5) aging and vacuum degassing to obtain the polyether polyol. The invention adopts a batch process and a multimetal cyanide complex catalyst to catalyze and synthesize the polyether polyol with high molecular weight and lower viscosity, and the viscosity of the polyether polyol is in a lower level by controlling the polymerization reaction speed of the epoxide and continuously adding a micromolecular initiator.
Description
Technical Field
The invention relates to the technical field of polyether polyol, in particular to a method for preparing polyether polyol with low viscosity and high molecular weight.
Background
The MMC (DMC) is adopted to catalyze and synthesize polyether polyol, and the commonly prepared polyether polyol has the advantages of low unsaturation degree, narrow molecular weight distribution and the like, but also has the phenomenon of ultrahigh molecular weight tailing. Due to the presence of ultra-high molecular weight substances, the viscosity of polyether polyols rises sharply when higher equivalent molecular weights are prepared, limiting later use of polyether polyols.
The process for synthesizing polyether polyol by MMC (DMC) catalysis mainly comprises a batch method and a continuous process. The batch production process has simple process flow and can control the yield more flexibly and effectively according to the requirement. Compared with the batch process, the continuous process is more suitable for producing a large amount of polyether polyol. At present, the Domestic MMC (DMC) catalytic synthesis process of polyether polyol is mainly a batch production process.
In general, polyethers synthesized using MMC (DMC) catalysts are often used in elastomeric materials where higher demands are placed on the viscosity of the polyether polyol during use, and where higher molecular weight polyether polyols are used where the relatively lower viscosity makes the polyether polyol easier to handle during use, it is desirable to reduce the viscosity of the polyether polyol as much as possible while maintaining its molecular weight.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a process for preparing relatively low viscosity high molecular weight polyether polyols. The method comprises the following steps: 1) adding an initial initiator, an unactivated multimetal cyanide complex catalyst and protonic acid into a reaction kettle, heating, and introducing inert gas for bubbling and degassing; 2) introducing inert gas into the reaction kettle again to ensure that the pressure in the reaction kettle is positive; 3) adding an epoxide to initiate the multimetal cyanide complex catalyst; 4) adding epoxide and small molecular initiator to carry out polymerization reaction; 5) aging and vacuum degassing to obtain the polyether polyol. The invention adopts a batch process and MMC (DMC) catalyst to catalyze and synthesize the polyether polyol with high molecular weight and lower viscosity, and the viscosity of the polyether polyol is in a lower level by controlling the polymerization reaction speed of epoxide and continuously adding a micromolecular initiator.
To achieve the above and other related objects, the present invention provides a method for preparing polyether polyol, comprising the steps of:
1) adding an initial initiator, an unactivated multimetal cyanide complex catalyst and protonic acid into a reaction kettle, heating, and introducing inert gas for bubbling and degassing;
2) continuously introducing inert gas into the reaction kettle to ensure that the pressure in the reaction kettle is positive;
3) adding an epoxide to initiate the multimetal cyanide complex catalyst;
4) adding epoxide and small molecular initiator to carry out polymerization reaction;
5) aging and vacuum degassing to obtain the polyether polyol.
The multimetal cyanide complex catalyst is the multimetal cyanide complex catalyst of patent No. 200910197582.6.
Preferably, in the step 1), the initial initiator is at least one selected from polyoxypropylene propylene glycol ether and polyoxypropylene trimethylene glycol ether, the number average molecular weight is 400-12000, and the hydroxyl functionality is 1-8.
Preferably, in the step 1), the temperature is raised to 95-105 ℃, and then inert gas is introduced for bubbling and degassing.
Preferably, in the step 1), the concentration of the multimetal cyanide complex catalyst in the finally prepared polyether polyol is 5-100 ppm; the concentration of the protonic acid in the initial initiator is 5-300 ppm.
Preferably, in the step 2), the relative pressure in the reaction kettle is 0-0.4 MPa, such as 0-0.05 MPa, 0.05-0.1 MPa, 0.1-0.2 MPa, 0.2-0.3 MPa or 0.3-0.4 MPa.
Preferably, in step 1) and step 2), the inert gas is selected from one or more of nitrogen, carbon dioxide, helium and argon.
Preferably, the molar ratio of epoxide added to the initiating multimetal cyanide complex catalyst in step 3) to the initial starter is from 2 to 0.1: 1.
preferably, in the step 4), the small molecule initiator is one or more selected from water, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol and glycerol, and the hydroxyl functionality is 1-3.
Preferably, in step 3) and step 4), the epoxide is selected from one or more of propylene oxide, ethylene oxide and butylene oxide.
Preferably, in the step 4), the temperature of the polymerization reaction is 115-135 ℃.
Preferably, in step 4), the polymerization reaction time is 10-14 hr, such as 10-10.5 hr, 10.5-11.5 hr, 11.5-12.6 hr, 12.6-13.5 hr or 13.5-14 hr.
The viscosity of the polyether polyol prepared by the method is greatly reduced compared with that of the polyether polyol prepared by the traditional DMC (MMC) process, the viscosity of the polyether polyol with the molecular weight of 12000 synthesized by a DMC (MMC) catalyst is about 25000mPa.s, while the viscosity of the polyether polyol with the same molecular weight prepared by the method is only about 6200mPa.s, and the viscosity of the polyether polyol with the molecular weight of 26714 synthesized is 15510mPa.s, which is greatly reduced compared with that in the prior patent.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The required raw materials are as follows:
initial starter: the difunctional polyether polyol has a hydroxyl value of 5-100 mgKOH/g, GE-220A (the number average molecular weight is 2000), GSE-2028 (the number average molecular weight is 4000) or GSE-2010 (the number average molecular weight is 11220) and the like, is purchased from China petrochemical Shanghai Gaoqiao corporation and is polyoxypropylene propylene glycol ether;
small molecule initiator: propylene glycol. Purchased from Shandong Shi Dashenghua chemical group, Inc.;
epoxide: and (3) propylene oxide. Purchased from Shandong Binshi group, Inc.;
examples 1 to 8: preparing polyether polyol, comprising the following steps:
(1) mixing an initial initiator, an unactivated multimetal cyanide complex catalyst (using the multimetal cyanide complex catalyst described in example 1 of patent No. 200910197582.6), and a protonic acid, feeding the mixture into a reaction vessel, raising the temperature to a predetermined temperature (the temperature of each example is shown in tables 1A and 1B), and introducing an inert gas, nitrogen, to perform bubbling degassing;
(2) continuously introducing inert gas nitrogen into the reaction kettle to ensure that the pressure in the reaction kettle is positive;
(3) slowly adding a quantity of propylene oxide to initiate the multimetal cyanide complex catalyst;
(4) continuously adding metered propylene oxide and a small molecule initiator (the types of each example are shown in tables 1A and 1B) into a reaction kettle to carry out polymerization reaction for 10-14 hr until the reaction is finished;
(5) after aging, vacuum degassing to obtain polyether polyol.
The reaction conditions and the indices of the polyether polyols are shown in Table 1.
Comparative example 1: preparing polyether polyol, comprising the following steps:
(1) mixing an initial initiator GE-220A, an unactivated multimetal cyanide complex catalyst and protonic acid, putting into a reaction kettle, heating to a certain temperature, and introducing inert gas nitrogen for bubbling and degassing;
(2) adding propylene oxide to initiate the multimetal cyanide complex catalyst;
(3) continuously adding metered propylene oxide into the reaction kettle to perform polymerization reaction for 1-4 hr until the reaction is finished;
(4) after aging, vacuum degassing to obtain polyether polyol.
The reaction conditions and the indices of the polyether polyols are shown in Table 1.
TABLE 1A
TABLE 1B
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A process for preparing a polyether polyol, comprising the steps of:
1) adding an initial initiator, an unactivated multimetal cyanide complex catalyst and protonic acid into a reaction kettle, heating, and introducing inert gas for bubbling and degassing;
2) continuously introducing inert gas into the reaction kettle to ensure that the pressure in the reaction kettle is positive;
3) adding an epoxide to initiate the multimetal cyanide complex catalyst;
4) adding epoxide and small molecular initiator to carry out polymerization reaction;
5) aging and vacuum degassing to obtain the polyether polyol;
in the step 2), the relative pressure in the reaction kettle is 0-0.4 MPa;
the molar ratio of the epoxide added with the initiating multimetal cyanide complex catalyst in the step 3) to the initial initiator is 2-0.1: 1.
2. the method according to claim 1, wherein in step 1), the initial initiator is at least one selected from the group consisting of polyoxypropylene propylene glycol ether and polyoxypropylene propylene glycol ether, has a number average molecular weight of 400-12000, and has a hydroxyl functionality of 1-8.
3. The method according to claim 1, wherein in the step 1), the temperature is raised to 95-105 ℃, and then inert gas is introduced for bubbling degassing.
4. The process according to claim 1, wherein in step 1), the concentration of multimetal cyanide complex catalyst in the finally prepared polyether polyol is from 5 to 100 ppm; the concentration of the protonic acid in the initial initiator is 5-300 ppm.
5. The method according to claim 1, wherein in step 1) and step 2), the inert gas is selected from one or more of nitrogen, carbon dioxide, helium and argon.
6. The method according to claim 1, wherein in step 4), the small molecule initiator is one or more selected from water, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol and glycerol, and the hydroxyl functionality is 1-3.
7. The method according to claim 1, wherein in step 3) and step 4), the epoxide is selected from one or more of propylene oxide, ethylene oxide and butylene oxide.
8. The method according to claim 1, wherein the polymerization temperature in step 4) is 115-135 ℃.
9. The method according to claim 1, wherein the polymerization time in step 4) is 10 to 14 hr.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110818889A (en) * | 2019-11-15 | 2020-02-21 | 山东蓝星东大有限公司 | Synthesis method of micromolecular polyether polyol with narrow molecular weight distribution |
| CN111518268B (en) * | 2020-05-28 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of polyether polyol |
| CN112011042B (en) * | 2020-08-12 | 2023-06-16 | 上海抚佳精细化工有限公司 | Preparation method of high molecular weight low viscosity polyether polyol |
| CN114409889A (en) * | 2021-12-13 | 2022-04-29 | 山东一诺威新材料有限公司 | Method for reducing tailing of high molecular weight part in polyether polyol synthesized by DMC catalysis |
| CN115181259B (en) * | 2022-08-11 | 2024-04-09 | 万华化学集团股份有限公司 | Method for continuously preparing polyether |
| WO2024126551A1 (en) * | 2022-12-14 | 2024-06-20 | Shell Internationale Research Maatschappij B.V. | Batch process for preparing a polyether alcohol using a double metal cyanide catalyst |
| WO2024126550A1 (en) * | 2022-12-14 | 2024-06-20 | Shell Internationale Research Maatschappij B.V. | Batch process for preparing a polyether alcohol using a double metal cyanide catalyst |
| CN119019670B (en) * | 2024-10-30 | 2025-01-24 | 中化东大(淄博)有限公司 | Low viscosity, high molecular weight polyether polyol and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302287A (en) * | 2008-05-09 | 2008-11-12 | 中国石油化工集团公司 | Method for preparing polyether polyol by continuous process |
| CN102040731A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工集团公司 | Method for preparing polyether polyol |
| CN103703052A (en) * | 2011-06-01 | 2014-04-02 | 拜耳知识产权有限责任公司 | Method for producing polyether polyols |
| CN103797046A (en) * | 2011-07-18 | 2014-05-14 | 拜耳知识产权有限责任公司 | Method for producing polyether polyols |
| CN104109234A (en) * | 2014-08-06 | 2014-10-22 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol with high molecular weight, low unsaturation degree and high primary hydroxyl group content |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04300920A (en) * | 1991-03-29 | 1992-10-23 | Asahi Glass Co Ltd | Production of polyethers |
| US5426081A (en) * | 1993-12-23 | 1995-06-20 | Arco Chemical Technology, L.P. | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302287A (en) * | 2008-05-09 | 2008-11-12 | 中国石油化工集团公司 | Method for preparing polyether polyol by continuous process |
| CN102040731A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工集团公司 | Method for preparing polyether polyol |
| CN103703052A (en) * | 2011-06-01 | 2014-04-02 | 拜耳知识产权有限责任公司 | Method for producing polyether polyols |
| CN103797046A (en) * | 2011-07-18 | 2014-05-14 | 拜耳知识产权有限责任公司 | Method for producing polyether polyols |
| CN104109234A (en) * | 2014-08-06 | 2014-10-22 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol with high molecular weight, low unsaturation degree and high primary hydroxyl group content |
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