CN113429557B - Continuous preparation method of low-viscosity polyether polyol - Google Patents
Continuous preparation method of low-viscosity polyether polyol Download PDFInfo
- Publication number
- CN113429557B CN113429557B CN202110687202.8A CN202110687202A CN113429557B CN 113429557 B CN113429557 B CN 113429557B CN 202110687202 A CN202110687202 A CN 202110687202A CN 113429557 B CN113429557 B CN 113429557B
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- polyether polyol
- catalyst
- reaction
- kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
- C08G65/2696—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 process or apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a continuous preparation method of polyether polyol with low viscosity and narrow molecular weight distribution, which selects proper stirring power according to the difference of catalyst concentration and material retention time in a reaction system, ensures that the chain transfer rate of the catalyst is greater than the intermolecular mixing rate in the reaction process under the condition of ensuring the conversion rate of reactants, can fully ensure the safety of a device, and can avoid the broadening of the molecular weight distribution caused by overhigh mixing efficiency, and the product achieves the effects of narrow molecular weight distribution and low viscosity.
Description
Technical Field
The invention belongs to the technical field of polyether polyol, and particularly relates to a continuous preparation method of low-viscosity narrow-molecular-weight-distribution soft-foam polyether polyol.
Background
Polyether polyol is an important chemical raw material, and polyurethane foam produced by using the polyether polyol is widely applied to the fields of furniture and household appliances, automobiles, aerospace, buildings, clothes, packaging and the like. Polyether polyol continuous production process generally adopts Double Metal Cyanide (DMC) catalyst for catalysis, has the advantages of high productivity, small occupied area, low cost and the like, and is adopted by a plurality of companies in the world. However, compared with the batch production process, the polyether product obtained by the continuous process has large viscosity and wide molecular weight distribution, thereby causing certain influence on the application of polyether polyol.
CN 100497438C and CN 103694465B respectively disclose a preparation method of continuous polyether polyol, the process can be used for continuously, efficiently and stably producing the soft-foam polyether polyol, but the problems of wide molecular weight distribution and high viscosity of polyether polyol products are still not solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for continuously producing polyether polyol with narrow molecular weight distribution and low viscosity.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing low-viscosity narrow molecular weight distribution continuous polyether comprises the following steps:
1) adding polyether polyol and Double Metal Cyanide (DMC) catalyst into a reaction kettle in advance, heating, introducing propylene oxide for induction,
2) after the catalyst is successfully induced, continuously introducing an epoxy compound, a DMC catalyst and a small molecule initiator into the reaction kettle for reaction, enabling a reaction product to flow out of the kettle top, enter the aging kettle, and enter a storage tank after aging;
wherein, the concentration (c) of the catalyst in the reaction kettle in the step 2) is controlled to be 15-100 ppm, the average residence time (t) of the mixed material in the reaction kettle is 0.5-10 h, the stirring power (P) is 1.1-2.1 kW, and the three satisfy the relation:
wherein P is in kW, t is in h, and c is in ppm.
In the method, in the step 1), the hydroxyl value of the polyether polyol added in advance is 20-280 mgKOH/g, preferably 40-120 mgKOH/g; in the reaction starting stage, the amount of the added catalyst is large, and the concentration of the DMC catalyst in the pre-added material is 20-5000 ppm, preferably 60-1000 ppm;
the temperature of the reaction kettle is raised to 130-190 ℃, and preferably 145-160 ℃;
the adding amount of the propylene oxide is 1 to 5 percent of the mass of the polyether glycol added in advance.
In the method, in the step 2), when the temperature in the reaction kettle obviously rises and the pressure rapidly drops, the successful induction of the catalyst is shown;
the epoxy compound is ethylene oxide, propylene oxide or a mixture of the two;
the micromolecule initiator is one or more of ethylene glycol, 1, 2-propylene glycol, glycerol and trimethylolpropane;
the proportion of the added epoxy compound and the small molecular initiator is controlled according to the hydroxyl value of the product of 20-168 mgKOH/g;
as can be understood by those skilled in the art, the average residence time (t) of the mixed materials in the reaction kettle is the ratio of the mass of the materials in the reaction kettle to the sum of the mass flow rates of all the materials fed in the reaction kettle during the stable operation of the system; the reaction kettle catalyst concentration (c) is the concentration of catalyst in the mixture of epoxy compound, DMC catalyst and small molecule starter;
the epoxy compound, DMC catalyst and small molecule starter may be fed in a manner conventional in the art;
after the system is stable, the temperature of the reaction kettle and the aging kettle is 130-190 ℃, and the pressure is 0-1 MPa.
The invention has the following advantages:
in the continuous reaction process, the chain transfer speed and the intermolecular mixing speed have a crucial influence on the molecular weight distribution of the product. The chain transfer speed is determined by the molecular weight and the type and concentration of the catalyst, and the mixing speed between molecules is influenced by the back mixing degree of the reaction kettle. If the mixing speed is higher than the chain transfer speed, the molecular weight distribution of the product is widened, and the viscosity is increased; if the mixing speed is too low, the reaction rate of the epoxy compound is lowered, and the safety risk of the apparatus is increased, so that it is important to control the mixing speed between molecules reasonably. The invention can determine the range of stirring power according to the concentration and the residence time of the catalyst, thereby reasonably controlling the back mixing degree of the system, and ensuring that the chain transfer rate of the catalyst is greater than the intermolecular mixing rate under the condition of ensuring the conversion rate of the epoxy compound, thereby obtaining the polyether polyol product with narrow molecular weight distribution and low viscosity.
Detailed Description
The method provided by the present invention is further illustrated by the following examples, but the present invention includes but is not limited to the examples listed, and also includes any other known variations within the scope of the claims of the present invention.
The product performance testing method comprises the following steps:
polyether polyol hydroxyl value test method reference: GB/T12008.3-2009
Polyether polyol viscosity test method reference: GB/T12008.7-2009
The polyether polyol molecular weight distribution test method adopts gel chromatography (GPC).
Example 1
(1) 0.2g of DMC catalyst (Huaian Bade polyurethane science and technology Co., Ltd.) was dispersed in advance into 1kg of polyether polyol (polyether base material, hydroxyl value 56mgKOH/g) to prepare a catalyst slurry, and the catalyst slurry was charged into a catalyst slurry tank.
0.06g of DMC catalyst was dispersed in 2kg of polyether polyol (polyether base material, hydroxyl value 56mgKOH/g) to obtain a dispersion, and the dispersion was put into a 5L reactor, heated to 150 ℃ and introduced with 50g of propylene oxide.
(2) When the pressure of the reaction kettle rapidly decreases and the temperature rapidly rises, the catalyst is successfully activated, then a mixture of glycerol, ethylene oxide and propylene oxide (the content of ethylene oxide in the epoxy compound is 10 wt%) and catalyst slurry are continuously fed according to the required proportion, after the reaction kettle is full of liquid, the polyether glycol overflows from the kettle top to the aging kettle for aging reaction, and after the aging kettle is full of liquid, the polyether glycol overflows from the kettle top of the aging kettle and enters a product storage tank. During the continuous and stable operation, the temperature of the reaction kettle is controlled to be 150 ℃, the pressure of the reaction kettle is controlled to be 0.4MPa, the concentration of the catalyst is controlled to be 30ppm, the residence time is 2 hours, and the stirring power of the reaction kettle is 1.4kW, so that the hydroxyl value of the product is 55.87mgKOH/g, the viscosity is 503cP (25 ℃), and the molecular weight distribution is 1.14.
Examples 2 to 6
The differences between examples 2-6 and example 1 are shown in table 1 below.
TABLE 1
Comparative example 1
Based on example 1, the stirring power was 1.9kW under otherwise identical conditions, and the product viscosity was 556cP @25 ℃ and the product molecular weight distribution was 1.31.
Comparative example 2
Based on example 4, under otherwise identical conditions, a stirring power of 2.3kW was used, and the product viscosity was 420cP @25 ℃ and the product molecular weight distribution was 1.22.
Claims (10)
1. A continuous preparation method of polyether polyol with low viscosity and narrow molecular weight distribution is characterized by comprising the following steps:
1) adding polyether polyol and DMC catalyst into a reaction kettle in advance, heating, raising the temperature, introducing propylene oxide for induction,
2) continuously introducing an epoxy compound, a DMC catalyst and a small molecule initiator into the reaction kettle for reaction after the catalyst is successfully induced;
wherein, the concentration (c) of the catalyst in the reaction kettle in the step 2) is controlled to be 15-100 ppm, the average residence time (t) of the mixed material in the reaction kettle is 0.5-10 h, the stirring power (P) is 1.1-2.1 kW, and the three satisfy the relation:
wherein P is in kW, t is in h, and c is in ppm.
2. The method as claimed in claim 1, wherein the polyether polyol added in advance to the reaction kettle in the step 1) has a hydroxyl value of 20 to 280 mgKOH/g.
3. The method as claimed in claim 1, wherein in the step 1), the DMC catalyst added in advance to the reaction kettle has a concentration of 20 to 5000 ppm.
4. The method according to any one of claims 1 to 3, wherein the temperature of the reaction vessel is raised to 130 to 190 ℃ in step 1).
5. The method according to any one of claims 1 to 3, wherein in step 1), the propylene oxide is added in an amount of 1% to 5% by mass of the previously added polyether polyol.
6. The method according to claim 1, wherein in step 2), the epoxy compound is ethylene oxide and/or propylene oxide;
the micromolecule initiator is one or more of ethylene glycol, 1, 2-propylene glycol, glycerol and trimethylolpropane.
7. The method as set forth in claim 1 or 6, wherein in the step 2), the ratio of the epoxy compound and the small molecule initiator is controlled according to the hydroxyl value of the product of 20 to 168 mgKOH/g.
8. The method of claim 1, wherein in the step 2), the reaction product flows out from the top of the reaction kettle, enters the aging kettle, and enters the storage tank after aging.
9. The method as claimed in claim 1 or 6, wherein in the step 2), the temperature of the reaction kettle is 130-190 ℃ and the pressure is 0-1 MPa.
10. The method as claimed in claim 8, wherein in the step 2), the temperature of the aging kettle is 130-190 ℃ and the pressure is 0-1 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110687202.8A CN113429557B (en) | 2021-06-21 | 2021-06-21 | Continuous preparation method of low-viscosity polyether polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110687202.8A CN113429557B (en) | 2021-06-21 | 2021-06-21 | Continuous preparation method of low-viscosity polyether polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113429557A CN113429557A (en) | 2021-09-24 |
| CN113429557B true CN113429557B (en) | 2022-07-12 |
Family
ID=77756805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110687202.8A Active CN113429557B (en) | 2021-06-21 | 2021-06-21 | Continuous preparation method of low-viscosity polyether polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113429557B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114106317B (en) * | 2021-12-08 | 2024-05-03 | 万华化学集团股份有限公司 | Polyether continuous synthesis method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5689012A (en) * | 1996-07-18 | 1997-11-18 | Arco Chemical Technology, L.P. | Continuous preparation of low unsaturation polyoxyalkylene polyether polyols with continuous additon of starter |
| US20050107643A1 (en) * | 2003-11-13 | 2005-05-19 | Thomas Ostrowski | Preparation of polyether alcohols |
| CN100497438C (en) * | 2007-08-07 | 2009-06-10 | 江苏钟山化工有限公司 | Continuous preparation method for polyether glycol |
| WO2011034030A1 (en) * | 2009-09-17 | 2011-03-24 | 旭硝子株式会社 | Polyether preparation method |
| CN103694465B (en) * | 2013-11-25 | 2016-06-01 | 黎明化工研究设计院有限责任公司 | The method for continuously synthesizing of a kind of polyethers |
-
2021
- 2021-06-21 CN CN202110687202.8A patent/CN113429557B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113429557A (en) | 2021-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108070082B (en) | Method for preparing low-viscosity high-molecular-weight polyether polyol | |
| CN111518268B (en) | Preparation method of polyether polyol | |
| CN103833919B (en) | A kind of air-dried unsaturated polyester resin and production method thereof | |
| CN106832397B (en) | The method of online reuse PET Polymerization Waste | |
| CN107090606A (en) | A kind of method for producing multifunctional different polyester fiber | |
| CN113429557B (en) | Continuous preparation method of low-viscosity polyether polyol | |
| CN106519236A (en) | A method of producing methyl vinyl silicone rubber | |
| CN203938629U (en) | The production unit of poly butylene succinate | |
| CN100491442C (en) | Preparing method for polymer polybasic alcohol | |
| CN104497294A (en) | Production method of polyethylene terephthalate | |
| CN212492943U (en) | Polyester polyol reaction kettle | |
| CN112679721B (en) | Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol | |
| CN100398577C (en) | Method for preparing polyalcohol of polymer | |
| CN101973884A (en) | Method for preparing triisononyl trimellitate (TINTM) | |
| CN107903387B (en) | Method for improving propylene oxide conversion rate in polyether polyol synthesis process | |
| CN102234342B (en) | Method for preparing rare earth catalyst applied to isoprene rubber production | |
| CN111100280A (en) | Method for adding catalyst in industrial production of optical film grade polyester chips | |
| CN107057053B (en) | A kind of preparation method of water-reducing agent monomer | |
| CN213977502U (en) | Continuous production device of hydroxyl acrylic resin | |
| CN115181259A (en) | Method for continuously preparing polyether | |
| CN115286796A (en) | Ring-opening continuous polymerization process for cyclosiloxane anion | |
| CN101333289B (en) | Controllable method for preparing methoxy polyethylene glycol methacrylate-styrene polymer under condition of high vacuum degree | |
| CN115850683B (en) | Preparation process of refined polyether suitable for textile auxiliary | |
| CN116693826B (en) | Continuous preparation method of polycaprolactone polyol | |
| CN115181201B (en) | Copolymerization method of C4-C8 alpha-mono-olefin and maleic anhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |