CN111057229A - Preparation method of pentaerythritol polyether polyol - Google Patents
Preparation method of pentaerythritol polyether polyol Download PDFInfo
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- CN111057229A CN111057229A CN201911306785.4A CN201911306785A CN111057229A CN 111057229 A CN111057229 A CN 111057229A CN 201911306785 A CN201911306785 A CN 201911306785A CN 111057229 A CN111057229 A CN 111057229A
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- pentaerythritol
- 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
- C08G65/26—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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
A preparation method of pentaerythritol polyether polyol, wherein pentaerythritol and PO are added in two stages, and the preparation method comprises the following steps: adding pentaerythritol with the set amount of 20-40% into a reaction kettle, adding a liquid phase initiator and a catalyst, stirring and heating, adding epoxy Propane (PO) with the set amount of 25-35% at the temperature of 85-95 ℃, cooling to 70 ℃ for curing reaction for 2h, adding the rest of pentaerythritol with the set amount into the reaction kettle, heating to 105-; after the reaction is finished, adding 50% phosphoric acid into the reaction system, neutralizing, refining and filtering to obtain the product pentaerythritol polyether polyol. The invention adopts two-stage feeding of pentaerythritol, reduces the consumption of crude pentaerythritol polyether, which only accounts for 8 percent of the consumption of pentaerythritol, avoids the production of low-functionality pentaerythritol polyether polyol, and ensures the quality of products.
Description
Technical Field
The invention relates to a preparation method of pentaerythritol polyether polyol, belonging to the technical field of chemical preparation.
Background
The melting point of pentaerythritol is higher (262 ℃), and when the pentaerythritol is directly applied to production of polyether polyol in production, the pentaerythritol in a full solid state cannot be stirred by the existing production equipment and cannot be directly produced in large scale.
In the traditional production process, hot water is adopted to dissolve pentaerythritol, and then polyether polyol is synthesized; because the solubility of pentaerythritol in water is low, a large amount of alcohol-dissolving water needs to be added, the pentaerythritol needs to be removed after the reaction is finished, the production period is long, the energy consumption is high, and a large amount of wastewater is also generated; water reacts with propylene oxide to generate partial propylene glycol polyether, which affects the functionality of the product and the quality stability of the product.
In addition, in the prior art, pentaerythritol is fed once, the use amount of a pentaerythritol polyether solvent is large and accounts for 50-200% of pentaerythritol, and the proportion of polyether with high molecular weight generated in the later period is increased, so that the quality of polyether is influenced.
Disclosure of Invention
The invention provides a preparation method of pentaerythritol polyether polyol, aiming at the problems in the prior art, the invention adopts two-section feeding of pentaerythritol, reduces the using amount of crude pentaerythritol polyether, which only accounts for 8% of the using amount of pentaerythritol, avoids the generation of low-functionality pentaerythritol polyether polyol, and ensures the quality of products.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of pentaerythritol polyether polyol, wherein pentaerythritol and PO are fed in two stages, and the preparation method comprises the following steps:
a. adding pentaerythritol with the set amount of 20-40% into a reaction kettle, adding a liquid phase initiator and a catalyst, stirring and heating, adding Propylene Oxide (PO) with the set amount of 25-35% at the temperature of 85-95 ℃, and carrying out curing reaction for 2-2 h;
b. cooling to 70 ℃, adding the rest amount of pentaerythritol into the reaction kettle, heating to 105-;
c. after the reaction is finished, adding 50% phosphoric acid into the reaction system, neutralizing, refining and filtering to obtain the product pentaerythritol polyether polyol.
In the preparation method of the pentaerythritol polyether polyol, the set addition ratio of the pentaerythritol to the propylene oxide is 1: (2.60-2.70).
According to the preparation method of the pentaerythritol polyether polyol, the liquid phase initiator is crude pentaerythritol polyether, and the addition amount of the liquid phase initiator is 30-50% of the feeding amount of the first-stage pentaerythritol.
In the preparation method of the pentaerythritol polyether polyol, the catalyst is one of potassium hydroxide, sodium hydroxide or cesium hydroxide.
In the preparation method of the pentaerythritol polyether polyol, in the step c, phosphoric acid is added to neutralize until the pH value is 4.2-5.5.
The method adopts a two-step feeding method to prepare the pentaerythritol polyether polyol, pentaerythritol is used as a raw material and is added in two steps, PO is used as a chain extender and is also added in two steps, 20-40% of pentaerythritol is added in the first step, crude pentaerythritol polyether is added as a liquid phase initiator, the adding amount is small and only accounts for 8% of the total amount of the pentaerythritol, the generation of polyether with high molecular weight in the later period is avoided, the quality of the pentaerythritol polyether polyol is ensured, the production period is short, and alcohol dissolving water is not needed; the preparation method of the invention avoids macromolecular polyether and water from participating in the reaction, which affects the hydroxyl value and viscosity of polyether, and ensures the quality of pentaerythritol polyether polyol; the high-quality polyether polyol described in the patent has a hydroxyl value of 445-.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Adding 0.09kg of crude pentaerythritol polyether, 0.01kg of KOH and 0.3kg of pentaerythritol into a 5L stainless steel experimental kettle, stirring, carrying out pressure reduction and replacement for 3 times, heating to 85 ℃, and adding 0.81kg of PO at 85-95 ℃; curing reaction for 2 hours at 85-95 ℃; reducing the temperature to 70 ℃, adding 0.7kg of pentaerythritol, carrying out pressure reduction and replacement for 3 times, increasing the temperature to 105 ℃, and adding 1.89kg of PO at the temperature of 105-; curing reaction is carried out for 2 hours at the temperature of 105 ℃ and 115 ℃, 50 percent phosphoric acid 0.035kg is added for neutralization, dehydration is carried out to 0.15 percent, and pentaerythritol polyether polyol with the hydroxyl value of 446mgKOH/g and the viscosity of 2350mpa.s/25 ℃ is obtained by filtration.
Example 2
Adding 0.8kg of pentaerythritol crude ether, 0.05kg of KOH and 2kg of pentaerythritol into a 25L stainless steel experimental kettle, stirring, carrying out pressure reduction replacement for 3 times, heating to 85 ℃, and adding 3.975kg of PO at 85-95 ℃; curing reaction for 2 hours at 85-95 ℃; reducing the temperature to 70 ℃, adding 3kg of pentaerythritol, replacing for 3 times under reduced pressure, increasing the temperature to 105 ℃, and adding 9.275kg of PO at the temperature of 105-; curing reaction is carried out for 2 hours at the temperature of 105 ℃ and 115 ℃, 50 percent phosphoric acid is added for neutralization, dehydration is carried out until the mixture reaches 0.15 percent, and pentaerythritol polyether polyol with the hydroxyl value of 450mgKOH/g and the viscosity of 2540mpa.s/25 ℃ is obtained by filtration.
Example 3
Adding 1kg of pentaerythritol crude ether, 0.1kg of KOH and 2kg of pentaerythritol into a 50L stainless steel experimental kettle, stirring, carrying out pressure reduction and replacement for 3 times, heating to 85 ℃, and adding 7.8kg of PO at 85-95 ℃; curing reaction for 2 hours at 85-95 ℃; reducing the temperature to 70 ℃, adding 7kg of pentaerythritol, replacing for 3 times under reduced pressure, increasing the temperature to 105 ℃, and adding 18.2kg of PO at the temperature of 105-; curing reaction is carried out for 2 hours at the temperature of 105 ℃ and 115 ℃, 50 percent phosphoric acid is added for neutralization, dehydration is carried out until the mixture reaches 0.15 percent, and pentaerythritol polyether polyol with the hydroxyl value of 454mgKOH/g and the viscosity of 2680mpa.s/25 ℃ is obtained by filtration.
Claims (5)
1. A preparation method of pentaerythritol polyether polyol is characterized by comprising the following steps: pentaerythritol and PO are added in a two-stage mode, and the preparation method comprises the following steps:
a. adding 20-40% of pentaerythritol with a set amount into a reaction kettle, adding a liquid phase initiator and a catalyst, stirring and heating, adding 25-35% of Propylene Oxide (PO) with a set amount at 85-95 ℃, and carrying out curing reaction for 2 hours (the curing time can only be 2-3 hours;
b. cooling to 70 ℃, adding the rest amount of pentaerythritol into the reaction kettle, heating to 105-;
c. after the reaction is finished, adding 50% phosphoric acid into the reaction system, neutralizing, refining and filtering to obtain the product pentaerythritol polyether polyol.
2. The process for producing pentaerythritol polyether polyol according to claim 1, characterized in that: the set addition ratio of the pentaerythritol to the propylene oxide is 1: (2.60-2.70).
3. The process for producing pentaerythritol polyether polyol according to claim 2, characterized in that: the liquid phase initiator is crude pentaerythritol polyether, and the addition amount of the liquid phase initiator is 30-50% of the feeding amount of the first-stage pentaerythritol.
4. A process for the preparation of pentaerythritol polyether polyols according to claim 3, characterized in that: the catalyst is one of potassium hydroxide, sodium hydroxide or cesium hydroxide.
5. The process for producing pentaerythritol polyether polyol according to claim 4, characterized in that: and in the step c, adding phosphoric acid to neutralize until the pH value is 4.2-5.5.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1922459A (en) * | 1933-08-15 | Their production | ||
| US4100328A (en) * | 1976-06-04 | 1978-07-11 | Basf Wyandotte Corporation | Binder composition and process for preparing pressure molded cellulosic articles |
| JPH05125141A (en) * | 1990-07-13 | 1993-05-21 | Toyo Tire & Rubber Co Ltd | Method for producing rigid polyurethane foam |
| JP2000063474A (en) * | 1998-08-24 | 2000-02-29 | Asahi Glass Co Ltd | Preparation of rigid expanded synthetic resin |
| CN102320936A (en) * | 2011-09-28 | 2012-01-18 | 宜兴市宏博乳化剂有限公司 | Synthesis method for pentaerythritol ethyoxyl or propyl compound |
| CN104086765A (en) * | 2014-07-04 | 2014-10-08 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol used for aliphatic coating |
-
2019
- 2019-12-18 CN CN201911306785.4A patent/CN111057229A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1922459A (en) * | 1933-08-15 | Their production | ||
| US4100328A (en) * | 1976-06-04 | 1978-07-11 | Basf Wyandotte Corporation | Binder composition and process for preparing pressure molded cellulosic articles |
| JPH05125141A (en) * | 1990-07-13 | 1993-05-21 | Toyo Tire & Rubber Co Ltd | Method for producing rigid polyurethane foam |
| JP2000063474A (en) * | 1998-08-24 | 2000-02-29 | Asahi Glass Co Ltd | Preparation of rigid expanded synthetic resin |
| CN102320936A (en) * | 2011-09-28 | 2012-01-18 | 宜兴市宏博乳化剂有限公司 | Synthesis method for pentaerythritol ethyoxyl or propyl compound |
| CN104086765A (en) * | 2014-07-04 | 2014-10-08 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol used for aliphatic coating |
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Application publication date: 20200424 |