CN115490844A - Preparation method of trimethylolethane polyether polyol - Google Patents
Preparation method of trimethylolethane polyether polyol Download PDFInfo
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- CN115490844A CN115490844A CN202211323824.3A CN202211323824A CN115490844A CN 115490844 A CN115490844 A CN 115490844A CN 202211323824 A CN202211323824 A CN 202211323824A CN 115490844 A CN115490844 A CN 115490844A
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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
- C08G65/2651—Alkaline earth 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
- C08G65/2696—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
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Abstract
The invention discloses a preparation method of trimethylolethane polyether polyol, which comprises the following steps: feeding: adding the trimethylolethane, the catalyst and the solvent into a reaction kettle in sequence, and starting stirring. Vacuumizing and replacing nitrogen for three times until the pressure in the kettle is less than or equal to-0.098 MPa, and then heating. Reaction: introducing one or two mixtures of epoxypropane and epoxyethane into the reaction kettle, and heating to the reaction temperature under the action of a catalyst to carry out ring-opening polymerization reaction under the reaction pressure of-0.10-0.4 MPa. Then keeping the temperature and curing until the pressure does not change. Solvent removal: after the curing is finished, the solvent is removed under negative pressure at a certain temperature until no solvent comes out. And (3) filtering and discharging: cooling to below 80 ℃, and filtering out the catalyst to obtain the trimethylolethane polyether polyol. The method has high feasibility, is beneficial to industrial production, and the obtained product has good performance.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a preparation method of trimethylolethane polyether polyol.
Background
Trimethylolethane is also called 1, 1-tris (hydroxymethyl) ethane and 2-methyl-2-hydroxymethyl-1, 3-propanediol, abbreviated as TME. Propionaldehyde and formaldehyde are generally used as raw materials, aldol condensation reaction is carried out under the action of a basic catalyst, and the condensation product and the formaldehyde are subjected to cross-Cannizzaro reaction or direct catalytic hydrogenation to prepare the catalyst. The structural formula is as follows:
the high hydroxyl content of a neopentyl structure contained in the molecule of the Trimethylolethane (TME) endows the Trimethylolethane (TME) with better application performance. TME is mainly used as raw materials of alkyd resin, polyurethane resin, hard polyurethane plastic, polyurethane coating and high-grade paint and coating, and is also an important intermediate of epoxy resin, explosive and special chemicals. The esters of TME are mainly used for synthesizing a lubricant, a plasticizer and an emulsifier, can also be used for preparing the plasticizer, a surfactant, a high-grade lubricant, a liquid fuel additive, a reactive diluent, synthetic leather and a heat-insulating material, and can also be used as a coating agent of titanium dioxide. In addition, TME is a novel solid-solid phase transition heat storage material. In the field of polyurethane, polyether polyol synthesized by trimethylolethane is applied to products such as polyurethane coating, elastomer, foamed plastic and the like, and has excellent heat resistance, light resistance, hydrolysis resistance and oxidation resistance.
At present, few reports on trimethylolethane polyether polyol are reported in China, and a preparation method of trifunctional polyurethane acrylate based on trimethylolethane (propane) is disclosed in patent CN 105859584B, wherein trimethylolethane or trimethylolpropane is reacted with ethylene oxide or propylene oxide under the action of a catalyst to prepare trihydroxy polyether, and then the trihydroxy polyether is reacted with isocyanate ethyl acrylate to prepare the trifunctional polyurethane acrylate. The preparation process of trihydroxymethyl ethane polyether includes the reaction of dropping epoxy ethane or epoxy propane at 155-165 deg.c under the action of sodium formate as catalyst to prepare polyether, and the post treatment with acid clay. The reaction temperature of the method is 155-165 ℃, the melting point of the trimethylolethane is about 200 ℃, and at the reaction temperature, the trimethylolethane is still solid and cannot be stirred, so that the method is not beneficial to reaction. Adsorbing and filtering with acid clay to obtain K in polyether + /Na + High content and large usage of acid clay.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the trimethylolethane polyether polyol, which has high feasibility, is beneficial to industrial production and has good product performance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of trimethylolethane polyether polyol comprises the following steps:
s1, feeding: adding the trimethylolethane, the catalyst and the solvent into a reaction kettle in sequence, and starting stirring. Vacuumizing and replacing nitrogen for three times until the pressure in the kettle is less than or equal to-0.098 MPa, and then heating.
S2, reaction: introducing one or two mixtures (hereinafter referred to as epoxy) of propylene oxide and ethylene oxide into a reaction kettle, and heating to the reaction temperature to carry out ring-opening polymerization reaction under the action of a catalyst, wherein the reaction pressure is-0.10-0.4 MPa. Then keeping the temperature and curing until the pressure does not change.
S3, desolventizing: after the ripening is finished, the solvent is removed under negative pressure at a certain temperature until no solvent comes out.
S4, filtering and discharging: cooling to below 80 deg.c, and filtering with wire net to obtain trihydroxymethyl ethane polyether polyol.
Further, the solvent is any one of acetone, ethyl acetate and dioxane, and the mass of the solvent is 50-150% of that of the trimethylolethane.
The molar ratio of the trimethylolethane to the epoxy is 1.
The catalyst is a magnesium-aluminum composite metal oxide, and the mass of the catalyst is 1-10 per mill of the total mass of the trimethylolethane and the epoxy.
The Mg/Al ratio in the magnesium-aluminum composite metal oxide catalyst is 3/1, 2/1 or 1/1.
The reaction temperature of the step S2 is 100-150 ℃.
The desolventizing temperature of the step S3 is 100-140 ℃.
The invention has the following beneficial effects:
(1) The solvent is selected to dissolve the trimethylolethane, so that the problem that the trimethylolethane has high melting point and cannot be stirred is solved, the industrial production reaction is facilitated, and the obtained polyether has good distributivity.
(2) The magnalium composite metal oxide catalyst is used as a solid base catalyst, has high activity and is easy to separate, and the synthesized polyether polyol does not need post-treatment and only needs to be filtered out. The process time is saved.
(3) The prepared trimethylolethane polyether polyol has high purity, good color and stable property, is applied to products such as polyurethane coating, elastomer, foamed plastic and the like, and has excellent heat resistance, light resistance, hydrolysis resistance and oxidation resistance.
The method has high feasibility, is beneficial to industrial production, and the obtained product has good performance.
Detailed Description
Example 1
To the reactor was added 120g trimethylolethane, 100g ethyl acetate, 1.2g magnesium aluminum composite metal oxide catalyst (Mg/Al = 3/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 500g of ethylene oxide is dripped to carry out ring-opening polymerization reaction, the reaction temperature is controlled to be 120-140 ℃, and the pressure is less than 0.4MPa. After the dropping of the ethylene oxide is finished, the mixture is cured for 1 hour at the temperature of 145 ℃. After the curing is finished, the solvent is removed under the negative pressure at the temperature of 110-130 ℃ until no solvent comes out. Then cooling to 80 ℃, filtering the catalyst by using an iron wire net, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 272mgKOH/g. Chroma: no. 12 (Pt-Co units).
Example 2
To the reactor was added 60g trimethylolethane, 80g dioxane, 2.5g magnesium aluminum composite metal oxide catalyst (Mg/Al = 1/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 800g of propylene oxide is dripped to carry out ring-opening polymerization reaction, the reaction temperature is controlled to be 110-120 ℃, and the pressure is less than 0.4MPa. After the dropping of the epoxypropane is finished, keeping the temperature at 125 ℃ for curing for 2h. After the curing is finished, the solvent is removed at the temperature of 120-140 ℃ under negative pressure until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 101mgKOH/g. Chroma: no. 8 (Pt-Co units).
Example 3
To the reactor was added 120g trimethylolethane, 120g acetone, 3g magnesium aluminum composite metal oxide catalyst (Mg/Al = 3/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 1000g of propylene oxide and ethylene oxide mixture (PO/EO = 7/3) is added dropwise to carry out ring-opening polymerization reaction, the reaction temperature is controlled to be 110-120 ℃, and the pressure is controlled to be less than 0.4MPa. After the dropping of the epoxypropane and epoxyethane mixture is finished, keeping the temperature at 125 ℃ and curing for 1.5h. After the curing is finished, the solvent is removed at 100-120 ℃ under negative pressure until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 153mgKOH/g. Chroma: no. 15 (Pt-Co units).
Example 4
To the reactor was added 120g trimethylolethane, 100g ethyl acetate, 1.5g magnesium aluminum composite metal oxide catalyst (Mg/Al = 2/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 500g of propylene oxide is added dropwise for ring-opening polymerization reaction, the reaction temperature is controlled to be 110-120 ℃, and the pressure is less than 0.4MPa. After the dropping of the epoxypropane is finished, keeping the temperature at 125 ℃ and curing for 1h. After the curing is finished, the solvent is removed under the negative pressure at the temperature of 110-130 ℃ until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated with hydroxyl value by a chemical method (GB/T12008.3-2009): 278mgKOH/g. Chroma: no. 12 (Pt-Co units).
Example 5
To the reactor was added 60g trimethylolethane, 60g ethyl acetate, 2g magnesium aluminum composite metal oxide catalyst (Mg/Al = 3/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 800g of propylene oxide is dripped to carry out ring-opening polymerization reaction, the reaction temperature is controlled to be 110-120 ℃, and the pressure is less than 0.4MPa. After the dropping of the epoxypropane is finished, keeping the temperature at 125 ℃ for curing for 2h. After the curing is finished, the solvent is removed under the negative pressure at the temperature of 110-130 ℃ until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 99.5mgKOH/g. Chroma: no. 8 (Pt-Co units).
Example 6
To the reactor was added 120g trimethylolethane, 100g acetone, 3.8g magnesium aluminum composite metal oxide catalyst (Mg/Al = 1/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 1200g of propylene oxide and ethylene oxide mixture (PO/EO = 5/5) is started to be dripped for ring-opening polymerization, the reaction temperature is controlled to be 110-120 ℃, and the pressure is controlled to be less than 0.4MPa. After the dropping of the epoxypropane and epoxyethane mixture is finished, keeping the temperature at 125 ℃ and curing for 1.5h. After the curing is finished, the solvent is removed at 100-120 ℃ under negative pressure until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 129mgKOH/g. Chroma: no. 12 (Pt-Co units).
Example 7
To the kettle were added 60g trimethylolethane, 60g epoxy hexacyclic, 3.2g magnesium aluminum composite metal oxide catalyst (Mg/Al = 2/1). The air in the kettle is replaced by nitrogen for three times, then the temperature is raised to 110 ℃, 700g of propylene oxide and ethylene oxide mixture (PO/EO = 3/7) is added dropwise to carry out ring-opening polymerization reaction, the reaction temperature is controlled to be 110-120 ℃, and the pressure is controlled to be less than 0.4MPa. After the dropping of the epoxypropane and epoxyethane mixture is finished, preserving heat and curing for 1.5h at 125 ℃. After the curing is finished, the solvent is removed at 120-140 ℃ under negative pressure until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 112mgKOH/g. Chroma: no. 14 (Pt-Co units).
Example 8
To the reactor was added 60g trimethylolethane, 60g ethyl acetate, 3.2g magnesium aluminum composite metal oxide catalyst (Mg/Al = 3/1). Replacing the air in the kettle with nitrogen for three times, heating to 110 ℃, starting to dropwise add 600g of propylene oxide, controlling the reaction temperature to be 110-120 ℃, controlling the pressure to be less than 0.4MPa, and preserving heat and aging at 125 ℃ for 2 hours after the dropwise addition is finished. Then 900g of epoxy ethane is dripped, the reaction temperature is controlled to be 120-130 ℃, the pressure is less than 0.4MPa, and after the dripping is finished, the heat preservation and curing are carried out for 1 hour at 135 ℃. After the curing is finished, the solvent is removed at 110-130 ℃ under negative pressure until no solvent comes out. Then cooling to 80 ℃, filtering and discharging to obtain the trimethylolethane polyether polyol.
The product is titrated by a chemical method (GB/T12008.3-2009) to have a hydroxyl value: 55.3mgKOH/g. Chroma: no. 18 (Pt-Co units).
The above description is provided for the purpose of describing the preferred embodiments of the present invention in more detail, and it should not be construed that the embodiments of the present invention are limited to the description above, and it will be apparent to those skilled in the art that the present invention can be implemented in many different forms without departing from the spirit and scope of the present invention.
Claims (9)
1. A preparation method of trimethylolethane polyether polyol is characterized by comprising the following steps:
s1, feeding: sequentially adding the trimethylolethane, the catalyst and the solvent into a reaction kettle, and starting stirring; vacuumizing and replacing nitrogen until the pressure in the kettle is less than or equal to-0.098 MPa, and then heating;
s2, reaction: introducing one or two mixtures of epoxypropane and epoxyethane into a reaction kettle, and heating to the reaction temperature under the action of a catalyst to carry out ring-opening polymerization reaction under the reaction pressure of-0.10-0.4 MPa; then preserving heat and curing until the pressure does not change;
s3, desolventizing: after the ripening is finished, carrying out negative pressure desolventizing at a certain temperature until no solvent is removed;
s4, filtering and discharging: cooling to below 80 deg.c, and filtering with wire net to obtain trihydroxymethyl ethane polyether polyol.
2. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: in the step S1, the nitrogen is vacuumized and replaced for three times until the pressure in the kettle is less than or equal to-0.098 MPa.
3. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: the molar ratio of the trimethylolethane to the epoxy is 1.
4. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: the solvent is any one of acetone, ethyl acetate and dioxane, and the mass of the solvent is 50-150% of that of the trimethylolethane.
5. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: the catalyst is a magnesium-aluminum composite metal oxide, and the mass of the catalyst is 1-10 per mill of the total mass of the trimethylolethane and the epoxy.
6. The method of producing a trimethylolethane polyether polyol according to claim 5, wherein: the Mg/Al ratio in the magnesium-aluminum composite metal oxide of the catalyst is 3/1, 2/1 or 1/1.
7. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: the reaction temperature of the step S2 is 100-150 ℃.
8. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: the desolventizing temperature of the step S3 is 100-140 ℃.
9. The method of producing a trimethylolethane polyether polyol according to claim 1, wherein: in the step S4, the catalyst is filtered out by using an iron wire.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315225A (en) * | 2000-03-27 | 2001-10-03 | 北京化工大学 | Compound Mg-Al oxide catalyst for alkoxylation reaction and its preparing process |
| JP2002241490A (en) * | 2001-02-15 | 2002-08-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Production method of polyether |
| CN105859584A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | Tri-functionality urethane acrylate based on trimethylolethane/trimethylolpropane and preparation method and application of tri-functionality urethane acrylate |
| CN110669213A (en) * | 2019-10-22 | 2020-01-10 | 武汉奥克特种化学有限公司 | Preparation method of bisphenol A polyether |
| CN113234217A (en) * | 2021-05-27 | 2021-08-10 | 万华化学集团股份有限公司 | Preparation method of solid base catalyst and application of solid base catalyst in continuous production of polyether polyol |
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2022
- 2022-10-27 CN CN202211323824.3A patent/CN115490844A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315225A (en) * | 2000-03-27 | 2001-10-03 | 北京化工大学 | Compound Mg-Al oxide catalyst for alkoxylation reaction and its preparing process |
| JP2002241490A (en) * | 2001-02-15 | 2002-08-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Production method of polyether |
| CN105859584A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | Tri-functionality urethane acrylate based on trimethylolethane/trimethylolpropane and preparation method and application of tri-functionality urethane acrylate |
| CN110669213A (en) * | 2019-10-22 | 2020-01-10 | 武汉奥克特种化学有限公司 | Preparation method of bisphenol A polyether |
| CN113234217A (en) * | 2021-05-27 | 2021-08-10 | 万华化学集团股份有限公司 | Preparation method of solid base catalyst and application of solid base catalyst in continuous production of polyether polyol |
Non-Patent Citations (1)
| Title |
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| XIAO-SHUANG FENG ET AL.: ""Toward an Easy Access to Dendrimer-like Poly(ethylene oxide)s"", 《J. AM. CHEM. SOC》, vol. 127, no. 31, pages 10956 - 10966, XP055154885, DOI: 10.1021/ja0509432 * |
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