CN115873230A - Synthesis method of 1,6-hexanediol polyoxypropylene ether - Google Patents
Synthesis method of 1,6-hexanediol polyoxypropylene ether Download PDFInfo
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- CN115873230A CN115873230A CN202211546138.2A CN202211546138A CN115873230A CN 115873230 A CN115873230 A CN 115873230A CN 202211546138 A CN202211546138 A CN 202211546138A CN 115873230 A CN115873230 A CN 115873230A
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Abstract
The invention relates to a synthetic method of 1,6-hexanediol polyoxypropylene ether, belonging to the technical field of organic compound synthesis. The invention relates to a method for synthesizing 1,6-hexanediol polyoxypropylene ether, which comprises the following steps: 1,6-hexanediol polyoxypropylene ether is used as a raw material, triphenyl aluminum and alkali metal hydroxide compound catalyst are added, and then propylene oxide is used as a reaction monomer to synthesize 1,6-hexanediol polyoxypropylene ether. The triphenyl aluminum has certain alkalinity, so that the ring opening of the epoxypropane reacts with 1,6-hexanediol; meanwhile, as the triphenyl aluminum has the characteristics of steric hindrance and relatively weak alkalinity, the isomerization of the propylene oxide is inhibited, and the production of the propylene alcohol byproduct is reduced.
Description
Technical Field
The invention relates to a method for synthesizing 1,6-hexanediol polyoxypropylene ether, belonging to the technical field of organic compound synthesis.
Background
A synthetic method of 1,6-hexanediol polyoxypropylene ether is an important intermediate of UV light curing, and is mainly used for synthesizing acrylate or methacrylate reactive diluents. Is applied to various fields, such as chemical coatings, 3D printing, mechanical production, automobile manufacturing, electronics, aerospace and the like.
1,6-hexanediol polyoxypropylene ether is prepared by polymerizing 1,6-hexanediol serving as an initiator with propylene oxide under the action of a catalyst, and belongs to one of polyether polyols. The traditional 1,6-hexanediol polyether polyol is usually prepared by using KOH as a catalyst (such as patent CN101225161A and the like), but the products obtained by the method have the defects of wide relative molecular mass distribution, easy isomerization of propylene oxide to form propylene alcohol under alkaline conditions, and reduced relative molecular mass and functionality.
There are also amine catalysts such as alkylamines (for example, U.S. Pat. No. 5, 3268593), and the amine catalysts such as alkylamines include: trimethylamine, triethylamine and the like. The catalyst has lower reaction activity, and the prepared product has poorer appearance and darker color.
The use of Double Metal Cyanide (DMC) catalysts (e.g., CN 107200837A) has also been reported in the literature, and polyether polyols produced by such catalysts have the advantages of narrow relative molecular mass distribution and low unsaturation. However, when preparing polyether polyols having a low molecular weight, there is a disadvantage that the induction period is long and the risk of catalyst deactivation is high. This makes the production process complicated, the quality of the product difficult to control, and the cost increases.
The existing method has the problems of poor distribution of synthesized products, more byproducts, poor color or unstable synthesis process, which reduces the added value and market competitiveness of the products.
Disclosure of Invention
Aiming at the defects of the existing production method, the invention provides a method for synthesizing 1,6-hexanediol polyoxypropylene ether by using a triphenyl aluminum and alkali metal hydroxide compounded catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing 1,6-hexanediol polyoxypropylene ether comprises the following steps: 1,6-hexanediol polyoxypropylene ether is used as a raw material, triphenyl aluminum and alkali metal hydroxide compound catalyst are added, and then propylene oxide is used as a reaction monomer to synthesize 1,6-hexanediol polyoxypropylene ether.
The alkali metal hydroxide is selected from one or more of lithium hydroxide, potassium hydroxide and sodium hydroxide.
The alkali metal hydroxide is selected from potassium hydroxide.
The compounding ratio of the triphenyl aluminum to the alkali metal hydroxide is 100 to 1-100.
The compounding ratio of the triphenyl aluminum to the alkali metal hydroxide is preferably 10.
The dosage of the triphenyl aluminum and alkali metal hydroxide compound catalyst is 0.1 to 10 per thousand of the mass sum of 1,6-hexanediol and propylene oxide.
The dosage of the triphenyl aluminum and the alkali metal hydroxide compound catalyst is 3 per mill of the sum of the mass of 1,6-hexanediol and propylene oxide.
In the synthesis process, the reaction temperature is 90 to 150 ℃, and the reaction pressure is-0.05 to 0.50MPa.
In the synthesis process, the reaction temperature is 110 +/-2 ℃, and the reaction pressure is-0.02 to 0.3MPa.
The 1,6-hexanediol is reacted with propylene oxide, which may be 1.
The 1,6-hexanediol polyoxypropylene ether prepared by the method has the content of propylene alcohol byproducts less than or equal to 10ppm.
The reaction formula of the invention is as follows:
the triphenyl aluminum has certain alkalinity, so that the ring opening of the propylene oxide reacts with 1,6-hexanediol; meanwhile, as the triphenyl aluminum has the characteristics of steric hindrance and relatively weak alkalinity, the isomerization of the propylene oxide is inhibited, and the production of the propylene alcohol byproduct is reduced. The triphenyl aluminum is compounded with the alkali metal hydroxide, the alkali metal hydroxide can improve or supplement the alkalinity of the triphenyl aluminum, and a certain synergistic effect is achieved when 1,6-hexanediol polyoxypropylene ether with larger molecular weight is synthesized.
Compared with the prior art, this patent has following outstanding advantage and positive effect:
1. the produced 1,6-hexanediol polyoxypropylene ether has the propylene alcohol by-product less than 10ppm.
2. The color (Pt-Co) is less than or equal to 20, and the color is lighter.
Specific examples
The analysis method comprises the following steps:
number average molecular weight (Mn) of the product was measured by gel chromatography using Agilent 1200 liquid chromatograph G1328B.
The hydroxyl number is measured according to the phthalic anhydride method of GB/T7383-2007.
The content of the by-product of acrylic alcohol was measured by using high performance liquid chromatography RID-10a, manufactured by Shimadzu corporation, japan.
Preparation of the reaction kettle before implementation: washing a 2.5L high-pressure glass reaction kettle with distilled water for 3 times, drying the reaction kettle, and cooling to normal temperature for later use.
The following examples and comparative examples were carried out with a fixed reaction time.
Example 1
The synthesis of 1,6-hexanediol polyoxypropylene ether with a number average molecular weight of 234 was designed.
Adding 1,6-hexanediol 504.3g into a reaction kettle, wherein the using amount of a triphenyl aluminum and potassium hydroxide compound catalyst (the proportion is 10. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 3ppm; the color (Pt-Co) of the product is 7, the number average molecular weight is 210, and the hydroxyl value is 535.2 mgKOH/g by chemical method.
In examples 2 to 6, a series of examples were conducted by adding 504.3g of 1,6-hexanediol to a reaction vessel, wherein the amount of propylene oxide was 496g, and the ratio and amount of the triphenylaluminum-potassium hydroxide complex catalyst and the reaction temperature were varied. Specific indices are shown in table 1.
Table 1 examples 1-6 statistical tables
Note: catalyst ratio is triphenyl aluminum and potassium hydroxide.
From the comparison of examples 1 to 4 in Table 1, it can be seen that the reaction temperature is 110. + -. 2 ℃ without changing the amount of catalyst and the catalyst ratio (example 2), and the reaction is optimum. If the reaction temperature is lower than 110 ℃ (example 1, 100 +/-2 ℃), the molecular weight of the product does not reach the theoretical value 234 because the reaction is incomplete and the molecular weight does not reach the set value. If the reaction temperature is higher than 110 ℃, the molecular weight of the product can reach a theoretical value of 234, but the higher temperature may cause higher content of the propylene alcohol by-product and darker color of the product.
As can be seen from the comparison of examples 2, 5 and 6 in Table 1, when the catalyst proportion and the reaction temperature are not changed, if the dosage of the catalyst is less than 3 per thousand, the molecular weight of the product is insufficient due to insufficient dosage of the catalyst, so that the reaction is incomplete, and the molecular weight of the product is smaller (example 5); if the amount of the catalyst is more than 3 per mill, the molecular weight of the product is larger due to the larger amount of the catalyst, and the content of the propenol by-product of the product is higher and the color of the product is darker (example 6).
It can be seen that for the product with number average molecular weight of 234 designed and synthesized 1,6-hexanediol polyoxypropylene ether, the product indexes which can be prepared under different conditions have certain difference. I next do an example of a larger number average molecular weight product.
Example 7
The synthesis of 1,6-hexanediol polyoxypropylene ether with a number average molecular weight of 234 was designed.
Adding 1,6-hexanediol 504.3g into a reaction kettle, wherein the using amount of a triphenyl aluminum and potassium hydroxide compound catalyst (the proportion is 30. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 3ppm; the color (Pt-Co) of the product is 7, the number average molecular weight is 226, and the hydroxyl value is 496.3 mgKOH/g through chemical method determination.
Comparing example 2 with example 7, it can be seen that, the higher the content of triphenyl aluminum in the triphenyl aluminum and potassium hydroxide compound catalyst, the catalyst activity tends to be weakened, resulting in a smaller molecular weight of the product.
Example 8
The product of 1,6-hexanediol polyoxypropylene ether with number average molecular weight of 234 was designed and synthesized.
Adding 1,6-hexanediol 504.3g and triphenyl aluminum and potassium hydroxide compound catalyst (the proportion is 5:1) in an amount of 3g into a reaction kettle, vacuumizing, replacing air in the reaction kettle with nitrogen, replacing the nitrogen for 3 times, heating until the materials are completely melted under the condition that the vacuum degree is more than or equal to-0.098 MPa, continuously introducing 496g of propylene oxide, controlling the reaction temperature to be 110 +/-2 ℃, keeping the pressure in the reaction kettle to be 0.30MPa, and keeping the temperature to continue the reaction until the system pressure in the reaction kettle is not reduced any more. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 6ppm; the color (Pt-Co) of the product is 8, the number average molecular weight is 234, and the hydroxyl value measured by a chemical method is 479.1 mgKOH/g.
Comparing example 2 with example 8, it can be seen that, the lower the content of triphenyl aluminum in the triphenyl aluminum and potassium hydroxide compound catalyst, the catalyst activity has an enhancement tendency, which results in the reaching of the product molecular weight, but the content of propylene alcohol by-product of the product is increased due to the enhancement of alkalinity.
Example 9
The synthesis of 1,6-hexanediol polyoxypropylene ether with a number average molecular weight of 234 was designed.
Adding 1,6-hexanediol 504.3g into a reaction kettle, wherein the using amount of a triphenyl aluminum and sodium hydroxide compound catalyst (the proportion is 10. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. The product is analyzed by liquid chromatography: the content of the propylene alcohol by-product is 3ppm; the color (Pt-Co) of the product is 8, the number average molecular weight is 230, and the hydroxyl value is 535.2 mgKOH/g by chemical method.
Comparing example 2 with example 7, it can be seen that, under the condition of consistent ratio of triphenyl aluminum and alkali metal hydroxide compounded catalyst, the molecular weight of the product is smaller because the activity of sodium hydroxide is lower than that of potassium hydroxide catalyst.
By way of example 2, example 7, example 8 and example 9, and by our experimental data, it is found that the preferred ratio of triphenylaluminum to potassium hydroxide combined catalyst is 10.
Example 10:
the synthesis of 1,6-hexanediol polyoxypropylene ether was designed to be a product with a number average molecular weight of about 1000 (i.e., the number of moles of propylene oxide was about 15.3).
Adding 1,6-hexanediol 117.4g, the using amount of a triphenyl aluminum and potassium hydroxide compound catalyst (the proportion is 10. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. The product is analyzed by liquid chromatography: the content of the propylene alcohol by-product is 3ppm; the color (Pt-Co) of the product is 8, the number average molecular weight is 1003, and the hydroxyl value is 111.9 mgKOH/g by chemical method.
Example 11:
the synthesis of 1,6-hexanediol polyoxypropylene ether was designed to be a product with a number average molecular weight of about 2000 (i.e., the number of moles of propylene oxide was about 32.5).
Adding 1,6-hexanediol 58.9g into a reaction kettle, using the dosage of a triphenyl aluminum and potassium hydroxide compound catalyst (the proportion is 10. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. The product is analyzed by liquid chromatography: the content of the propylene alcohol by-products is 3ppm; the color (Pt-Co) of the product is 11, the number average molecular weight is 2001, and the hydroxyl value is 56.2 mgKOH/g by chemical method.
Comparative example 1
Adding 1,6-hexanediol 117.4g and potassium hydroxide 3g (3 ‰), vacuumizing, replacing air in the reaction kettle with nitrogen for 3 times, heating to melt the material completely under the condition that the vacuum degree is more than or equal to-0.096 MPa, continuously introducing 883g of propylene oxide, controlling the reaction temperature at 110 +/-2 ℃, keeping the pressure in the reaction kettle at 0.30MPa, and keeping the temperature to continue the reaction until the system pressure in the reaction kettle is not reduced. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 63ppm; the color (Pt-Co) of the product is 15, the number average molecular weight is 1001, and the hydroxyl value is 112.3mgKOH/g by chemical method.
Compared with the example 10, the content of the propenol byproduct is higher and the color of the product is darker in the comparative example 1, and the catalyst adopted in the patent has certain advantages.
Comparative example 2
Adding 1,6-hexanediol 117.4g and DMC 1.0g (60 ppm, the optimal dosage of the catalyst), vacuumizing, replacing air in the reaction kettle with nitrogen, replacing the nitrogen for 3 times, heating until the materials are completely melted under the condition that the vacuum degree is more than or equal to-0.096 MPa, continuously introducing 883g of propylene oxide, controlling the reaction temperature to be 110 +/-2 ℃, keeping the pressure in the reaction kettle to be about 0.30MPa, and continuing the reaction until the system pressure in the reaction kettle is not reduced any more. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 10ppm; the color (Pt-Co) of the product is 12, the number average molecular weight is 890, and the hydroxyl value is 125.6mgKOH/g by chemical method.
Comparative example 2 in contrast to example 10, multiple activations of the DMC were required during the product synthesis, probably due to the DMC synthesis process requiring a starter of larger molecular weight, while 1,6-hexanediol had a smaller molecular weight. Comparative example 2 is similar to the product of example 10 in color but appears to have a faint pink color in appearance, which is characteristic of DMC catalyst products and is due to the Co element in the DMC catalyst, and it can be seen that the catalyst used in this patent has certain excellent characteristics.
Comparative example 3
Adding 1,6-hexanediol 117.4g and triethylamine 3.0g into a reaction kettle, vacuumizing, replacing air in the reaction kettle with nitrogen for 3 times, heating until the materials are completely melted under the condition that the vacuum degree is more than or equal to-0.096 MPa, continuously introducing 883g of propylene oxide, controlling the reaction temperature to be 110 +/-2 ℃, and keeping the pressure in the reaction kettle to be 0.30MPa, and continuing the reaction until the system pressure in the reaction kettle is not reduced any more. After the reaction is finished, cooling to 100 ℃, vacuum degassing, and discharging to obtain a finished product. And (3) analyzing a product by liquid chromatography: the content of the propylene alcohol by-product is 10ppm; the color (Pt-Co) of the product is 23, the number average molecular weight is 950, and the hydroxyl value is 118.5mgKOH/g by chemical method.
In comparison with example 10, the molecular weight of the product prepared by the triethylamine catalyst is lower, which is probably caused by weaker activity of the triethylamine catalyst. In addition, the product prepared by the triethylamine has darker color. In addition, the product prepared by the amine catalyst has certain special taste of the amine product, and the application field of the product is influenced. Therefore, the catalyst adopted by the method has certain excellent characteristics.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (9)
1. A method for synthesizing 1,6-hexanediol polyoxypropylene ether is characterized by comprising the following steps: 1,6-hexanediol polyoxypropylene ether is used as a raw material, a triphenyl aluminum and alkali metal hydroxide compound catalyst is added, and propylene oxide is used as a reaction monomer to synthesize 1,6-hexanediol polyoxypropylene ether.
2. The method of claim 1 for synthesizing 1,6-hexanediol polyoxypropylene ether, wherein: the alkali metal hydroxide is selected from one or more of lithium hydroxide, potassium hydroxide and sodium hydroxide.
3. The method of claim 2, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: the alkali metal hydroxide is selected from potassium hydroxide.
4. The method of claim 1, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: the compounding ratio of the triphenyl aluminum to the alkali metal hydroxide is 100 to 1-100.
5. The method of claim 4, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: the compounding ratio of the triphenyl aluminum to the alkali metal hydroxide is 10:1.
6. the method of claim 1, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: the dosage of the triphenyl aluminum and the alkali metal hydroxide compound catalyst is 0.1 to 10 per thousand of the mass sum of 1,6-hexanediol and propylene oxide.
7. The method of claim 6, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether comprises: the dosage of the triphenyl aluminum and alkali metal hydroxide compounded catalyst is 3 per mill of the mass sum of the dosages of 1,6-hexanediol and propylene oxide.
8. The method of claim 1, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: in the synthesis process, the reaction temperature is 90 to 150 ℃, and the reaction pressure is-0.05 to 0.50MPa.
9. The method of claim 8, wherein the synthesis of 1,6-hexanediol polyoxypropylene ether is as follows: in the synthesis process, the reaction temperature is 110 +/-2 ℃, and the reaction pressure is-0.02 to 0.3MPa.
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