Preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether

Abstract

The invention discloses a preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether, which comprises the following steps: 1) taking isomeric alcohol as an initiator and an alkaline earth metal complex as a catalyst, introducing epoxypropane for reaction, and then introducing ethylene oxide for reaction to obtain a crude product of isomeric alcohol polyoxypropylene polyoxyethylene ether; and 2) carrying out adsorption refining on the isomeric alcohol alkoxylate crude product to obtain the isomeric alcohol polyoxypropylene polyoxyethylene ether. The preparation method has the remarkable advantages of being high in conversion rate, low in production cost and the like, the reaction speed is obviously higher than that of a traditional base catalysis process, and the prepared isomeric alcohol polyoxypropylene polyoxyethylene ether is clear and transparent in appearance, good in compatibility, narrow in relative molecular mass distribution, extremely low in residual alcohol content, higher in surface activity and suitable for industrial production. The cleaning agent can be effectively applied to the fields of textile assistants, industrial and commercial cleaning, leather papermaking and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to polyether polyols, in particular to a preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether. BACKGROUND

[0002] Isomeric alcohol alkoxylate, also known as isomeric alcohol polyoxypropylene polyoxyethylene ether, is prepared by reacting isomeric alcohol with propylene oxide and ethylene oxide under the action of different types of catalysts such as acid, base and alkaline earth metal complex. Isomeric alcohol alkoxylate is widely used in daily cleaning, textile auxiliaries, industrial and commercial cleaning and other fields, mainly used as low-temperature cleaning agent in high-end cleaning field, and also commonly used as wetting penetrant, refining agent, emulsifier, leather degreasing agent, etc.

[0003] Isomeric alcohol polyoxypropylene polyoxyethylene ether is a kind of surfactant with excellent comprehensive performance, which has better wetting penetration, gel performance and low-temperature fluidity than conventional fatty alcohol polyoxyethylene ether (AEO), especially better oil removal cleaning effect at low temperature. The narrower the relative molecular mass distribution of isomeric alcohol polyoxypropylene polyoxyethylene ether, the lower the content of free alcohol and high molecular weight components, and the more excellent the surface activity of the product.

[0004] Patent CN103387486B discloses a preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether, which is prepared by condensation reaction of isomeric alcohol with propylene oxide and ethylene oxide catalyzed by alkaline catalysts such as calcium hydroxide and barium hydroxide. Although this process improves the fluidity of the product to some extent, the product is turbid at low temperature, the molecular weight distribution of the product is wide, the oil removal efficiency and gel performance are reduced, which is not conducive to the downstream application of the product, and the reaction speed of isomeric alcohol with propylene oxide is slow under alkaline catalyst system, the PO curing time is long, and the production efficiency is reduced. Patent CN117624579A discloses a narrow-distribution isomeric alcohol polyoxyethylene ether and a preparation method thereof, which adopts a two-step process. First, an intermediate is obtained by reacting isomeric alcohol with ethylene oxide catalyzed by boron trifluoride ether, and then the isomeric alcohol polyoxyethylene ether is prepared by using conventional alkaline catalysts such as potassium hydroxide. This process reduces the free alcohol content by vacuum distillation, although the molecular weight distribution is narrowed, but there are still a large number of low-EO grafted polyether products, which affects the comprehensive performance of the product, and the process is complicated and the production cost is high. SUMMARY

[0005] The present application aims to provide a preparation method of isomeric alcohol alkoxylate, which has excellent low-temperature oil removal performance, good wetting penetration, low-temperature fluidity and other properties, and can effectively replace alkylphenol polyoxyethylene ether.

[0006] Another object of the present application is to provide a preparation method of isomeric alcohol alkoxylate, and a new synthesis system is proposed, which has a simple production process and higher production efficiency compared with the traditional base catalytic system.

[0007] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0008] A preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether, comprising the following steps:

[0009] (1) taking isomeric alcohol as a starting agent, and introducing propylene oxide into the reaction system under the catalysis of an alkaline earth metal complex until the reaction pressure no longer decreases;

[0010] (2) introducing ethylene oxide into the reaction system until the reaction pressure no longer decreases, to obtain a crude product of isomeric alcohol polyoxypropylene polyoxyethylene ether;

[0011] (3) adding an adsorbent to the crude product of isomeric alcohol polyoxypropylene polyoxyethylene ether to obtain isomeric alcohol polyoxypropylene polyoxyethylene ether.

[0012] Further, the isomeric alcohol in step (1) includes at least one of isooctanol, isononyl alcohol, isodecanol, isoundecanol, 2-butyl-1-octanol, and isotridecanol.

[0013] Further, the alkaline earth metal complex catalyst in step (1) is prepared by reacting an alkaline earth metal compound and a polyether polyol, which can be prepared according to CN116102728B. Specifically, the alkaline earth metal compound includes one or more of magnesium oxide, magnesium hydroxide, magnesium carboxylate, calcium oxide, calcium hydroxide, calcium carboxylate, barium oxide, barium hydroxide, strontium oxide, and strontium hydroxide; and the polyether polyol is polyoxyethylene ether, including at least one of polyethylene glycol (preferably having a molecular weight of 200-1000 g / mol) and diethylene glycol monoethyl ether. The alkaline earth metal complex catalyst described in the present application is the alkaline earth metal catalyst described in CN116102728B (which is incorporated herein by reference in its entirety).

[0014] In some preferred embodiments, the preparation process of the alkaline earth metal complex catalyst can include:

[0015] (1) under an inert atmosphere, an alkaline earth metal compound is added to a polyether polyol, and the temperature is controlled at 80-150°C (preferably 90-120°C, for example, 100°C, 110°C, 130°C, or 140°C, etc.), and the reaction is stirred;

[0016] (2) reducing the temperature to 10-90℃ (preferably 20-50℃, such as 30℃, 40℃, 60℃, 70℃ or 80℃, etc.), dropping inorganic oxyacid (such as phosphoric acid, nitric acid or sulfuric acid, preferably sulfuric acid) into the reaction solution of step (1), stirring the reaction to obtain the alkaline earth metal-polyether polyol complex catalyst.

[0017] In step (1), the weight ratio of the alkaline earth metal compound to the polyether polyol is 0.05:1-1:1, preferably 0.1:1-1:1.

[0018] In step (1), the stirring reaction time is 2-6h.

[0019] In step (2), the molar ratio of the alkaline earth metal compound to the inorganic oxyacid is 10:1-1:1, preferably 4:1-1.2:1.

[0020] In step (2), the stirring reaction time is 1-24h.

[0021] In step (2), before obtaining the catalyst, vacuum distillation is performed to remove impurities, the conditions of the vacuum distillation being: temperature 120-240℃, pressure -0.05MPa to -0.098MPa, time 1-8h.

[0022] Further, the amount of the alkaline earth metal complex catalyst added in step (1) is 0.002-0.5% of the total mass of the isomeric alcohol and the epoxide, preferably 0.01-0.2%.

[0023] Specifically, the epoxide includes ethylene oxide and propylene oxide.

[0024] Further, step (1) specifically is that the isomeric alcohol and the alkaline earth metal complex are placed in a reactor, dehydrated after being replaced by inert gas for multiple times, and then propylene oxide is introduced after being heated to the reaction temperature.

[0025] Specifically, the inert gas is nitrogen, and the number of times of replacement is preferably 3-5 times.

[0026] Specifically, the dehydration temperature is 85-95℃, and the dehydration time is 1-2.5h, until the water content of the system is less than 0.5wt%.

[0027] Further, the reaction temperature in step (1) is 135-175℃, preferably 140-160℃.

[0028] Further, the molar ratio of the isomeric alcohol, propylene oxide and ethylene oxide is 1:0.5-8:2-15, preferably 1:1.5-5:3-10.

[0029] Further, the reaction temperature after the step (2) is 135-175℃, preferably 140-160℃ after the introduction of the ethylene oxide.

[0030] Further, the reaction temperature after the step (2) is consistent with or inconsistent with the reaction temperature after the introduction of the propylene oxide, preferably the reaction temperature is consistent.

[0031] Further, the adsorbent in the step (3) is one or more of diatomite, aluminum silicate, magnesium silicate, activated carbon, and aluminum oxide.

[0032] Further, the adsorbent is used in an amount of 0.02-3wt% of the mass of the crude isomeric alcohol polyoxypropylene polyoxyethylene ether product; preferably, the adsorption process is carried out at a temperature of 75-105℃ for 1-3h. The adsorption is to remove calcium ions, magnesium ions, and other salts, and also to remove high molecular weight PEG or other high molecular polyether components generated in the reaction, so as to reduce the turbidity of the product and improve the appearance of the product.

[0033] Further, the adsorption process is accompanied by stirring, and the stirring rate is preferably 800-1500rpm, so as to promote the adsorption and make the adsorption more complete.

[0034] Further, the adsorbent is removed by filtration after the adsorption, to obtain the isomeric alcohol polyoxypropylene polyoxyethylene ether.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] (1) The present application provides a preparation method of isomeric alcohol polyoxypropylene polyoxyethylene ether, which uses a new type of catalytic system of alkaline earth metal complex catalyst, and combines with a subsequent impurity removal process. The isomeric alcohol ether product prepared by the method has excellent comprehensive performance, good biocompatibility, and can be used to replace traditional alkyl phenol polyoxyethylene ether.

[0037] (2) The production process of the present application is simple, and solves the problems of slow reaction speed, long maturation time, and the need for acid neutralization of the product in the traditional alkali catalysis of isomeric alcohol and propylene oxide reaction. The production efficiency is higher under the process of the present application, and the production cost is reduced.

[0038] (3) The isomeric alcohol polyoxypropylene polyoxyethylene ether prepared by the present application has a narrower molecular weight distribution, better low-temperature oil removal and defatting performance, good low-temperature clear appearance and flowability, and strong product applicability, and can be applied to high-end industrial and commercial cleaning, textile auxiliaries, and papermaking deinking and other fields. DETAILED DESCRIPTION

[0039] The present application will be further described below through specific examples, and the examples of the present application are only used to illustrate the present application, and do not limit the scope of the present application.

[0040] Calcium-based alkaline earth metal complex catalyst 1: prepared according to Example 3 of Chinese patent CN116102728B;

[0041] Calcium-based alkaline earth metal complex catalyst 2: prepared according to Example 5 of Chinese patent CN116102728B;

[0042] Magnesium-based alkaline earth metal complex catalyst: prepared according to Example 1 of Chinese patent CN116102728B;

[0043] Strontium-based alkaline earth metal complex catalyst: prepared according to Example 4 of Chinese patent CN116102728B.

[0044] Example 1

[0045] Into a self-suction stirring reaction kettle, 344 g of isooctanol, 1.5 g of calcium-based alkaline earth metal complex catalyst 1 were added, the reaction kettle was closed and replaced with nitrogen three times, dehydrated at 85°C under negative pressure for 1 h, then heated to 140°C and 16 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 150°C, and 291 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 349 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70°C, and the product was discharged to obtain a crude product of isooctanol alkoxylate.

[0046] Into a three-necked flask, 850 g of isooctanol alkoxylate crude product, 17 g of magnesium silicate were added, the adsorption process was controlled at a temperature of 75°C, the stirring speed was 1000 rpm, and the adsorption control time was 1.5 h, then the mixture was added to a positive pressure filter to obtain isooctanol alkoxylate.

[0047] Example 2

[0048] Into a self-suction stirring reaction kettle, 187 g of isononyl alcohol, 0.3 g of calcium-based alkaline earth metal complex catalyst 2 were added, the reaction kettle was closed and replaced with nitrogen three times, dehydrated at 85°C under negative pressure for 1 h, then heated to 145°C and 20 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 155°C, and 280 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 513 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70°C, and the product was discharged to obtain a crude product of isononyl alcohol alkoxylate.

[0049] Into a three-necked flask, 800 g of isononyl alcohol alkoxylate crude product, 1.6 g of diatomite were added, the adsorption process was controlled at a temperature of 75°C, the stirring speed was 1000 rpm, and the adsorption control time was 2 h, then the mixture was added to a positive pressure filter to obtain isononyl alcohol alkoxylate.

[0050] Example 3

[0051] Into a self-priming stirred reaction vessel was added 236 g of isononyl alcohol, 1.0 g of magnesium-based alkaline earth metal complex catalyst, the reaction vessel was closed and purged with nitrogen three times, dehydrated at 85 °C under negative pressure for 1.5 h, then heated to 150 °C and 25 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 160 °C, and 450 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 289 g of ethylene oxide was introduced until the pressure in the reaction vessel did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain a crude product of isononyl alcohol alkoxylate.

[0052] Into a three-necked flask was added 850 g of crude isononyl alcohol alkoxylate, 8.5 g of magnesium silicate, the adsorption process was controlled at a temperature of 85 °C, the stirring speed was 1000 rpm, and the adsorption control time was 1.5 h, then the mixture was added to a positive pressure filter to obtain isononyl alcohol alkoxylate.

[0053] Example 4

[0054] Into a self-priming stirred reaction vessel was added 261 g of 2-butyl-1-octanol, 1.5 g of strontium-based alkaline earth metal complex catalyst, the reaction vessel was closed and purged with nitrogen three times, dehydrated at 95 °C under negative pressure for 1 h, then heated to 140 °C and 20 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 155 °C, and 224 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 495 g of ethylene oxide was introduced until the pressure in the reaction vessel did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain a crude product of isododecanol alkoxylate.

[0055] Into a three-necked flask was added 800 g of crude isododecanol alkoxylate, 12.0 g of aluminum silicate, the adsorption process was controlled at a temperature of 95 °C, the stirring speed was 1000 rpm, and the adsorption control time was 1 h, then the mixture was added to a positive pressure filter to obtain isododecanol alkoxylate.

[0056] Example 5

[0057] Into a self-priming stirred reaction vessel was added 336 g of isotridecanol, 0.6 g of calcium-based alkaline earth metal complex catalyst 1, the reaction vessel was closed and purged with nitrogen three times, dehydrated at 95 °C under negative pressure for 1 h, then heated to 150 °C and 15 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 160 °C, and 131 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 518 g of ethylene oxide was introduced until the pressure in the reaction vessel did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain a crude product of isotridecanol alkoxylate.

[0058] Into a three-necked flask, 800 g of isomeric tridecanol alkoxylate crude product, 0.8 g of magnesium silicate was added, the adsorption process was controlled at 100 °C, the stirring speed was 1000 rpm, the adsorption control time was 1.5 h, then the mixture was added to a pressure filter to obtain isomeric tridecanol alkoxylate.

[0059] Comparative Example 1

[0060] Into a self-suction stirring reaction kettle, 344 g of isooctanol, 2.0 g of sodium hydroxide were added, the reaction kettle was sealed, replaced with nitrogen three times, dehydrated at 85 °C under negative pressure for 1 h, then heated to 140 °C and 16 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 150 °C, and 291 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 349 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain isooctanol alkoxylate.

[0061] Comparative Example 2

[0062] Into a self-suction stirring reaction kettle, 187 g of isononyl alcohol, 5.0 g of KOH aqueous solution (50 wt%) were added, the reaction kettle was sealed, replaced with nitrogen three times, dehydrated at 85 °C under negative pressure for 1 h, then heated to 145 °C and 20 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 155 °C, and 280 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 513 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain isononyl alcohol alkoxylate.

[0063] Comparative Example 3

[0064] Into a self-suction stirring reaction kettle, 261 g of 2-butyl-1-octanol, 6.0 g of sodium methoxide methanol solution (30%) were added, the reaction kettle was sealed, replaced with nitrogen three times, dehydrated at 95 °C under negative pressure for 1 h, then heated to 140 °C and 20 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 155 °C, and 224 g of propylene oxide was continuously introduced, until the propylene oxide was completely reacted (the pressure did not decrease), 495 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70 °C, and the product was discharged to obtain isomeric dodecanol alkoxylate.

[0065] Comparative Example 4

[0066] Into a self-suction stirring reaction kettle, 261 g of 2-butyl-1-octanol, 1.5 g of strontium-based alkaline earth metal complex catalyst were added, the reaction kettle was closed and replaced with nitrogen three times, dehydrated at 95℃ under negative pressure for 1 h, then heated to 140℃ and 20 g of propylene oxide was introduced, after the reaction was activated, the temperature was increased to 155℃, and 224 g of propylene oxide was continuously introduced, after the propylene oxide was completely reacted (the pressure did not decrease), 495 g of ethylene oxide was introduced until the pressure in the reaction kettle did not decrease, and then the temperature was cooled to below 70℃, and the product was discharged. Isomerized dodecanol alkoxylate without adsorption refining was obtained.

[0067] <TEST METHODS>

[0068] The determination method of the molecular weight distribution index PDI refers to GB / T 27843-2011 "Chemicals Determination of Low Molecular Weight Components in Polymers Gel Permeation Chromatography (GPC)".

[0069]

[0070] Wetting performance determination method:

[0071] 1. In a 1000 ml beaker, 800 ml of isomeric alcohol alkoxylate aqueous solution with a concentration of 1.0 g / L was prepared, and after stirring uniformly, it was kept at 25℃ for 3 h.

[0072] 2. A 35 mm diameter circular pure cotton canvas piece was clamped at the liquid surface of the beaker with tweezers, and the timing was started, until the canvas piece settled to the bottom of the beaker, the timing was stopped and the time was recorded, each sample was determined in parallel for 5 times, and the arithmetic mean value was taken. The shorter the wetting time, the better the wetting performance.

[0073] The determination method of metal cleaning power refers to GB / T 35759-2017 "Metal Cleaning Agent", the higher the oil removal rate, the stronger the metal cleaning power.

[0074] Low temperature appearance test method: 50 ml of isomeric alcohol alkoxylate product was taken into a 100 ml test tube, and after being kept at-5℃ for 12 h, the appearance of the sample was observed.

[0075]

[0076]

[0077] Unless specifically limited, the terms used in the present application have the meanings generally understood by those skilled in the art.

[0078] The embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present invention, and various other substitutions, changes and improvements can be made by those skilled in the art within the scope of the present invention, and thus the present invention is not limited to the above-described embodiments but is defined only by the claims.

Claims

1. A process for the preparation of isomeric polyoxypropylene polyoxyethylene glycol ethers, characterized in that, The preparation method comprises the following steps: (1) reacting isomeric alcohol with propylene oxide under the catalysis of an alkaline earth metal complex until the reaction pressure no longer decreases; (2) reacting the product of step (1) with ethylene oxide until the reaction pressure no longer decreases to obtain a crude isomeric alcohol polyoxypropylene polyoxyethylene ether; (3) adding an adsorbent to the crude isomeric alcohol polyoxypropylene polyoxyethylene ether to obtain an isomeric alcohol polyoxypropylene polyoxyethylene ether.

2. The production method according to claim 1, characterized by, The isomeric alcohol comprises at least one of isooctanol, isononyl alcohol, isodecanol, isoundecanol, 2-butyl-1-octanol and isotridecanol.

3. The production method according to claim 1, characterized by, The alkaline earth metal complex catalyst is prepared by reacting an alkaline earth metal compound with a polyether polyol.

4. The production method according to claim 3, characterized by, The alkaline earth metal compound comprises one or more of magnesium oxide, magnesium hydroxide, magnesium carboxylate, calcium oxide, calcium hydroxide, calcium carboxylate, barium oxide, barium hydroxide, strontium oxide and strontium hydroxide; and / or the polyether polyol is at least one of polyoxyethylene ether and diethylene glycol monoethyl ether.

5. The preparation method according to any one of claims 1-4, wherein the alkaline earth metal complex catalyst is added in an amount of 0.002-0.5 wt%, preferably 0.01-0.2 wt%, based on the total mass of the isomeric alcohol, propylene oxide and ethylene oxide.

6. The method of claim 1, wherein, In step (1), the isomeric alcohol and the alkaline earth metal complex are placed in a reactor, dehydrated by replacing with inert gas for multiple times, and then propylene oxide is introduced after the temperature is raised to the reaction temperature; preferably, the dehydration temperature is 85-95℃, the dehydration time is 1-2.5 h, and the water content in the system is less than 0.5 wt%.

7. The preparation method according to claim 1, characterized in that, The molar ratio of the isomeric alcohol, propylene oxide and ethylene oxide is 1:0.5-8:2-15, preferably 1:1.5-5:3-10.

8. The method of claim 1, wherein, The reaction temperature after introducing propylene oxide in step (1) and / or the reaction temperature after introducing ethylene oxide in step (2) is 135-175℃, preferably 140-160℃.

9. The method of claim 1, wherein, The adsorbent is at least one of diatomite, aluminum silicate, magnesium silicate, activated carbon and aluminum oxide; preferably, the adsorbent is used in an amount of 0.02-3 wt% of the crude isomeric alcohol polyoxypropylene polyoxyethylene ether; preferably, the adsorption temperature is 75-105℃, and the adsorption time is 1-3 h.

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