Isononyl alcohol polyoxyethylene ether as well as preparation method and application thereof
The preparation of isononyl alcohol polyoxyethylene ether by loading palladium-cobalt catalyst on a modified support solves the problems of strong catalyst corrosivity and uneven molecular weight distribution, and achieves green preparation with narrow molecular weight distribution and low by-products, which can be applied to cotton textile refining agent.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-19
- Publication Date
- 2026-03-27
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the technical field of surfactants, and more particularly to an isononyl alcohol polyoxyethylene ether, its preparation method, and its application. Background Technology
[0002] Isononol polyoxyethylene ether is a mixture of alcohol ethers with varying degrees of polymerization, obtained by the ethoxylation reaction of isononol and ethylene oxide in the presence of a catalyst. The most important factors affecting the molecular weight distribution of the isononol ethoxylation products are the properties of the alcohol and the catalyst. Once the isononol is determined, the catalyst becomes the primary factor influencing the reaction products. Different catalysts produce ethoxylation products with significantly different molecular weight distributions. Alkaline catalysts produce products with a wider molecular weight distribution and more free alcohol. Acidic catalysts produce products with a narrower molecular weight distribution but more byproducts. Furthermore, temperature has a significant impact on the reaction; too low a temperature prevents the reaction from proceeding properly, while too high a temperature easily generates excessive byproducts. The molecular weight distribution of the isononol polyoxyethylene ether products directly affects their application, and both alkaline and acidic catalysts are highly corrosive, difficult to separate, and generate a lot of waste. Long-term use can easily damage equipment, which is inconsistent with the current trend of green and safe development. Summary of the Invention
[0003] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an isononol polyoxyethylene ether, its preparation method, and its applications. The isononol polyoxyethylene ether prepared by the method described in this invention has a high degree of polymerization and a low molecular weight distribution coefficient.
[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a method for preparing isononyl alcohol polyoxyethylene ether, comprising the following steps: (1) Add isononol and catalyst to the reactor, then introduce nitrogen into the reactor and heat and stir; the catalyst is a modified supported palladium-cobalt catalyst; (2) Continue to heat up and add ethylene oxide into the reactor to induce the reaction. After the pressure and temperature are constant, vacuum dehydration is carried out. (3) Continue to heat up and introduce ethylene oxide into the reactor again until the pressure of ethylene oxide in the reactor is constant at 70 kPa. (4) When the amount of ethylene oxide added reaches the theoretical value, stop the ethylene oxide feeding, cool down, age until the pressure is constant at 20 kPa, remove the ethylene oxide gas in the reactor under vacuum, purge with nitrogen and discharge to obtain isononyl alcohol polyoxyethylene ether.
[0005] The ratio of isononol to total ethylene oxide in this invention is calculated as a mass ratio of 1:(3~12) based on the number of cycloadditions.
[0006] Preferably, the heating temperature in step (1) is 60~100℃.
[0007] Preferably, the amount of catalyst added in step (1) is 0.04~0.06% of the total mass of isononol and ethylene oxide in the reactor.
[0008] Preferably, the heating temperature in step (2) is 160~180℃.
[0009] Preferably, the amount of ethylene oxide added in step (2) is 5-15% of the total amount of ethylene oxide added. If the amount of ethylene oxide added is too low, the pre-reaction effect will be poor and the reaction time will be too long; if the amount of ethylene oxide added is too high, it will affect the molecular weight distribution. Therefore, controlling the amount of ethylene oxide added in step (2) is beneficial to improving the reaction efficiency.
[0010] Preferably, the cooling temperature in step (4) is 60~100℃.
[0011] Preferably, the preparation method of the modified supported palladium-cobalt catalyst includes the following steps: S1: By weight, add 10-20 parts of palladium salt, 10-20 parts of cobalt salt and 2-4 parts of acidic solution to 20-40 parts of deionized water, stir evenly to obtain a premixed solution. Add 60-80 parts of sodium borohydride to 10-20 parts of deionized water and stir until homogeneous to obtain a sodium borohydride solution. S2: Add 30-50 parts of the modified carrier to the premixed solution, stir and impregnate, then add pH adjuster to adjust the pH of the solution to 8-10, stir evenly to obtain a mixed solution; S3: Add sodium borohydride solution to the mixed solution, continue stirring the reaction, filter and separate to obtain filter cake, then wash the filter cake until the filtrate is neutral, and dry to obtain modified supported palladium-cobalt catalyst.
[0012] Preferably, the acidic solution in S1 includes at least one of concentrated hydrochloric acid, sulfuric acid, and nitric acid.
[0013] Preferably, the pH adjuster in S2 is a saturated solution of sodium carbonate or a saturated solution of sodium bicarbonate.
[0014] Preferably, the method for preparing the modified carrier in S2 includes the following steps: The carrier and modifier were added to deionized water, heated and stirred under reflux, filtered, and the filter cake was washed until the filtrate was neutral. After drying, the modified carrier was obtained.
[0015] Preferably, the carrier includes one of alumina, activated carbon, silica gel, and molecular sieve.
[0016] Preferably, the specific surface area of the carrier is 100-1000 m². 2 / g, with a particle size range of 5-20 nm.
[0017] Preferably, the modifier includes at least one of hydrogen peroxide, concentrated nitric acid, concentrated hydrochloric acid, ammonia, and sodium hydroxide.
[0018] Preferably, the mass ratio of the carrier, modifier and deionized water is (1~3):10:(80~100).
[0019] If the mass ratio of carrier to modifier is too high, the carrier structure will be damaged; if the mass ratio is too low, it will lead to low or uneven metal dispersion. Therefore, controlling the mass ratio of carrier to modifier is beneficial to improving the activity of the modified carrier.
[0020] Secondly, the present invention also provides an isononyl alcohol polyoxyethylene ether prepared by the above method. The isononyl alcohol polyoxyethylene ether prepared by the present invention exhibits a narrower gelation range, or even no gelation phenomenon, and is miscible with water at any concentration.
[0021] Thirdly, the present invention also provides the application of isononyl alcohol polyoxyethylene ether in basic cotton textile refining agents.
[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention uses palladium-cobalt metal as a catalyst and activated carbon and other materials as catalyst supports. The supports are modified and then mixed with palladium and cobalt salts. The catalyst supported on the supports exhibits excellent catalytic performance. The modified supports have a significantly reduced wetting angle, allowing for rapid and smooth dispersion in water, thus improving the loading efficiency of palladium-cobalt metal. This forms a modified support-supported palladium-cobalt catalyst, which is then mixed with raw materials to prepare isononyl alcohol polyoxyethylene ether. The reaction products can be directly filtered and collected, resulting in fewer byproducts. The operation is simple, reducing the difficulty of subsequent separation and purification. Furthermore, compared to traditional acid-base catalysts, the modified support-supported palladium-cobalt catalyst is safer and more environmentally friendly in its preparation process, improving the product quality stability of isononyl alcohol polyoxyethylene ether and meeting green environmental protection requirements. Detailed Implementation
[0023] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection and implementation of the present invention are not limited thereto.
[0024] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.
[0025] Example 1 A method for preparing isononyl alcohol polyoxyethylene ether includes the following steps: (1) Add activated carbon and hydrogen peroxide to deionized water, place it in a constant temperature oil bath magnetic stirrer, heat it to 90°C and stir and reflux for 4 hours, filter it to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, vacuum dry it to obtain modified activated carbon; the mass ratio of activated carbon, hydrogen peroxide and deionized water is 1:10:80.
[0026] (2) Weigh 10 parts palladium salt, 10 parts cobalt salt, 2 parts concentrated hydrochloric acid, 30 parts modified activated carbon, 60 parts sodium borohydride, and 30 parts deionized water by weight.
[0027] (3) Add palladium salt, cobalt salt and concentrated hydrochloric acid to 2 / 3 of deionized water and stir until homogeneous to obtain a premixed solution.
[0028] (4) Add the modified activated carbon to the premixed solution, stir slowly at room temperature on a magnetic stirrer, add sodium carbonate saturated solution to adjust the pH to 8, and continue stirring to obtain a mixed solution.
[0029] (5) Add sodium borohydride to the remaining 1 / 3 of the deionized water and stir until homogeneous to obtain sodium borohydride solution.
[0030] (6) Add sodium borohydride solution in batches to the mixed solution in step (4), continue stirring the reaction, filter and separate to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, and vacuum dry to obtain modified activated carbon supported palladium cobalt catalyst.
[0031] (7) Isononol (468g) and modified activated carbon supported palladium cobalt catalyst were vacuum-inhaled into the reactor. The amount of modified activated carbon supported palladium cobalt catalyst added was 0.04% of the total mass of the materials (isononol and ethylene oxide) in the reactor. Nitrogen gas was introduced into the reactor and the temperature was raised to 60°C and stirred for 0.5h to remove low-boiling-point substances and water from the reactor.
[0032] (8) After the low-boiling-point substances and water in the reactor are removed, the temperature is raised to 160°C and ethylene oxide is added to the reactor. The amount of ethylene oxide added is 5% of the total amount of ethylene oxide added. The reaction is initiated. After the pressure and temperature are constant, a vacuum is drawn for secondary dehydration.
[0033] (9) After the second dehydration is completed, the temperature is continuously increased, and ethylene oxide is continuously introduced into the reactor again to keep the ethylene oxide pressure in the reactor constant at 70 kPa.
[0034] (10) When the amount of ethylene oxide added reaches the theoretical value (430g), stop feeding ethylene oxide, cool down to 60°C, age until the pressure is constant at 20kPa, remove the ethylene oxide gas in the reactor under vacuum, and discharge the material with nitrogen to obtain isononyl alcohol polyoxyethylene ether.
[0035] Example 2 A method for preparing isononyl alcohol polyoxyethylene ether includes the following steps: (1) Add aluminum oxide and concentrated nitric acid to deionized water, place it in a constant temperature oil bath magnetic stirrer, heat it to 90°C and stir and reflux for 4 hours, filter it to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, and vacuum dry it to obtain modified aluminum oxide; the mass ratio of aluminum oxide, concentrated nitric acid and deionized water is 2:10:90.
[0036] (2) Weigh out 15 parts palladium salt, 15 parts cobalt salt, 3 parts concentrated hydrochloric acid, 40 parts modified activated carbon, 70 parts sodium borohydride, and 45 parts deionized water by weight.
[0037] (3) Add palladium salt, cobalt salt and concentrated hydrochloric acid to 2 / 3 of deionized water and stir until homogeneous to obtain a premixed solution.
[0038] (4) Add the modified alumina to the premixed solution, stir slowly at room temperature on a magnetic stirrer, add sodium carbonate saturated solution to adjust the pH to 9, and continue stirring to obtain a mixed solution.
[0039] (5) Add sodium borohydride to the remaining 1 / 3 of the deionized water and stir until homogeneous to obtain sodium borohydride solution.
[0040] (6) Add sodium borohydride solution in batches to the mixed solution in step (4), continue stirring the reaction, filter and separate to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, and vacuum dry to obtain modified alumina supported palladium cobalt catalyst.
[0041] (7) Isononol (468g) and modified alumina supported palladium cobalt catalyst were vacuum-introduced into the reactor. The amount of modified alumina supported palladium cobalt catalyst added was 0.05% of the total mass of the materials (isononol and ethylene oxide) in the reactor. Nitrogen gas was introduced into the reactor and the temperature was raised to 80°C and stirred for 0.5h to remove low-boiling-point substances and water from the reactor.
[0042] (8) After the low-boiling-point substances and water in the reactor are removed, the temperature is raised to 170°C and ethylene oxide is added to the reactor. The amount of ethylene oxide added is 10% of the total amount of ethylene oxide added. The reaction is initiated. After the pressure and temperature are constant, a vacuum is drawn for secondary dehydration.
[0043] (9) After the second dehydration is completed, the temperature is continuously increased, and ethylene oxide is continuously introduced into the reactor again to keep the ethylene oxide pressure in the reactor constant at 70 kPa.
[0044] (10) When the amount of ethylene oxide added reaches the theoretical value (430g), stop feeding ethylene oxide, cool down to 80℃, age until the pressure is constant at 20kpa, remove the ethylene oxide gas in the reactor under vacuum, and discharge the material with nitrogen to obtain isononyl alcohol polyoxyethylene ether.
[0045] Example 3 A method for preparing isononyl alcohol polyoxyethylene ether includes the following steps: (1) Add silica gel and sodium hydroxide to deionized water, place them in a constant temperature oil bath magnetic stirrer, heat to 90°C and stir and reflux for 4 hours, filter to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, vacuum dry to obtain modified silica gel; the mass ratio of silica gel, sodium hydroxide and deionized water is 3:10:100.
[0046] (2) Weigh 20 parts palladium salt, 20 parts cobalt salt, 4 parts concentrated hydrochloric acid, 50 parts modified activated carbon, 80 parts sodium borohydride, and 60 parts deionized water by weight.
[0047] (3) Add palladium salt, cobalt salt and concentrated hydrochloric acid to 2 / 3 of deionized water and stir until homogeneous to obtain a premixed solution.
[0048] (4) Add the modified silica gel to the premixed solution, stir slowly at room temperature on a magnetic stirrer, add sodium carbonate saturated solution to adjust the pH to 10, and continue stirring to obtain a mixed solution.
[0049] (5) Add sodium borohydride to the remaining 1 / 3 of the deionized water and stir until homogeneous to obtain sodium borohydride solution.
[0050] (6) Add sodium borohydride solution in batches to the mixed solution in step (4), continue stirring the reaction, filter and separate to obtain filter cake, then wash the filter cake with deionized water until the filtrate is neutral, and vacuum dry to obtain modified silica gel supported palladium cobalt catalyst.
[0051] (7) Isononol (468g) and modified silica gel supported palladium cobalt catalyst were vacuum-inhaled into the reactor. The amount of modified silica gel supported palladium cobalt catalyst added was 0.06% of the total mass of the materials (isononol and ethylene oxide) in the reactor. Nitrogen gas was introduced into the reactor and the temperature was raised to 100°C and stirred for 0.5h to remove low-boiling-point substances and water from the reactor.
[0052] (8) After the low-boiling-point substances and water in the reactor are removed, the temperature is raised to 180°C and ethylene oxide is added to the reactor. The amount of ethylene oxide added is 15% of the total amount of ethylene oxide added. The reaction is initiated. After the pressure and temperature are constant, a vacuum is drawn for secondary dehydration.
[0053] (9) After the second dehydration is completed, the temperature is continuously increased, and ethylene oxide is continuously introduced into the reactor again to keep the ethylene oxide pressure in the reactor constant at 70 kPa.
[0054] (10) When the amount of ethylene oxide added reaches the theoretical value (430g), stop the ethylene oxide feeding, cool down to 100℃, age until the pressure is constant at 20kpa, remove the ethylene oxide gas in the reactor under vacuum, and discharge the material with nitrogen to obtain isononyl alcohol polyoxyethylene ether.
[0055] Example 4 The difference from Example 1 is that the mass ratio of activated carbon, hydrogen peroxide and deionized water in step (1) is 0.5:10:80.
[0056] Example 5 The difference from Example 1 is that the mass ratio of activated carbon, hydrogen peroxide and deionized water in step (1) is 5:10:80.
[0057] Example 6 The difference from Example 1 is that in step (2), 5 parts palladium salt, 10 parts cobalt salt, 2 parts concentrated hydrochloric acid, 30 parts modified activated carbon, 60 parts sodium borohydride, and 30 parts deionized water are weighed respectively.
[0058] Example 7 The difference from Example 1 is that in step (2), 10 parts palladium salt, 5 parts cobalt salt, 2 parts concentrated hydrochloric acid, 30 parts modified activated carbon, 60 parts sodium borohydride, and 30 parts deionized water are weighed respectively.
[0059] Example 8 The difference from Example 1 is that in step (2), 10 parts palladium salt, 10 parts cobalt salt, 2 parts concentrated hydrochloric acid, 20 parts modified activated carbon, 60 parts sodium borohydride, and 30 parts deionized water are weighed respectively.
[0060] Example 9 The difference from Example 1 is that in step (7), the amount of modified activated carbon supported palladium-cobalt catalyst added is 0.03% of the total mass of the materials in the reactor.
[0061] Example 10 The difference from Example 1 is that in step (7), the amount of modified activated carbon supported palladium-cobalt catalyst added is 0.08% of the total mass of the materials in the reactor.
[0062] Comparative Example 1 The difference from Example 1 is that in step (7), an equal mass of sulfuric acid is used to replace the modified activated carbon-supported palladium-cobalt catalyst.
[0063] Comparative Example 2 The difference from Example 1 is that in step (7), an equal mass of sodium hydroxide is used to replace the modified activated carbon supported palladium-cobalt catalyst.
[0064] Comparative Example 3 The difference from Example 1 is that in step (7), an equal mass of commercial palladium on carbon catalyst is used instead of the modified activated carbon supported palladium-cobalt catalyst.
[0065] experiment The conversion rate, degree of polymerization, and molecular weight distribution coefficient of the isononyl alcohol polyoxyethylene ethers prepared in the above examples and comparative examples were determined. The results are shown in Table 1.
[0066] Table 1 As can be seen from the comparison between Examples 1-3 and Comparative Examples 1-3, the present invention uses palladium and cobalt salts as raw materials and modified activated carbon as a carrier to prepare a modified activated carbon-supported palladium-cobalt catalyst. This catalyst is then mixed with the raw materials to prepare isononyl alcohol polyoxyethylene ether. The product conversion rates all exceed 94%. With a theoretical degree of polymerization of 5, the isononyl alcohol polyoxyethylene ethers prepared in Examples 1-3 all have a degree of polymerization of not less than 4.9, and a molecular weight distribution coefficient of less than 1.2. Therefore, compared with traditional acid-base catalysts and commercial palladium-carbon catalysts, the modified activated carbon-supported palladium-cobalt catalyst of the present invention produces isononyl alcohol polyoxyethylene ether with higher product conversion rates and higher degrees of polymerization, and a lower molecular weight distribution coefficient. Furthermore, the method of the present invention allows for direct filtration and collection of the reaction products, resulting in fewer byproducts. The operation is simple, reducing the difficulty of subsequent separation and purification. Simultaneously, the preparation process is safe and environmentally friendly, and the product quality is stable, meeting green environmental protection requirements.
[0067] This invention discloses a basic cotton textile refining agent formula: 50 parts isononyl alcohol polyoxyethylene ether, 10 parts anionic surfactant, 2 parts chelating agent, 3 parts defoamer, 1 part preservative, 5 parts thickener, 5 parts citric acid, and 24 parts water.
[0068] The basic cotton textile refining agent formulation underwent tests for capillary effect, fabric sinking, and acid and alkali resistance, with values of 13.2 cm, 7 s, and 60 g / L, respectively. The high capillary effect indicates that the isononyl alcohol polyoxyethylene ether prepared in this invention has strong hydrophilicity and plays a significant role in improving the subsequent dyeing and finishing processes of the fabric. The fabric sinking test, which assists in assessing the capillary effect, also demonstrates that the fabric treated with the refining agent has good hydrophilicity.
[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing isononyl alcohol polyoxyethylene ether, characterized in that, Includes the following steps: (1) Add isononol and catalyst to the reactor, then introduce nitrogen into the reactor and heat and stir; the catalyst is a modified supported palladium-cobalt catalyst; (2) Continue to heat up and add ethylene oxide into the reactor to induce the reaction. After the pressure and temperature are constant, vacuum dehydration is carried out. (3) Continue to heat up and introduce ethylene oxide into the reactor again until the pressure of ethylene oxide in the reactor is constant; (4) When the amount of ethylene oxide added reaches the theoretical value, stop the ethylene oxide feeding, cool down, age until the pressure is constant, remove the ethylene oxide gas in the reactor under vacuum, purge with nitrogen and discharge to obtain isononyl alcohol polyoxyethylene ether.
2. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 1, characterized in that, The heating temperature in step (1) is 60~100℃; And / or, the amount of catalyst added in step (1) is 0.04~0.06% of the total mass of isononol and ethylene oxide in the reactor.
3. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 1, characterized in that, The heating temperature in step (2) is 160~180℃; And / or, the amount of ethylene oxide added in step (2) is 5-15% of the total amount of ethylene oxide added.
4. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 1, characterized in that, The cooling temperature in step (4) is 60~100℃.
5. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 1, characterized in that, The preparation method of the modified support-supported palladium-cobalt catalyst in step (1) includes the following steps: S1: By weight, add 10-20 parts of palladium salt, 10-20 parts of cobalt salt and 2-4 parts of acidic solution to 20-40 parts of deionized water, stir evenly to obtain a premixed solution. Add 60-80 parts of sodium borohydride to 10-20 parts of deionized water and stir until homogeneous to obtain a sodium borohydride solution. S2: Add 30-50 parts of the modified carrier to the premixed solution, stir and impregnate, then add pH adjuster to adjust the pH of the solution to 8-10, stir evenly to obtain a mixed solution; S3: Add sodium borohydride solution to the mixed solution, continue stirring the reaction, filter and separate to obtain filter cake, then wash the filter cake until the filtrate is neutral, and dry to obtain modified supported palladium-cobalt catalyst.
6. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 5, characterized in that, The preparation method of the modified support in S1 includes the following steps: The carrier and modifier were added to deionized water, heated and stirred under reflux, filtered, and the filter cake was washed until the filtrate was neutral. After drying, modified activated carbon was obtained.
7. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 6, characterized in that, The modifier includes at least one of hydrogen peroxide, concentrated nitric acid, concentrated hydrochloric acid, ammonia, and sodium hydroxide. And / or, the mass ratio of the carrier, modifier and deionized water is (1~3):10:(80~100); And / or, the carrier includes one of alumina, activated carbon, silica gel, and molecular sieve.
8. The method for preparing isononyl alcohol polyoxyethylene ether as described in claim 5, characterized in that, The pH adjuster in S2 is a saturated solution of sodium carbonate or a saturated solution of sodium bicarbonate.
9. An isononyl alcohol polyoxyethylene ether prepared by the preparation method according to any one of claims 1-8.
10. The application of isononyl alcohol polyoxyethylene ether as described in claim 9 in a basic cotton textile refining agent.