Method for preparing glycosyl modified nonylphenol polyoxyethylene ether

Abstract

The invention discloses a method for preparing glycosyl modified nonylphenol polyoxyethylene ether, and belongs to the technical field of surfactants. The preparation method of the glycosyl modified nonylphenol polyoxyethylene ether comprises the following steps: mixing glucose, nonylphenol polyoxyethylene ether and an acid catalyst to obtain a precursor, and carrying out aldolization to complete glycosyl modification. The nonylphenol polyoxyethylene ether is subjected to efficient grafting modification through glucose, on the basis that the original performance advantages of the nonylphenol polyoxyethylene ether are kept, the cloud point, alkali resistance and other working performance are further improved, the application value of the nonylphenol polyoxyethylene ether in an actual scene is expanded, and the nonylphenol polyoxyethylene ether has economical efficiency and functionality and is worthy of popularization and application. The method has important significance in promoting the progress and development of the surfactant industry.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, in particular to a method for preparing sugar-modified nonylphenol polyoxyethylene ether. Background Art

[0002] In the field of surfactants, nonylphenol polyoxyethylene ether (NP10) as a typical nonionic surfactant occupies an important market position. This compound is formed by the addition polymerization between nonylphenol and ethylene oxide. With its good emulsification, dispersion, solubilization and wetting properties, it is widely used in many industries such as detergents, textile printing and dyeing, papermaking and pesticide emulsifiers, greatly promoting the production efficiency and product quality of related industries.

[0003] However, despite its many advantages, NP10 also has certain limitations in practical applications. For example, under extreme pH conditions, especially in strong alkaline systems, the stability of NP10 shows obvious deficiencies, which limits its applicability in certain specific environments. In addition, the sensitivity of NP10's cloud point to temperature changes is also an important factor affecting its performance stability in wide temperature range applications; this temperature dependence may make it difficult to ensure the effectiveness and stability of NP10 under process conditions with large temperature changes, thereby affecting the quality and production efficiency of the final product.

[0004] In view of the rapid development of technology in the field of surfactants and the growing global demand for high-performance, environmentally friendly chemicals, modifying and optimizing traditional NP10 to improve its stability under extreme conditions and broaden its application range has become a key issue that the industry needs to solve urgently. Summary of the invention

[0005] The object of the present invention is to provide a method for sugar-modified nonylphenol polyoxyethylene ether to solve the above-mentioned problems in the background technology. The present invention aims to develop a new surfactant with lower price, better performance and better market demand. The present invention further improves the working properties such as cloud point and alkali resistance by efficiently grafting nonylphenol polyoxyethylene ether with glucose while maintaining its original performance advantages, expands its application value in actual scenarios, and has both economy and functionality, which is of great significance for promoting the progress and development of the surfactant industry.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention: Provide a method for glycosylating nonylphenol polyoxyethylene ether. Glycosylate nonylphenol polyoxyethylene ether with glucose to prepare phenol ether glycoside (glycosylated nonylphenol polyoxyethylene ether).

[0008] Further preferably, the glycosylation includes the following steps:

[0009] Mix glucose, nonylphenol polyoxyethylene ether and an acidic catalyst to obtain a precursor, and carry out an acetal reaction to complete the glycosylation.

[0010] The above reaction formula is:

[0011]

[0012] Preferably, the molar ratio of nonylphenol polyoxyethylene ether to glucose is 1-8:1 and not 1:1.

[0013] The final product obtained by the present invention is a mixture of NP10 and glycosylated NP10. The ratio of the two in the mixture has a great influence on the working performance of the product. It is not that the higher the proportion of phenol ether glycoside in the product, the better the performance. Therefore, the molar ratio of NP10 to glucose in the raw materials is very important.

[0014] Preferably, the acidic catalyst is one or more of sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, heteropolyacid and acidic resin.

[0015] Preferably, the addition amount of the acidic catalyst is 0.1-3 wt% of the precursor.

[0016] More preferably, the addition amount of the acidic catalyst is 0.5-3 wt% of the precursor.

[0017] Preferably, the temperature of the acetal reaction is 80-150 °C, the time is 2-10 hours, and the vacuum degree is 0-10 mmHg.

[0018] Preferably, the acetal reaction is carried out under stirring conditions, and the stirring speed is 200-600 r / min.

[0019] Preferably, before the acetal reaction, a pretreatment step is further included, and the pretreatment is: Stir at a speed of 200 r / min for 5-30 min, and remove water by vacuum while stirring to complete the pretreatment.

[0020] Two of the technical solutions of the present invention: Provide a glycosylated nonylphenol polyoxyethylene ether prepared according to the above method.

[0021] Three of the technical solutions of the present invention: Provide an application of the above glycosylated nonylphenol polyoxyethylene ether in the field of surfactants.

[0022] Fourth technical solution of the present invention: Provide a method for improving the alkali resistance of nonylphenol polyoxyethylene ether, and perform glycosylation modification on nonylphenol polyoxyethylene ether using glucose.

[0023] Fifth technical solution of the present invention: Provide a method for improving the performance stability of nonylphenol polyoxyethylene ether under wide temperature range conditions, and perform glycosylation modification on nonylphenol polyoxyethylene ether using glucose.

[0024] The present invention innovatively uses glucose, a raw material that is widely sourced, renewable, and environmentally friendly, to modify nonylphenol polyoxyethylene ether, bringing about performance improvements in multiple aspects. On the one hand, this modification can improve the cloud point, alkali resistance and other properties of nonylphenol polyoxyethylene ether, thereby expanding its application value; on the other hand, from an economic benefit perspective, the modified product (phenol ether glycoside) can also generate a market premium space due to its unique performance advantages, having dual driving forces of cost competitiveness and increased added value. The present invention has the feasibility of large-scale production and provides a new technical solution for the sustainable development of the industry.

[0025] The beneficial technical effects of the present invention are as follows:

[0026] In response to the growing market demand for high-performance surfactants, the present invention proposes a preparation method for modifying nonylphenol polyoxyethylene ether (NP10) using renewable resource glucose as a raw material. Glycosylation modification develops a new type of surfactant, phenol ether glycoside, which combines cost advantages and improved application performance by successfully introducing glycosyl groups into the molecular structure of nonylphenol polyoxyethylene ether. In addition, compared with traditional modification technologies, the process route of the present invention is simple, and the reaction process does not require post-treatment procedures, effectively overcoming the defects of high organic solvent usage rate and complex purification steps in traditional modification technologies.

[0027] Through the efficient graft modification of nonylphenol polyoxyethylene ether with glucose, the present invention further improves the working properties such as cloud point and alkali resistance on the basis of maintaining its original performance advantages, expands its application value in actual scenarios, and combines economy and functionality, which is of great significance for promoting the progress and development of the surfactant industry.

[0028] The cloud point of non-ionic surfactants is reflected by the formation of hydrogen bonds between the surfactant and water molecules. Glucose is introduced into NP10 as a hydrophilic group, increasing the sites for forming hydrogen bonds between NP10 molecules and water molecules, thus raising the cloud point.

[0029] In an alkaline environment, after glucose is grafted, the hydroxyl groups will dissociate to a certain extent, making the molecule negatively charged and generating electrostatic repulsion between molecules, avoiding excessive aggregation, enhancing the solubility and stability of the surfactant in alkaline solutions, and thus improving the alkali resistance; on the other hand, the grafting of glucose increases the steric hindrance of the molecule, and the larger spatial structure can block OH- Attack to reduce the damage of alkaline substances to the molecular structure, thereby improving the alkali resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0031] Figure 1 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1-4 varying with the material ratio.

[0032] Figure 2 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 5 varying with the reaction time.

[0033] Figure 3 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 6 varying with the reaction temperature.

[0034] Figure 4 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 7 varying with the catalyst addition amount.

[0035] Figure 5 It is an infrared spectrum diagram of the product of Example 1.

[0036] Figure 6 It is a physical diagram of the products of Examples 1-3. DETAILED DESCRIPTION OF THE INVENTION

[0037] Now, various exemplary embodiments of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention. It should be understood that the terms described in the present invention are only for describing specific implementation modes and are not used to limit the present invention.

[0038] In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0039] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of this invention. It should be noted that the aspects not detailed in this invention are all conventional operating means in the art and are not the focus of this invention.

[0040] Regarding the terms "comprising", "including", "having", "containing", etc. used in this invention, they are all open-ended terms, meaning including but not limited to.

[0041] This invention discloses a method for glycosyl-modifying nonylphenol polyoxyethylene ether, comprising the following steps:

[0042] (1) Accurately weigh the raw materials: Use a high-precision electronic balance to separately weigh nonylphenol polyoxyethylene ether (NP10) and glucose, mix NP10 and glucose in a molar ratio of 1 - 8:1, and then pour them into a four-necked flask for pre-mixing;

[0043] (2) Add a catalyst: Add an acidic catalyst (one or more of sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, heteropolyacid, and acidic resin) to the reaction system, and its addition amount is 0.1 - 3% of the total mass of the reaction system;

[0044] (3) Turn on the mechanical stirring device. First, stir at a low speed of 200 r / min for 5 - 30 min to initially mix the overall materials, and then continue to stir and react at a speed of 200 - 600 r / min; During stirring, simultaneously start the vacuum system and adjust the vacuum degree to 0 - 10 mmHg to ensure that the moisture in the reaction system can be removed promptly and thoroughly, thereby effectively promoting the reaction to continuously proceed in the forward reaction direction;

[0045] (4) Use an oil bath heating system to carry out programmed heating on the reaction device, and raise the system temperature to the target reaction temperature of 80 - 150 °C; Start timing from when the system temperature reaches the set value, and maintain a constant temperature reaction for 2 - 10 hours to obtain glycosyl-modified nonylphenol polyoxyethylene ether;

[0046] (5) Data collection: After the reaction ends, determine the reaction endpoint based on the remaining glucose content: Weigh a certain amount of the reaction mixture (W0), make up the volume to V1 to obtain the mixture; Take 10 mL each of Fehling's solution A and B on an electric furnace and boil them within 1 - 2 min. Absorb the mixture and titrate it to Fehling's solution until the blue color disappears, and record the volume V2 of the consumed lower layer solution. If the mixture cannot decolorize Fehling's solution, continue to titrate with the prepared standard sugar solution until the blue color disappears, and record the volume V3 of the consumed standard sugar solution. Calculate the residual sugar content and glucose conversion rate through the formula.

[0047]

[0048] In the formula, V0' is the volume of the standard sugar solution consumed when standardizing Fehling's solutions A and B. m1 is the mass of anhydrous glucose before the reaction, m2 is the total mass of the system after the reaction, and w is the residual sugar content.

[0049] All raw materials used in the following examples and comparative examples of the present invention are commercially available products.

[0050] Example 1

[0051] A method for glycosyl-modifying nonylphenol polyoxyethylene ether, the steps are as follows:

[0052] (1) Accurately weigh the raw materials: Weigh nonylphenol polyoxyethylene ether (NP10) and glucose (AGU) respectively using a high-precision electronic balance, mix NP10 and glucose according to a molar ratio of 5:1, and then pour them into a four-necked flask for premixing;

[0053] (2) Add a catalyst: Add an acidic catalyst (p-toluenesulfonic acid) to the reaction system, and its addition amount is 1% of the total mass of the reaction system;

[0054] (3) Turn on the mechanical stirring device. First, stir at a low speed of 200 r / min for 5 min to preliminarily mix the overall materials, and then continue to stir and react at a speed of 500 r / min; During stirring, start the vacuum system synchronously and adjust the vacuum degree to 3 mmHg;

[0055] (4) System heating and constant-temperature reaction: Use an oil bath heating system to perform programmed heating on the reaction device, and raise the system temperature to the target reaction temperature of 110 °C; Start timing from when the system temperature reaches the set value, and maintain a constant-temperature reaction for 6 hours to obtain glycosyl-modified nonylphenol polyoxyethylene ether (phenolic ether glycoside);

[0056] (5) Data collection: After the reaction is completed, determine the reaction end point based on the remaining glucose content: Weigh 5.28 g of the reaction mixture and make it up to 100 mL to obtain the mixture; Take 10 mL each of Fehling's solutions A and B and boil them on an electric furnace. Absorb the mixture and titrate the Fehling's solution until the blue color disappears, and the volume of the lower layer solution consumed is 86.6 mL. The mixture cannot decolorize the Fehling's solution, and continue to titrate with the standard sugar solution until the blue color disappears, and the volume of the standard sugar solution consumed is 13.7 mL. The measured residual sugar content is 0.16% and the glucose conversion rate is 97.00%.

[0057]

[0058] In the formula, V0' is the volume of the standard sugar solution consumed when standardizing Fehling's solutions A and B. m1 is the mass of anhydrous glucose before the reaction, m2 is the total mass of the system after the reaction, and w is the residual sugar content.

[0059] The Fourier transform infrared spectroscopy (FT-IR) was used to accurately analyze the structure of the product, and the test results are as Figure 5 shown.

[0060] Figure 5 Figure 7 is a comparison diagram of the infrared spectra of the product of Example 1 and NP10.

[0061] Figure 5 The comparative study of the infrared spectra of NP10 and phenol ether glycoside shown clearly reveals the key information of the product structure. In the hydroxyl vibration region of 3400 cm -1 , the absorption peak intensity of the modified product is significantly enhanced and broadened, proving the successful introduction of the hydroxyl group of glucose molecules; the red-shifted composite vibration mode in the ether bond vibration region of 1100 cm -1 indicates the vibration coupling of the polyoxyethylene chain ether bond of NP10 and the glucose glycoside bond, which is an important basis for the formation of glycoside bonds; the obvious weakening of the out-of-plane bending vibration peak of the benzene ring in the region of 830-570 cm -1 reflects the influence of the glucose hydroxyl condensation reaction on the benzene ring substitution pattern. At the same time, the characteristic peaks of the benzene ring skeleton C=C stretching vibration at 1609 cm -1 , 1511 cm -1 and 1458 cm -1 , the vibration absorption peak of the specific C-C bond of the alkyl chain at 1960 cm -1 , and the broad absorption peak caused by the vibration of methylene and methyl in the region of 2850-2960 cm -1 remain consistent before and after modification, confirming the stability of the C-H structure of the benzene ring skeleton, long-chain alkyl and EO chain during the modification process. Combining the results of FT-IR analysis, it is firmly proved that anhydrous glucose has been successfully grafted onto nonylphenol polyoxyethylene ether to form a new product with a clear structure, and the modification reaction has a high regioselectivity.

[0062] In the performance determination of the product of Example 1, a series of key and significantly advantageous data were obtained. After measurement, its residual sugar content is 0.16%; the emulsification time for liquid paraffin is 11.23 min; the cloud point is 71 °C; the salt tolerance threshold is 251 g / L; in a 360 g / L alkaline solution, the alkali resistance stability is improved by 41% compared with NP10.

[0063] While the emulsification time of NP10 for liquid paraffin is 10.92 min; the cloud point is 66.50 °C; the salt tolerance threshold is 225 g / L; in a 360 g / L alkaline solution, the transmittance is 45.02%.

[0064] The test method for the emulsifying performance of liquid paraffin adopts the graduated cylinder water separation method. The specific operation is as follows: Use a pipette to take 40 mL of the solution to be tested, and add 40 mL of liquid paraffin or soybean oil to a 100 mL stoppered graduated cylinder respectively; Manually shake 5 times, let it stand for 1 minute, repeat 5 times, and quickly pour in the emulsion; Use a stopwatch to record the time for separating 10 mL of the aqueous phase; Repeat 3 times for each sample and take the average value.

[0065] The test method for salt and alkali resistance (the alkali solution is NaOH solution, and the salt solution is NaCl solution): Take 1 mL of the sample solution with a concentration of 1 g / L and place it in a 10 mL colorimetric tube; Add 1 mL, 2 mL, 3 mL, 4 mL, 5 mL, 6 mL, 7 mL, 8 mL, 9 mL of NaCl / NaOH solution to the colorimetric tube respectively and make up to 10 mL; Invert the colorimetric tube up and down 10 times (about 2 s each time), let it stand at 25 °C for 2 h, and observe the turbidity of the solution; Use a UV-visible spectrophotometer to measure the transmittance of the sample solution at 600 nm at different NaCl / NaOH concentrations.

[0066] The results of these performance determinations demonstrate that the products of the present invention have excellent performance and good adaptability in a variety of application scenarios, providing solid data support for their practical applications.

[0067] Example 2

[0068] The difference from Example 1 is only that the molar ratio of NP10 to glucose in step (1) is modified to 4:1.

[0069] It is measured that the residual sugar content of Example 2 is 0.24%; the emulsification duration for liquid paraffin is 11.34 min; the cloud point is 71.5 °C; the salt tolerance threshold is 253 g / L; in a 360 g / L alkaline solution, the alkali resistance stability is increased by 42%.

[0070] Example 3

[0071] The difference from Example 1 is only that the molar ratio of NP10 to glucose in step (1) is modified to 3:1.

[0072] It is measured that the residual sugar content of Example 3 is 0.31%; the emulsification duration for liquid paraffin is 11.94 min; the cloud point is 72 °C; the salt tolerance threshold is 258 g / L; in a 360 g / L alkaline solution, the alkali resistance stability is increased by 42%.

[0073] Table 1 Data comparison table of Examples 1 - 3

[0074]

[0075] Example 4

[0076] The difference from Example 1 is only that the molar ratios of NP10 and glucose in step (1) are respectively modified to 2:1 and 1.5:1.

[0077] Example 5

[0078] The difference from Example 1 is only that the reaction temperatures in step (4) are respectively modified to 4, 5, 7, and 8 hours from 6 hours.

[0079] Example 6

[0080] The difference from Example 1 is only that the reaction temperatures in step (4) are respectively modified to 100°C, 105°C, 115°C, and 120°C from 110°C.

[0081] Example 7

[0082] The difference from Example 1 is only that the dosages of the catalyst in step (2) are respectively modified to 0.75%, 1.25%, 1.5%, and 1.75% of the total mass of the reaction system.

[0083] Figure 1 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 - 4 varying with the material ratio.

[0084] Figure 2 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 5 varying with the reaction time.

[0085] Figure 3 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 6 varying with the reaction temperature.

[0086] Figure 4 It is a graph showing the residual sugar content and sugar conversion rate in the products of Examples 1 and 7 varying with the catalyst addition amount.

[0087] Figure 6 It is a physical diagram of the products of Examples 1 - 3.

[0088] Figure 6 Among them, from left to right are Example 3, Example 2, and Example 1 respectively.

[0089] The above-described examples are only descriptions of the preferred modes of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing glycosyl-modified nonylphenol polyoxyethylene ether, characterized in that: The phenol ether glycoside was prepared by glycosylation of nonylphenol polyoxyethylene ether with glucose.

2. The method according to claim 1, characterized in that The glycosyl modification comprises the following steps: Glucose, nonylphenol polyoxyethylene ether and an acidic catalyst are mixed to obtain a precursor, and then an acetal reaction is performed to complete the glycosyl modification.

3. The method according to claim 2, characterized in that The molar ratio of the nonylphenol polyoxyethylene ether to glucose is 1-8:1 and is not 1:

1.

4. The method according to claim 2, characterized in that: The acid catalyst is one or more of sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, heteropoly acid and acidic resin.

5. The method according to claim 2, characterized in that: The amount of the acid catalyst added is 0.1-3 wt % of the precursor.

6. The method according to claim 2, characterized in that The acetalization reaction is carried out at a temperature of 80-150° C., for a time of 2-10 hours, and at a vacuum degree of 0-10 mmHg.

7. A glycosyl-modified nonylphenol polyoxyethylene ether prepared according to the method according to any one of claims 1 to 6.

8. Use of the glycosyl-modified nonylphenol polyoxyethylene ether according to claim 7 in the field of surfactants.

9. A method for improving the alkali resistance of nonylphenol polyoxyethylene ether, characterized in that: Glucose was used to modify nonylphenol polyoxyethylene ether.

10. A method for improving the performance stability of nonylphenol polyoxyethylene ether under wide temperature range conditions, characterized in that: Glucose was used to modify nonylphenol polyoxyethylene ether.

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