Alkyl glycoside block polyether and preparation method thereof
By introducing epoxy compounds to the alkyl glycoside glycosyl skeleton, synthesis of alkyl glycoside block polyethers, the resistance and water solubility of existing low-foam surfactants are solved, and low foam characteristics and excellent performance are achieved. Combined, it is suitable for industrial cleaning and simplifies the preparation process.
Patent Information
- Application Number
- CN202411326568.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-23
- Publication Date
- 2024-12-27
AI Technical Summary
The impermanence of existing low-foam surfactants at high temperatures, high alkalis and shear forces limits their application scenarios, and the unsatisfactory water solubility of alkyl glycosides leads to difficulties in preparation and alcohol ether residues.
By introducing ethylene oxide, propylene oxide and butylene oxide to the alkyl glycoside glycosyl backbone, alkyl glycoside block polyether is synthesized, and an alkaline catalyst is used to carry out heating reaction under high pressure and nitrogen atmosphere to control The reaction temperature and pressure of the synthetic product has low bubble characteristics and low freezing point.
It realizes the combination of low foam characteristics and excellent performance of alkyl glycosides. It is suitable for industrial cleaning. The products are green and environmentally friendly and easy to rinse. It is suitable for low foam application scenarios. The preparation process is simplified and industrial production is facilitated.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of surfactants, and particularly relates to an alkyl glycoside block polyether and a preparation method thereof. Background Art
[0002] In the context of water conservation and energy conservation, low-foam surfactants are widely used in spray cleaning, machine dishwashing, pesticide spraying, overflow dyeing and other fields, and are in line with the social development trend of water conservation and energy conservation. The most common way to reduce foam is to add defoamers, but there are also problems such as high temperature resistance, high alkali resistance, and shear resistance. The development of low-foam surfactant products can fundamentally solve the foam problem.
[0003] Alkyl polyglycoside is currently recognized as a "green" functional surfactant in the world, with many advantages, such as: low surface tension, no cloud point, adjustable HLB value, strong wetting power, strong detergency, strong compatibility, non-toxic, harmless, non-irritating to the skin, rich, delicate and stable foam. However, the application scenarios of low foam are limited. Through modification, alkyl polyglycoside has both the original excellent performance and low foam characteristics to broaden its application scenarios.
[0004] Although alkyl glycosides have excellent performance and are used in many fields, long-chain alkyl glycosides also have defects such as unsatisfactory water solubility. At present, the modification of alkyl glycosides usually involves modifying the fatty alcohols used to prepare alkyl glycosides. Using fatty alcohol polyoxyethylene ethers with low EO addition numbers instead of fatty alcohols to prepare alcohol ether glycosides makes mass transfer more difficult, affects glycoside synthesis, and leaves a large amount of alcohol ether residues that are difficult to remove. Direct alkoxylation of alkyl glycosides is more efficient and convenient. Summary of the invention
[0005] In view of the above problems, the present invention provides an alkyl glycoside block polyether and a preparation method thereof. The polyhydroxyl groups on the glycosyl skeleton of the alkyl glycoside are modified by introducing ethylene oxide, propylene oxide and butylene oxide. The synthesized alkyl glycoside block polyether not only retains the original excellent properties of the alkyl glycoside, but also has obvious low-foaming characteristics and a low freezing point, and is suitable for industrial cleaning.
[0006] To achieve the above object, the present invention adopts the following technical solutions:
[0007] The invention provides a method for preparing an alkyl glycoside block polyether. Alkyl glycoside and epoxy compound are used as raw materials, and the epoxy compound is introduced into the polyhydroxyl groups on the alkyl glycoside sugar skeleton for modification. The epoxy compound is at least one of propylene oxide and butylene oxide.
[0008] Furthermore, the epoxy compound is a combination of ethylene oxide and at least one of propylene oxide and butylene oxide.
[0009] Furthermore, the alkyl glycoside is a linear alkyl glycoside or a branched alkyl glycoside, and the linear alkyl glycoside includes APG0810, APG1214 and the like.
[0010] Furthermore, the polyhydroxyl groups on the glycosyl skeleton of the alkyl glycoside are modified by introducing epoxy compounds, specifically:
[0011] Step 1, melting the alkaline catalyst and the alkyl glycoside together, heating and reacting them under a nitrogen atmosphere and high pressure, and continuously stirring during the reaction;
[0012] Step 2: first introduce a portion of ethylene oxide, propylene oxide or butylene oxide to induce reaction, control the reaction temperature, continue to introduce a portion of ethylene oxide, propylene oxide or butylene oxide, continue to maintain the reaction temperature, and after the pressure no longer decreases, cool and take out the product.
[0013] Furthermore, in step 1, the melting temperature is 110-120° C., the heating reaction temperature is 160-180° C., the stirring speed is 600 r / min, and the high pressure is 0.3-0.4 MPa.
[0014] Furthermore, in step 1, the alkaline catalyst is potassium hydroxide, and the amount of the alkaline catalyst is 1-3% of the mass of the alkyl glycoside block polyether.
[0015] Furthermore, in step 2, the reaction temperature is controlled to be 160-180°C.
[0016] Furthermore, in step 2, the average addition number of ethylene oxide is 0-8, the average addition number of propylene oxide is 0-8, and the average addition number of butylene oxide is 0-8, but the average addition numbers of ethylene oxide, propylene oxide and butylene oxide cannot be 0 at the same time.
[0017] The reaction synthesis route of the present invention is shown in the figure below:
[0018]
[0019] Among them, a, b, c, d, e, f, g, h, i, j, k, and l are the added mole numbers of ethylene oxide, propylene oxide, and butylene oxide.
[0020] The present invention also provides an alkyl glycoside block polyether prepared by the above preparation method, and the active matter content of the product reaches more than 99%. The present invention prepares a new surfactant alkyl glycoside block polyether, the molecule contains glycoside units, polyoxyethylene chains, polyoxypropylene chains, polyoxybutylene chains, and has the advantages of hydrophilicity, low foaming, low freezing point, etc.
[0021] Compared with the prior art, the present invention has the following advantages:
[0022] (1) The raw materials used in the present invention are obtained from natural raw materials, and the product is green and environmentally friendly.
[0023] (2) The novel surfactant alkyl glycoside block polyether developed by the present invention has the advantages of low foaming and easy rinsing, which is beneficial to water and energy saving.
[0024] (3) The product developed by the present invention has a low freezing point, is easy to transport, and is convenient for mixing ingredients.
[0025] (4) The product preparation process developed by the present invention is simple and mature, which is conducive to industrial production and suitable for low-foam application scenarios. DETAILED DESCRIPTION
[0026] In order to further illustrate the technical solution of the present invention, the present invention is further described below through embodiments.
[0027] Example 1
[0028] Raw material APG0810 150g, catalyst KOH 3g, PO 120g, EO 37g.
[0029] The catalyst and APG0810 were melted at 110-120°C and all added to a high-pressure reactor. The gas was replaced with high-purity nitrogen for 3 times. The high-pressure reactor was heated to 180°C, the speed of the reactor was controlled at 600r / min, the reaction pressure was controlled at 0.3-0.4MPa, a small amount of PO was introduced first for induction reaction, the reaction temperature was controlled at 160-180°C, and a target amount of PO was continuously introduced into the reactor; after the addition was completed, the reaction temperature was maintained, and after the pressure in the reactor no longer decreased, a target amount of EO was continuously introduced into the reactor; after the addition was completed, the reaction temperature was maintained, and after the pressure in the reactor no longer decreased, the product APGP5E2 was cooled and taken out (the average addition number of PO was 5, the average addition number of EO was 2, and the same applies to the other embodiments).
[0030] Example 2
[0031] Raw material APG0810130g, catalyst KOH 3g, PO 104g, EO 64g.
[0032] The catalyst and APG0810 are melted at 110-120°C and all added to a high-pressure reactor. The high-purity nitrogen is replaced for 3 times. The high-pressure reactor is heated to 180°C, the speed of the reactor is controlled at 600r / min, the reaction pressure is controlled at 0.3-0.4MPa, a small amount of PO is introduced first to induce the reaction, the reaction temperature is controlled at 160-180°C, and the target amount of PO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continued to be maintained, and after the pressure in the reactor no longer decreases, the target amount of EO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continued to be maintained, and after the pressure in the reactor no longer decreases, the product APGP5E4 is cooled and taken out.
[0033] Example 3
[0034] Raw material APG1214150g, catalyst KOH 4g, PO 190g, EO 72g.
[0035] The catalyst and APG1214 were melted at 110-120°C and all added to the autoclave. The autoclave was replaced with high-purity nitrogen for 3 times. The autoclave was heated to 180°C. The speed of the autoclave was controlled at 600r / min and the reaction pressure was controlled at 0.3-0.4MPa. A small amount of PO was introduced to induce the reaction. The reaction temperature was controlled at 160-180°C. The target amount of PO was continuously introduced into the autoclave. After the addition was completed, the reaction temperature was maintained. After the pressure in the autoclave stopped decreasing, the target amount of EO was continuously introduced into the autoclave. After the addition was completed, the reaction temperature was maintained. After the pressure in the autoclave stopped decreasing, the product APGP8E4( was cooled and taken out.
[0036] Example 4
[0037] Raw material APG1214130g, catalyst KOH 4g, BO 199g, EO 94g.
[0038] The catalyst and APG1214 are melted at 110-120°C and all added to a high-pressure reactor. The gas is replaced with high-purity nitrogen for 3 times, and the high-pressure reactor is heated to 180°C. The speed of the reactor is controlled at 600r / min, and the reaction pressure is controlled at 0.3-0.4MPa. A small amount of BO is introduced first to induce the reaction, and the reaction temperature is controlled at 160-180°C. The target amount of BO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continuously maintained, and after the pressure in the reactor no longer decreases, the target amount of EO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continuously maintained, and after the pressure in the reactor no longer decreases, the product APGB8E6 is cooled and taken out.
[0039] Example 5
[0040] The raw material is APG1214130g, the catalyst is KOH 4g, BO accounts for 98g, PO accounts for 81g, and EO accounts for 125g.
[0041] The catalyst and APG1214 are melted at 110-120°C and all added to a high-pressure reactor. The gas is replaced with high-purity nitrogen for 3 times, the high-pressure reactor is heated to 180°C, the speed of the reactor is controlled at 600r / min, the reaction pressure is controlled at 0.3-0.4MPa, a small amount of BO is introduced first for induction reaction, the reaction temperature is controlled at 160-180°C, and a target amount of BO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is maintained, and after the pressure in the reactor no longer decreases, a target amount of PO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is maintained, and after the pressure in the reactor no longer decreases, a target amount of EO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is maintained, and after the pressure in the reactor no longer decreases, a product APGB4P4E8 is taken out after cooling.
[0042] Example 6
[0043] Raw material: APG1214150g, catalyst: KOH 3g, EO 36g.
[0044] The catalyst and APG0810 were melted at 110-120°C and all added to a high-pressure reactor. The gas was replaced with high-purity nitrogen for 3 times. The high-pressure reactor was heated to 180°C, the speed of the reactor was controlled at 600r / min, the reaction pressure was controlled at 0.3-0.4MPa, a small amount of EO was introduced first to induce the reaction, the reaction temperature was controlled at 160-180°C, and the target amount of EO was continuously introduced into the reactor. After the addition was completed, the reaction temperature was maintained, and when the pressure in the reactor no longer decreased, the product APGE2 was cooled and taken out.
[0045] Example 7
[0046] Raw material APG1214100g, catalyst KOH 2g, BO153g.
[0047] The catalyst and APG1214 were melted at 110-120°C and added into a high-pressure reactor. The gas was replaced with high-purity nitrogen for 3 times. The high-pressure reactor was heated to 180°C, the speed of the reactor was controlled at 600r / min, the reaction pressure was controlled at 0.3-0.4MPa, a small amount of BO was introduced to induce the reaction, the reaction temperature was controlled at 160-180°C, and the target amount of BO was continuously introduced into the reactor. After the addition was completed, the reaction temperature was maintained, and when the pressure in the reactor no longer decreased, the product APGB8 was cooled and taken out.
[0048] Comparative Example 1
[0049] The raw material is APG1214130g, the catalyst double metal cyanide complex is 1g, PO accounts for 165, and EO accounts for 63g.
[0050] The catalyst and APG1214 are melted at 110-120°C and all added to a high-pressure reactor. The high-purity nitrogen is replaced for 3 times, the high-pressure reactor is heated to 180°C, the speed of the reactor is controlled at 600r / min, the reaction pressure is controlled at 0.3-0.4MPa, a small amount of PO is introduced first to induce the reaction, the reaction temperature is controlled at 160-180°C, and the target amount of PO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continued to be maintained, and after the pressure in the reactor no longer decreases, the target amount of EO is continuously introduced into the reactor; after the addition is completed, the reaction temperature is continued to be maintained, and after the pressure in the reactor no longer decreases, the product APGP8E4 is cooled and taken out.
[0051] The foam performance of the products prepared in the above examples was tested. Surfactant solutions of each product with a mass concentration of 0.25% were prepared respectively, and the foam performance of the surfactant was measured by a Roche foam meter at 50°C according to the GB / T13173.6-1991 method. The foaming ability and foam stability of the surfactant were evaluated according to the foam height generated when a certain volume of surfactant solution flowed into the Roche foam meter from a certain height. The results are shown in Table 1.
[0052] Table 1 Foam properties of the products in the examples
[0053]
[0054] As can be seen from Table 1, the prepared series of alkyl glycoside block polyether products have low foam and are a type of low-foam nonionic surfactant. In Examples 4 and 5, butylene oxide (BO) is added, and the products hardly produce foam, and the foam performance of the products is better than that of Examples 1-3. After adding ethylene oxide (EO) alone to Example 6, foam is generated in the product within 5 minutes, and it is obvious that the foam performance of the product is relatively poor. In Example 7, butylene oxide (BO) is added alone, and no foam is generated in the product within 5 minutes. Obviously, adding butylene oxide can significantly improve the foam performance of the product. Comparative Example 1 uses a double metal cyanide complex as a catalyst, and its foam performance is worse than that of Example 3.
Claims
1. A method for preparing an alkyl glycoside block polyether, characterized in that: Alkyl glycoside and epoxy compound are used as raw materials, and epoxy compound is introduced into the polyhydroxyl groups on the sugar skeleton of alkyl glycoside for modification, wherein the epoxy compound is at least one of propylene oxide and butylene oxide.
2. The method for preparing an alkyl glycoside block polyether according to claim 1, characterized in that: The epoxy compound is a combination of ethylene oxide and at least one of propylene oxide and butylene oxide.
3. The method for preparing an alkyl glycoside block polyether according to claim 1 or 2, characterized in that: The alkyl glycoside is a straight-chain alkyl glycoside or a branched-chain alkyl glycoside.
4. The method for preparing an alkyl glycoside block polyether according to any one of claims 1 to 3, characterized in that: The polyhydroxyl groups on the glycosyl skeleton of the alkyl glycoside are modified by introducing epoxy compounds, specifically: Step 1, melting the alkaline catalyst and the alkyl glycoside together, heating and reacting them under a nitrogen atmosphere and high pressure, and continuously stirring during the reaction; Step 2: first introduce a portion of ethylene oxide, propylene oxide or butylene oxide to induce reaction, control the reaction temperature, continue to introduce a portion of ethylene oxide, propylene oxide or butylene oxide, continue to maintain the reaction temperature, and after the pressure no longer decreases, cool and take out the product.
5. The method for preparing an alkyl glycoside block polyether according to claim 4, characterized in that: In the step 1, the melting temperature is 110-120° C., the heating reaction temperature is 160-180° C., the stirring speed is 600 r / min, and the high pressure is 0.3-0.4 MPa.
6. The method for preparing an alkyl glycoside block polyether according to claim 4, characterized in that: In the step 1, the alkaline catalyst is potassium hydroxide, and the amount of the alkaline catalyst used is 1-3% of the mass of the alkyl glycoside block polyether.
7. The method for preparing an alkyl glycoside block polyether according to claim 4, characterized in that: In step 2, the reaction temperature is controlled to be 160-180°C.
8. The method for preparing an alkyl glycoside block polyether according to claim 4, characterized in that: In step 2, the average addition number of ethylene oxide is 0-8, the average addition number of propylene oxide is 0-8, and the average addition number of butylene oxide is 0-8, but the average addition numbers of ethylene oxide, propylene oxide and butylene oxide cannot be 0 at the same time.
9. The alkyl glycoside block polyether prepared by the preparation method according to any one of claims 1 to 8.