An epoxide derivative, its preparation method and application

Abstract

This invention discloses an epoxide derivative, its preparation method, and its application. The epoxide derivative has the chemical structure shown in formula (I): R-O-(EO). a -(PO) b - [(EO) c -(PO) d ] n - (EO) e -(PO) f -H (I); where R represents a C4-C32 straight-chain or branched alkyl group, and the [(EO)] c -(PO) d ] n The total block unit represents n (EO)-(PO) blocks linked together, where n ranges from 2 to 16. c and d represent the average molar number of EO and PO in the total block unit, with values ​​ranging from 1 to 10 and 1 to 2.5, respectively. a, b, e, and f each represent the average molar number, with values ​​of a and e ranging from 0 to 10, and values ​​of b and f ranging from 0 to 30. The epoxy alkyl derivatives of this invention combine low-temperature flowability, water solubility, and safety, and can be used as high-performance surfactants.

Description

Technical Field

[0001] This invention relates to the field of polymer technology, specifically to an epoxide derivative, its preparation method, and its application. Background Technology

[0002] Fatty alcohol polyoxyethylene ethers, as an important class of nonionic surfactants, possess significant advantages such as wide availability of raw materials, mature preparation processes, and suitability for large-scale industrial production. Furthermore, their production cost is lower than other types of surfactants, leading to their widespread application in various technological fields, including cosmetics, household detergents, industrial cleaning agents, and textile printing and dyeing auxiliaries. However, existing fatty alcohol polyoxyethylene ethers all have limitations in their applications due to differences in performance.

[0003] Some traditional short-chain fatty alcohol polyethers (such as lauryl ether-4 and C12-14 secondary alkyl alcohol polyether-5) are difficult to dissolve in water at room temperature, requiring the addition of an additional co-solvent to achieve uniform dissolution in water. To improve the water solubility of these substances, existing technologies typically employ increasing the molar number of ethylene oxide additions to enhance the hydrophilic-lipophilic balance (HLB) value of the target product. However, for fatty alcohol polyoxyethylene ethers, excessively long ethylene oxide (EO) segments in their molecular structure significantly increase the crystallization temperature of the surfactant, leading to poor low-temperature fluidity. They may exhibit a solid or soft solid state at room temperature and are highly susceptible to stability issues such as layering and solidification. This phenomenon increases the number of operational steps during production, thus limiting their widespread application in low-temperature environments. Furthermore, solid solubilizers at room temperature increase the complexity of the process. Solid solubilizers need to be heated and mixed with the solubilized substance before solubilization, which not only increases the difficulty of operation but may also cause other problems: if the solubilized substance is a fragrance, there is a risk of fragrance volatilization; if the solubilized substance is a substance that is unstable at high temperatures, such as retinol, its efficacy will be greatly reduced due to heating; if used in cleaning products, the product may precipitate fatty alcohol polyoxyethylene ethers at low temperatures, which will lead to a significant reduction in cleaning performance.

[0004] Furthermore, existing technologies can also improve water solubility by introducing propylene oxide (PO) to increase the molecular weight of the product. Studies have found that when the molecular weight of such substances reaches a suitable range, their water solubility also improves. However, it should be noted that if EO / PO forms a large, regularly arranged molecular chain structure through block copolymerization, it will also lead to poor low-temperature flowability; if EO / PO adopts random addition, although it solves the problems of low-temperature flowability and water solubility, the randomness of the molecular chain structure will lead to a decrease in surface activity, reducing its cleaning, emulsifying, and other properties.

[0005] Although existing low molecular weight (weight average molecular weight below 1000) isomeric fatty alcohol polyethers or secondary alkanol polyethers can balance low-temperature flowability, water solubility, and surface activity, significant safety defects have been exposed in practical applications. Specifically, lower molecular weight isomeric fatty alcohol polyethers or secondary alkanol polyethers are highly lipophilic, readily binding to lipids in the skin barrier, disrupting intercellular lipid arrangement, thereby damaging the skin barrier, causing irritation, and raising safety concerns.

[0006] Therefore, none of the reported fatty alcohol polyoxyethylene ethers can simultaneously maintain good surface activity while ensuring low-temperature stability, water solubility, and safety. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the purpose of this invention is to provide an epoxide derivative, its preparation method, and its application.

[0008] The objective of this invention is achieved through the following technical solution: In a first aspect, the present invention provides an alkylene oxide derivative having the chemical structure shown in formula (I): RO-(EO) a -(PO) b -[(EO) c -(PO) d ] n - (EO) e -(PO) f -H (I) Wherein, R represents a straight-chain or branched alkyl group of C4 to C32, and R is connected to O through any one of its carbon atoms; EO is vinyl oxide, and PO is propylene oxide; The aforementioned [(EO)] c -(PO) d ] n The total block unit represents n (EO)-(PO) blocks connected together, where n ranges from 2 to 16. c and d represent the total average number of moles of EO and PO in the total block unit, where c ranges from 1 to 10 and d ranges from 1 to 2.5. In each (EO)-(PO) block, the average number of moles of EO may be the same or different, and the average number of moles of PO may be the same or different. The values ​​a, b, e, and f represent the average number of moles, with a and e each ranging from 0 to 10, and b and f each ranging from 0 to 30.

[0009] As a preferred embodiment, in the chemical structure shown in formula (I), a and f take values ​​of 0, b and e take values ​​other than 0, c takes values ​​of 2 to 7, and d takes values ​​of 1 to 2.5.

[0010] As a preferred embodiment, in the chemical structure shown in formula (I), a and f take values ​​of 0, b takes values ​​of 3 to 15, and e takes values ​​of 4 to 7.

[0011] As a preferred embodiment, in the chemical structure shown in formula (I), a takes the value of 1 to 10; b takes the value of 1 to 30; e takes the value of 0; and f takes the value of 1 to 30.

[0012] As a preferred embodiment, in the chemical structure shown in formula (I), a takes the value of 8; b takes the value of 1 to 2; e takes the value of 0; and f takes the value of 9 to 12.

[0013] As a preferred embodiment, in the chemical structure shown in formula (I), R represents a straight-chain alkyl group of C4 to C18 or a branched alkyl group of C4 to C32; The C4-C32 branched alkyl groups include C4-C32 secondary alkyl groups and other C4-C32 branched alkyl groups.

[0014] As a preferred embodiment, R represents a straight-chain alkyl group of C12 to C18, a secondary-chain alkyl group of C9 to C24, or other branched alkyl groups of C12 to C24.

[0015] As a preferred embodiment, the weight-average molecular weight of the epoxy alkyl derivative is 1000~5000; when the weight-average molecular weight of the epoxy alkyl derivative is greater than 5000, the molecular diffusion rate will be slowed down, resulting in low cleaning efficiency; and if applied to skin cleansing products, the skin feel will become thick and sticky.

[0016] As a further preferred embodiment, the weight-average molecular weight of the epoxide derivative is 1500-3000. Performance is optimal within this weight-average molecular weight range.

[0017] Secondly, the present invention provides a method for preparing the aforementioned epoxide derivatives, characterized by comprising the following steps: Under catalytic conditions, straight-chain or branched alkanols of C4 to C32 are subjected to addition reactions with ethylene oxide and propylene oxide in the order of adducts to obtain the alkyl oxide derivatives.

[0018] As a preferred embodiment, the C4-C32 straight-chain or branched alkanols are selected from C4-C18 straight-chain alkanols or C4-C32 branched alkanols; The C4-C32 branched alkanols include C4-C32 secondary alkanols and other C4-C32 branched alkanols.

[0019] As described above, the C4-C18 straight-chain alkanols include at least one of n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, and n-octadecanol. When the number of carbon atoms in the straight-chain alkanol used in this invention is greater than 18, it will result in a crystallization point higher than 20°C and poor low-temperature fluidity.

[0020] The C4 to C32 secondary alkanols mentioned above include at least one of the following: 1-ethyloctanol, 1-ethyldecanol, 1-ethylundecanol, 1-ethyldodecanol, 1-propylnonanol, 1-propyldecanol, 1-propylundecanol, 1-butyloctanol, 1-butylnonanol, 1-butyldecanol, 1-butyldodecanol, 1-butyltetradecanol, 1-pentylheptanol, 1-pentyloctanol, 1-pentylnonanol, 1-hexylheptanol, 1-hexyloctanol, 1-hexyldecanol, 1-hexyldodecanol, 1-hexyltetradecanol, 1-hexylhexadecanol, 1-heptadecanol, 1-octyldecanol, 1-octyldodecanol, 1-octyltetradecanol, 1-octylhexadecanol, 1-octyloctadecanol, 1-decyltetradecanol, etc. Other branched alkanols of C4 to C32 as described above include at least one of isobutanol, isopentanol, isohexylol, isohepanol, isooctanol, isononanol, isodecanol, isotriadecanol, isohexadecanol, isostearyl alcohol, isoeicoserotonol, isoeicoserotonol, 2-butyl-1-octanol, 2-hexyl-1-decanol, 2-octyl-1-dodecylol, 2-decyl-1-tetradecylol, and 2-myristyl-1-octadecylol.

[0021] As a further preferred embodiment, the C4-C32 straight-chain or branched alkanols are selected from C12-C18 straight-chain alkanols, C9-C24 secondary alkanols, or other C12-C24 branched alkanols.

[0022] Thirdly, the present invention provides the use of the aforementioned epoxide derivatives in the preparation of surfactants.

[0023] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention provides an epoxy alkane derivative formed by incorporating multiple (EO)-(PO) blocks into straight-chain or branched alkanols of C4 to C32. This derivative has excellent low-temperature fluidity, water solubility and safety, and good surface activity, and can be used to prepare surfactants.

[0024] 2. By further optimizing the structure of epoxide derivatives, this invention can significantly improve solubility and cleaning performance. Attached Figure Description

[0025] Figure 1Photographs showing the solubility evaluation of the alkyl oxide derivatives prepared in Examples 1 and 3 and Comparative Examples 1 and 3; Figure 2 The fouling removal rates of the epoxy alkane derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3 were evaluated by gravimetric method. Figure 3 Photos of the washing solutions prepared using the epoxy alkyl derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3 for soiled cloth before and after cleaning. Figure 4 The dirt removal rate results of the epoxy alkyl derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3 were obtained by evaluating the whiteness value method. Figure 5 Time-of-flight mass spectra of the epoxy alkane derivatives prepared in Example 1; Figure 6 This is a magnified view of the time-of-flight mass spectrometry region of the epoxide derivatives prepared in Example 1. Detailed Implementation

[0026] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0027] The terms "preferred," "more preferably," and "most preferably" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0028] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention. It is not at all an attempt to limit the application of the doctrine of equivalents to the scope of the claims; each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0029] Although the numerical ranges and parameters illustrating the broad scope of the invention are approximate, the values ​​listed in the specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in their respective test measurements.

[0030] In a specific embodiment of the present invention, an epoxide derivative is provided, the epoxide derivative having the chemical structure shown in formula (I): RO-(EO) a -(PO) b -[(EO) c -(PO) d ] n - (EO) e -(PO) f -H (I) In formula (I), R represents a straight-chain or branched alkyl group of C4 to C32; preferably, R represents a straight-chain alkyl group of C4 to C18 or a branched alkyl group of C4 to C32, wherein the branched alkyl group of C4 to C32 includes secondary alkyl groups of C4 to C32 and other branched alkyl groups of C4 to C32; more preferably, R represents a straight-chain alkyl group of C12 to C18, a secondary alkyl group of C9 to C24 or other branched alkyl groups of C12 to C24, which can further improve low-temperature fluidity.

[0031] In equation (I), [(EO)] c -(PO) d ] n The total block unit represents n (EO)-(PO) blocks connected together, where n ranges from 2 to 16. c and d represent the average total molar number of EO and PO in the total block unit, where c ranges from 1 to 10 and d ranges from 1 to 2.5. The values ​​of c and d have a significant impact on low-temperature fluidity; exceeding these ranges will lead to poor low-temperature fluidity. In a specific embodiment of the invention, c ranges from 2 to 7.

[0032] In each (EO)-(PO) block, the average molar number of EO may be the same or different, and the average molar number of PO may be the same or different. Specifically, the [(EO)]... c -(PO) d ] n For [(EO) c1 -(PO) d1 -(EO) c2 -(PO) d2 -(EO) c3 -(PO) d3 -……1-(EO) cn -(PO) dn], where c1, c2, c3...c n The average number of moles may be the same or different, d1, d2, d3...d n The average number of moles may be the same or different; c is c1, c2, c3...c n The average value of d is d1, d2, d3...d n The average value. When the values ​​of c1, c2, c3...c n The average number of moles is the same and d1, d2, d3...d n When the average number of moles is the same, it represents n repeated (EO)-(PO) blocks; when the c1, c2, c3...c n The average number of moles varies and / or d1, d2, d3...d n When the average number of moles is not the same, it represents n (EO)-(PO) blocks with different average moles of EO and / or different average moles of PO.

[0033] In equation (I), a, b, e, and f each represent the number of moles, with a and e each taking values ​​from 0 to 10, and b and f each taking values ​​from 0 to 30. Preferably, a and b are not simultaneously 0, and e and f are not simultaneously 0, that is, in the total block unit [(EO)] c -(PO) d ] n At least one end needs to be connected to the EO block and / or the PO block. More preferably, a and f are 0, and b and e are not 0, that is, in the total block unit [(EO)] c -(PO) d ] n The front end needs to be connected to the PO block and the rear end needs to be connected to the EO block. This structure can improve solubility and cleaning performance.

[0034] In one specific embodiment, the weight-average molecular weight of the epoxide derivative is 1000-5000.

[0035] In a specific embodiment of the present invention, a method for preparing alkyl oxide derivatives is also provided. Under catalytic conditions, straight-chain or branched alkanols of C4 to C32 are subjected to addition reactions with ethylene oxide and propylene oxide in the order of adducts to obtain the alkyl oxide derivatives.

[0036] In one specific embodiment, the C4-C32 straight-chain or branched alkanols used can be a single raw material or a mixture of raw materials. The C12-14 secondary alkanol mixture, C22-24 secondary alkanol mixture, and C9-11 secondary alkanol mixture used in the following examples can all be prepared by conventional methods. For example, they can be obtained by oxidizing or alcoholizing a mixture of corresponding saturated aliphatic hydrocarbons; this invention does not impose any particular limitation. The proportions of the individual secondary alkanols in the C12-14, C22-24, or C9-11 secondary alkanol mixtures are arbitrary and this invention does not impose any particular limitation.

[0037] In one specific embodiment, the reaction is carried out using conventional ethylene oxide addition methods and propylene oxide addition methods. When ethylene oxide and propylene oxide are added in each step, with 1 mole of hydroxyl groups in the C4-C32 straight-chain or branched alkanols, the corresponding feed moles of ethylene oxide and propylene oxide are as follows: ethylene oxide 0-10 moles, propylene oxide 0-30 moles, ethylene oxide 2-7 moles, propylene oxide 1-2.5 moles, ethylene oxide 2-7 moles, propylene oxide 1-2.5 moles… ethylene oxide 0-10 moles, propylene oxide 0-30 moles, thereby obtaining the corresponding structure described in formula (I). Further, when the C4-C32 straight-chain or branched alkanols undergo an addition reaction with ethylene oxide to form -EO… a -In the block stage, ethylene oxide can undergo a one-step ethylene oxide addition reaction with a single feed, or it can undergo a two-step ethylene oxide addition reaction with two feeds to obtain -EO. a - Block. When a straight-chain or branched alkanol (C4-C32) directly adds to propylene oxide to form -PO b - In the block stage, the propylene oxide addition reaction can be carried out in a single feed in one step, or in two feeds in a two-step propylene oxide addition reaction to obtain -PO. b - Segmentation.

[0038] In the following examples, all raw materials used were commercially available. For example, the mixture of saturated aliphatic hydrocarbons with 12-14 carbon atoms was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., which produced a standard mixture of n-paraffin (including C12, C13, and C14); the mixture of saturated aliphatic hydrocarbons with 22-24 carbon atoms was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., which produced a standard mixture of n-paraffin (including C22, C23, and C24); 1-dodecanool (lauratel) was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.; C24 branched alkanol was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., which produced 2-decyl-1-tetradecanool; and the mixture of saturated aliphatic hydrocarbons with 9-11 carbon atoms was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., which produced a standard mixture of n-paraffin (including C9, C12, C13, and C14). C10 and C11); n-Butanol was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.; 2-Myristyl-1-octadecyl alcohol was purchased from THIAI (Shanghai) Chemical Industry Development Co., Ltd.

[0039] Example 1 This embodiment provides an epoxide derivative (I-1) with the following chemical structure: C12~C14 secondary alkyl-O-PO 13 -(EO 4.25 -PO1)4-EO4-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 13, c is 4.25, d is 1, e is 4, f is 0, and n is 4.

[0040] The specific preparation steps of the epoxide derivative (I-1) are as follows: (1) Oxidation process and alcoholization process 1.1 A mixture of 1000 g (5.43 mol) of saturated aliphatic hydrocarbons with 12-14 carbon atoms (average molecular weight: 184) and 25 g (0.40 mol) of metaboric acid were added to a cylindrical reactor with a capacity of 3 L. A gas with an oxygen concentration of 3.5 vol% and a nitrogen concentration of 96.5 vol% was blown in at a ratio of 430 L per hour. The oxidation reaction was carried out at atmospheric pressure and 170 °C for 2 hours.

[0041] 1.2 Half of the oxidation reaction mixture obtained in step 1.1 was taken out and hydrolyzed with a large volume of hot water (95 °C). The generated alcohol entered the oil phase, which was then separated. The remaining half of the oxidation reaction mixture was mixed with the above oil phase, and boric acid (adjusted to 1.04 equivalents) was added. The mixture was then borate esterified at 200 hPa and 170 °C. The mixture containing the orthoborate ester was heated to 170 °C at 7 hPa for flash evaporation to remove unreacted saturated aliphatic hydrocarbons. Next, the residue was hydrolyzed with a large volume of hot water at 95 °C, and the boric acid was removed by dissolving in water. The resulting oil phase was saponified and washed with water to remove organic acids and organic esters. The resulting oil phase was fractionated at 7 hPa. The first fraction (boiling point range above 95 °C and below 120 °C) was a mixture of small amounts of paraffin, carbonyl compounds, and monohydric primary alcohols. The second fraction (boiling point range 120–150 °C) is a mixture of C12–14 secondary alkanols, containing only trace amounts of carbonyl compounds and polyols.

[0042] (2) Propylene oxide addition process One kg (4.99 mol) of the C12-14 secondary alkanol mixture obtained in step (1) above was added to a 3 L SUS autoclave equipped with a stirrer, thermometer, and propylene oxide (PO) and purged with nitrogen. Then, 1.68 g (0.01 mol) of BF3-Et catalyst (BF3: 46-49%) was added, and addition was carried out at an initial nitrogen pressure of 0.05 MPa and 55 ± 5 °C, with 1.7 mol of propylene oxide (PO) fed relative to 1 mol of hydroxyl group. NaOH solution was then added, and the reaction solution was washed at 90 °C, followed by further washing with water until the pH was below 7. Next, the washed reaction solution was transferred to a 3 L glass three-necked flask, and a distillation column (40 mm inner diameter, 200 mm length, and 3 theoretical plates) was installed for distillation, thereby obtaining a propylene oxide adduct with an average addition of 3 mol of hydroxyl group. The hydroxyl value of the propylene oxide adduct was measured to be 155.0.

[0043] (3) Addition process of ethylene oxide and propylene oxide 3.1 400 g (1.07 mol) of the propylene oxide adduct obtained in step (2) was mixed with 3.4 g (0.06 mol) of potassium hydroxide and placed into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120 °C under nitrogen protection. Then, under safe pressure and at 120 °C, 620.0 g (10.68 mol) of propylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the adduct obtained in this step was measured to be 63.7.

[0044] 3.2 Weigh 62.0 g (1.07 mol) of propylene oxide and 200.0 g (4.54 mol) of ethylene oxide, respectively. First, under constant temperature of 120 °C, introduce ethylene oxide into the reactor over 30 minutes, and then maintain this temperature for 1 hour. Next, introduce propylene oxide into the reactor over 10 minutes and maintain the temperature at 120 °C for 1 hour. Repeat the above procedure three times. The hydroxyl value of the adduct obtained in this step was measured to be 34.0.

[0045] 3.3 Then, under the same pressure and temperature conditions, 188.5 g (4.27 mol) of ethylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0046] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the mixture was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-1). The hydroxyl value of the final product I-1 was found to be 32.5.

[0047] Example 2 This embodiment provides an epoxide derivative (I-2) with the following chemical structure: C22~C24 secondary alkyl chain -O-PO3+(EO) 6.33 +PO1)6+EO7-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 3, c is 6.33, d is 1, e is 7, f is 0, and n is 6.

[0048] The specific preparation steps for the epoxide derivative (I-2) are as follows: (1) Oxidation process and alcoholization process The process is the same as step (1) in Example 1, except that the mixture of saturated aliphatic hydrocarbons with 12 to 14 carbon atoms is replaced with a mixture of saturated aliphatic hydrocarbons with 22 to 24 carbon atoms (average molecular weight: 324). The final fraction with a boiling point range of 210 to 240 °C is a mixture of C22 to C24 secondary alkanols.

[0049] (2) Propylene oxide addition process The procedure is the same as step (1) in Example 1, except that the C12-14 secondary alkanol mixture is replaced with a C22-24 secondary alkanol mixture. The hydroxyl value of the resulting propylene oxide adduct was determined to be 115.0.

[0050] (3) Addition process of ethylene oxide and propylene oxide 3.1 Mix 515 g (1.00 mol) of the propylene oxide adduct obtained in step (2) with 3.2 g (0.06 mol) of potassium hydroxide, and then put the mixture into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge and nitrogen inlet pipe. After replacing the nitrogen, heat the mixture to 120 °C under nitrogen protection.

[0051] 3.2 Weigh 59.0 g (1.00 mol) of propylene oxide and 279.0 g (6.33 mol) of ethylene oxide, respectively. First, under a constant temperature of 120 °C, introduce the ethylene oxide into the reactor over 30 minutes, and then maintain this temperature for 1 hour. Next, introduce the propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. Repeat the above procedure five times. The hydroxyl value of the adduct obtained in this step was measured to be 28.2.

[0052] 3.3 Then, under the same pressure and temperature conditions, 309.0 g (7.00 mol) of ethylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0053] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-2). The hydroxyl value of the final product I-2 was 25.7.

[0054] Example 3 This embodiment provides an epoxide derivative (I-3), whose chemical structure is as follows: C12~C14 secondary alkyl chain -O-EO8-PO1-(EO 3.25 -PO1)4-PO 12 -H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 8, b is 1, c is 3.25, d is 1, e is 0, f is 12, and n is 4.

[0055] The specific preparation steps for the epoxide derivative (I-3) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 1.

[0056] (2) Ethylene oxide addition process One kg (4.99 mol) of the C12-14 secondary alkanol mixture obtained in step (1) above was added to a 3L SUS autoclave equipped with a stirrer, thermometer, and ethylene oxide (EO) and purged with nitrogen. Then, 1.68 g (0.01 mol) of BF3-Et catalyst (BF3: 46-49%) was added, and addition was carried out at an initial nitrogen pressure of 0.05 MPa and 55±5 °C, with 1.7 mol of ethylene oxide (EO) fed relative to 1 mol of hydroxyl group. NaOH solution was then added, and the reaction solution was washed at 90 °C, followed by further washing with water until the pH was below 7. Next, the washed reaction solution was transferred to a 3L glass three-necked flask, and a distillation column (Dixon packing, 40 mm inner diameter, 200 mm length, 3 theoretical plates) was installed for distillation, thereby obtaining an ethylene oxide adduct with an average addition of 3 mol of hydroxyl group. The hydroxyl value of the obtained ethylene oxide adduct was determined to be 173.5.

[0057] (3) Addition process of ethylene oxide and propylene oxide 3.1 333 g (1.00 mol) of the ethylene oxide adduct obtained in step (2) was mixed with 3.2 g (0.06 mol) of potassium hydroxide and placed in a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120°C under nitrogen protection. Then, under safe pressure and maintaining the temperature at 120°C, 221.0 g (5.00 mol) of ethylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the adduct was measured to be 106.3. Next, under the same pressure and temperature conditions, 59.0 g (1.00 mol) of propylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour. The hydroxyl value of the adduct obtained in this step was measured to be 96.6.

[0058] 3.2 Weigh 59.0 g (1.00 mol) of propylene oxide and 144.0 g (3.25 mol) of ethylene oxide, respectively. First, inject the ethylene oxide into the reactor at a constant temperature of 120 °C over 30 minutes, and then maintain this temperature for 1 hour. Next, inject the propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. Repeat the above procedure three times. The hydroxyl value of the adduct obtained in this step was measured to be 44.4.

[0059] 3.3 Then, under the same pressure and temperature conditions, 697.0 g (12.00 mol) of propylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0060] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-3). The hydroxyl value of the final product I-3 was found to be 35.0.

[0061] Example 4 This embodiment provides an epoxide derivative (I-4) with the following chemical structure: lauryl-O-PO 13 -(EO 4.25 -PO1)4-EO4-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 13, c is 4.25, d is 1, e is 4, f is 0, and n is 4.

[0062] The specific preparation steps of the epoxide derivative (I-4) are as follows: (1) Propylene oxide addition process The procedure is the same as step (2) in Example 1, except that the C12-14 secondary alkanol mixture is replaced with lauryl alcohol. The hydroxyl value of the resulting propylene oxide adduct is 160.9.

[0063] (2) Addition process of ethylene oxide and propylene oxide The same as step (3) in Example 1, including steps 2.1, 2.2, and 2.3 in sequence. The only difference is that in step 2.1, 386 g (1.07 mol) of the propylene oxide adduct obtained in step (1) is mixed with 3.4 g (0.06 mol) of potassium hydroxide.

[0064] The hydroxyl value of the propylene oxide adduct obtained in step 2.1 was 64.9. The hydroxyl value of the adduct obtained in step 2.2 was 34.5.

[0065] (3) After completing the addition reaction in step (2), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-4). The hydroxyl value of the final product I-4 was 32.0.

[0066] Example 5 This embodiment provides an epoxide derivative (I-5) with the following chemical structure: 2-decyl-1-tetradecyl-O-PO 13 -(EO 4.25 -PO1)4-EO4-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 13, c is 4.25, d is 1, e is 4, f is 0, and n is 4.

[0067] The specific preparation steps of the epoxide derivative (I-5) are as follows: (1) Propylene oxide addition process The procedure was the same as step (2) in Example 1, except that the C12-14 secondary alkanol mixture was replaced with 2-decyl-1-tetradecyl alcohol. The hydroxyl value of the resulting propylene oxide adduct was 112.6.

[0068] (2) Addition process of ethylene oxide and propylene oxide The same as step (3) in Example 1, including steps 2.1, 2.2, and 2.3 in sequence. The only difference is that in step 2.1, 566 g (1.07 mol) of the propylene oxide adduct obtained in step (1) is mixed with 3.4 g (0.06 mol) of potassium hydroxide.

[0069] The hydroxyl value of the propylene oxide adduct obtained in step 2.1 was 57.1. The hydroxyl value of the adduct obtained in step 2.2 was 33.3.

[0070] (3) After completing the addition reaction in step (2), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-5). The hydroxyl value of the final product I-5 was found to be 31.2.

[0071] Example 6 This embodiment provides an epoxide derivative (I-6) with the following chemical structure: C9~C11 secondary alkyl-O-PO 15 -(EO3-PO1-EO5-PO1-EO4-PO1)-EO6-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 15, c is 4 (where c1 is 3, c2 is 5, and c3 is 4), d is 1 (where d1, d2, and d3 are all 1), e is 6, f is 0, and n is 3.

[0072] The specific preparation steps for the epoxide derivative (I-6) are as follows: (1) Oxidation process and alcoholization process The procedure is the same as step (1) in Example 1, except that the mixture of saturated aliphatic hydrocarbons with 12 to 14 carbon atoms is replaced with a mixture of saturated aliphatic hydrocarbons with 9 to 11 carbon atoms (average molecular weight: 142). The final fraction with a boiling point range of 90 to 120 °C is a mixture of C9 to C11 secondary alkanols.

[0073] (2) Propylene oxide addition process Same as step (2) in Example 1. The hydroxyl value of the obtained propylene oxide adduct was determined to be 173.2.

[0074] (3) Addition process of ethylene oxide and propylene oxide 3.1 333 g (1.00 mol) of the propylene oxide adduct obtained in step (2) was mixed with 3.2 g (0.06 mol) of potassium hydroxide and placed into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120 °C under nitrogen protection. Then, under safe pressure and maintaining the temperature at 120 °C, 697.0 g (12.00 mol) of propylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the adduct obtained in this step was measured to be 59.0.

[0075] 3.2 Weigh 59.0 g (1.00 mol) of propylene oxide and 132.5 g (3.00 mol) of ethylene oxide respectively. First, under constant temperature of 120 °C, inject ethylene oxide into the reactor over 30 minutes, and then maintain this temperature for 1 hour. Next, inject propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. The hydroxyl value of the resulting adduct was determined to be 50.5. Then, inject 220.5 g (5.00 mol) of ethylene oxide into the reactor over 30 minutes, and then maintain this temperature for 1 hour. Next, inject 59.0 g (1.00 mol) of propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. The hydroxyl value of the resulting adduct was measured to be 41.9. Then 176.5 g (4.00 mol) of ethylene oxide was injected into the reactor over 30 minutes, and the temperature was maintained for 1 hour; then 59.0 g (1.00 mol) of propylene oxide was injected into the reactor over 10 minutes and maintained for 1 hour. The hydroxyl value of the resulting adduct was measured to be 36.9.

[0076] 3.3 Then, under the same pressure and temperature conditions, 264.5 g (6.00 mol) of ethylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0077] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-6). The hydroxyl value of the final product I-6 was 32.6.

[0078] Example 7 This embodiment provides an epoxide derivative (I-7) with the following chemical structure: C22~C24 secondary alkyl chain -O-EO8-PO2-(EO5-PO 1.5)4-PO9-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in formula I, a is 8, b is 2, c is 5, d is 1.5, e is 0, f is 9, and n is 4.

[0079] The specific preparation steps for the epoxide derivative (I-7) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 2.

[0080] (2) Ethylene oxide addition process Same as step (2) in Example 3. The hydroxyl value of the obtained ethylene oxide adduct was determined to be 124.2.

[0081] (3) Addition process of ethylene oxide and propylene oxide 3.1 473 g (1.00 mol) of the ethylene oxide adduct obtained in step (2) was mixed with 3.2 g (0.06 mol) of potassium hydroxide and placed in a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120°C under nitrogen protection. Then, under safe pressure and maintaining the temperature at 120°C, 220.5 g (5.00 mol) of ethylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the resulting adduct was 86.5. Next, under the same pressure and temperature conditions, 116.5 g (2.00 mol) of propylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour. The hydroxyl value of the adduct obtained in this step was measured to be 74.8.

[0082] 3.2 Weigh 87.5 g (1.50 mol) of propylene oxide and 220.5 g (5.00 mol) of ethylene oxide, respectively. First, inject the ethylene oxide into the reactor at a constant temperature of 120 °C over 30 minutes, and then maintain this temperature for 1 hour. Next, inject the propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. Repeat the above procedure three times. After the fourth block addition, the hydroxyl value of the adduct obtained in this step was determined to be 33.0.

[0083] 3.3 Then, under the same pressure and temperature conditions, 523.0 g (9.00 mol) of propylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0084] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-7). The hydroxyl value of the final product I-7 was 27.4.

[0085] Example 8 This embodiment provides an epoxide derivative (I-8) with the following chemical structure: C12~C14 secondary alkyl-O-PO 11 -(EO3-PO1-EO4-PO2-EO3-PO2-EO7-PO1)-EO4-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 11, c is 4.25 (where c1 is 3, c2 is 4, c3 is 3, and c4 is 7), d is 1.5 (where d1 is 1, d2 is 2, d3 is 2, and d4 is 1), e is 4, f is 0, and n is 4.

[0086] The specific preparation steps for the epoxide derivative (I-8) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 1.

[0087] (2) Propylene oxide addition process Same as step (2) in Example 1. The hydroxyl value of the propylene oxide adduct was measured to be 155.0.

[0088] (3) Addition process of ethylene oxide and propylene oxide 3.1 400 g (1.07 mol) of the propylene oxide adduct obtained in step (2) was mixed with 3.4 g (0.06 mol) of potassium hydroxide and placed into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120 °C under nitrogen protection. Then, under safe pressure and at 120 °C, 496.5 g (8.54 mol) of propylene oxide was introduced into the reactor over 3 hours, and this temperature was maintained for 5 hours. The hydroxyl value of the propylene oxide adduct obtained in this step was 72.0.

[0089] 3.2 Weigh 62.0 g (1.07 mol) of propylene oxide and 141.5 g (3.20 mol) of ethylene oxide respectively. First, inject the ethylene oxide into the reactor at a constant temperature of 120 °C over 30 minutes, and then maintain this temperature for 1 hour. Next, inject the propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. The hydroxyl value of the resulting adduct was determined to be 59.7. Then, inject 188.5 g (4.27 mol) of ethylene oxide into the reactor over 30 minutes, and then maintain this temperature for 1 hour. Next, inject 124.0 g (2.14 mol) of propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. The hydroxyl value of the resulting adduct was determined to be 47.6.

[0090] 3.3 Under the same temperature conditions, 141.5 g (3.30 mol) of ethylene oxide was injected into the reactor over 30 minutes, and this temperature was maintained for 1 hour. Then, 124.0 g (2.14 mol) of propylene oxide was injected into the reactor over 10 minutes and maintained for 1 hour. The hydroxyl value of the resulting adduct was measured to be 40.9. Next, under isothermal conditions at 120 °C, 329.5 g (7.47 mol) of ethylene oxide was injected into the reactor over 30 minutes, and this temperature was maintained for 1 hour. Then, 62.0 g (1.07 mol) of propylene oxide was injected into the reactor over 10 minutes and maintained for 1 hour. The hydroxyl value of the resulting adduct was measured to be 34.2.

[0091] 3.4 Then, under the same pressure and temperature conditions, 188.5 g (4.27 mol) of ethylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0092] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-8). The hydroxyl value of the final product I-8 was found to be 31.8.

[0093] Example 9 This embodiment provides an epoxide derivative (I-9) with the following chemical structure: n-Butyl-O-PO 13 - (EO 4.25 -PO1)4-EO4-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 13, c is 4.25, d is 1, e is 4, f is 0, and n is 4.

[0094] The specific preparation steps for the epoxide derivative (I-9) are as follows: (1) Propylene oxide addition process The procedure is the same as step (2) in Example 1, except that the C12-14 secondary alkanol mixture is replaced with commercially available n-butanol. The resulting propylene oxide adduct has a hydroxyl value of 229.9.

[0095] (2) Addition process of ethylene oxide and propylene oxide The same as step (3) in Example 1, including steps 2.1, 2.2, and 2.3 in sequence. The only difference is that in step 2.1, 266 g (1.07 mol) of the propylene oxide adduct obtained in step (1) is mixed with 3.4 g (0.06 mol) of potassium hydroxide.

[0096] The hydroxyl value of the propylene oxide adduct obtained in step 2.1 was 71.7. The hydroxyl value of the adduct obtained in step 2.2 was 35.0.

[0097] (3) After completing the addition reaction in step (2), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-9). The hydroxyl value of the final product I-9 was 32.2.

[0098] Example 10 This embodiment provides an epoxide derivative (I-10) with the following chemical structure: 2-Myristyl-1-octadecyl-O-PO 15 -(EO5-PO1)3-EO6-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, a is 0, b is 15, c is 5, d is 1, e is 6, f is 0, and n is 3.

[0099] The specific preparation steps for the epoxide derivative (I-10) are as follows: (1) Propylene oxide addition process The procedure is the same as step (2) in Example 1, except that the C12-14 secondary alkanol mixture is replaced with 2-myristyl-1-octadecyl alcohol. The resulting propylene oxide adduct has a hydroxyl value of 93.5.

[0100] (2) Addition process of ethylene oxide and propylene oxide 2.1 The only difference from step 3.1 in Example 6 is that 641 g (1.00 mol) of the propylene oxide adduct obtained in step (2) was mixed with 3.2 g (0.06 mol) of potassium hydroxide. The hydroxyl value of the adduct obtained in this step was measured to be 47.9.

[0101] 2.2 Weigh out 59.0 g (1.00 mol) of propylene oxide and 220.5 g (5.00 mol) of ethylene oxide. First, inject ethylene oxide into the reactor at a constant temperature of 120 °C over 30 minutes, and then maintain this temperature for 1 hour. Next, inject propylene oxide into the reactor over 10 minutes and maintain this temperature for 1 hour. Repeat the above procedure twice. The hydroxyl value of the adduct obtained in this step was measured to be 31.8.

[0102] 2.3 Same as step 3.3 in Example 6.

[0103] (3) After completing the addition reaction in step (2), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (I-10). The hydroxyl value of the final product I-10 was tested to be 29.0.

[0104] Comparative Example 1 This comparative example provides an epoxide derivative (II-1) with the following chemical structure: C12~C14 secondary alkyl chain -O-EO8-PO6-EO6-Random-PO9-H; wherein PO is CH3CH2CH-O and EO is CH2CH2-O.

[0105] The specific preparation steps of the epoxide derivative (II-1) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 1.

[0106] (2) Ethylene oxide addition process Same as step (2) in Example 3. The hydroxyl value of the resulting ethylene oxide adduct is 173.5.

[0107] (3) Addition process of ethylene oxide and propylene oxide 3.1 333 g (1.00 mol) of the ethylene oxide adduct obtained in step (2) was mixed with 3.2 g (0.06 mol) of potassium hydroxide and placed in a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120 °C under nitrogen protection. Then, under safe pressure and maintaining the temperature at 120 °C, 220.5 g (5.00 mol) of ethylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the resulting adduct was determined to be 106.3. Next, under the same pressure and temperature conditions, 349.0 g (6.00 mol) of propylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour. The hydroxyl value of the resulting adduct was determined to be 67.0.

[0108] 3.2 Weigh 264.5 g (6.00 mol) of propylene oxide and 523.0 g (9.00 mol) of ethylene oxide, respectively. Under constant temperature of 120℃, inject ethylene oxide and propylene oxide into the reactor simultaneously over 30 minutes, and then continue to maintain this temperature for 1 hour.

[0109] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (II-1). The hydroxyl value of the final product II-1 was tested to be 38.0.

[0110] Comparative Example 2 This comparative example provides an epoxide derivative (II-2) with the following chemical structure: C12~C14 secondary alkyl-O-EO8-PO13 -H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, c is 0 and d is 0.

[0111] The specific preparation steps of the epoxide derivative (II-1) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 3.

[0112] (2) Ethylene oxide addition process Same as step (2) in Example 3. The hydroxyl value of the resulting ethylene oxide adduct is 173.5.

[0113] (3) Addition process of ethylene oxide and propylene oxide The process is the same as step (3) in Example 3, except that the addition step 3.2 is not performed. The hydroxyl value of the adduct obtained after the addition of ethylene oxide in step 3.1 is 106.3.

[0114] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (II-2). The hydroxyl value of the final product II-2 was tested to be 47.7.

[0115] Comparative Example 3 This comparative example provides an epoxide derivative (II-3) with the following chemical structure: C12~C14 secondary alkyl-O-PO 17 -EO 21 -H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in Equation I, c is 0 and d is 0.

[0116] The specific preparation steps of the epoxide derivative (II-3) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 1.

[0117] (2) Propylene oxide addition process Same as step (2) in Example 1. The hydroxyl value of the resulting propylene oxide adduct is 155.0.

[0118] (3) Addition process of propylene oxide and ethylene oxide 400 g (1.07 mol) of the propylene oxide adduct obtained in step (2) was mixed with 3.4 g (0.06 mol) of potassium hydroxide and placed in a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet pipe. After purging with nitrogen, the mixture was heated to 120 °C under nitrogen protection. Then, under safe pressure and at 120 °C, 868.5 g (14.95 mol) of propylene oxide was introduced into the reactor over 3 hours, and the temperature was maintained for 5 hours. The hydroxyl value of the resulting adduct was determined to be 51.7. Next, under the same pressure and temperature conditions, 988.0 g (22.42 mol) of ethylene oxide was introduced into the reactor over 1 hour, and the temperature was maintained for 1 hour.

[0119] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (II-3). The hydroxyl value of the final product II-3 was found to be 31.0.

[0120] Comparative Example 4 This comparative example provides an epoxide derivative (II-4) with the following chemical structure: C22~C24 secondary alkyl chain -O-EO8-PO2-(EO 11 -PO 0.8 )4PO9-H; where PO is CH3CH2CH-O and EO is CH2CH2-O. Corresponding to the structure in formula I, a is 8, b is 2, c is 11, d is 0.8, e is 0, f is 9, and n is 4.

[0121] The specific preparation steps of the epoxide derivative (II-4) are as follows: (1) Oxidation process and alcoholization process Same as step (1) in Example 7.

[0122] (2) Ethylene oxide addition process Same as step (2) in Example 7. The resulting ethylene oxide adduct has a hydroxyl value of 124.2.

[0123] (3) Addition process of ethylene oxide and propylene oxide 3.1 Same as step 3.1 in Example 7. The hydroxyl value of the ethylene oxide adduct obtained in this step was measured to be 86.5. The hydroxyl value of the propylene oxide adduct obtained was 74.8.

[0124] 3.2 Same as step 3.2 in Example 7, except that 46.5 g (0.8 mol) of propylene oxide and 485.0 g (11.00 mol) of ethylene oxide were weighed as a set of raw materials. The hydroxyl value of the adduct obtained in this step was measured to be 24.6.

[0125] 3.3 Same as step 3.3 in Example 7.

[0126] (4) After completing the addition reaction in step (3), potassium hydroxide was neutralized by adding oxalic acid aqueous solution, and the product was dehydrated and filtered under reduced pressure to finally obtain polyoxyolefin alkyl ether (II-4). The hydroxyl value of the final product II-4 was found to be 23.6.

[0127] Characterization methods: 1. Hydroxyl value determination method: The hydroxyl values ​​of the various examples and comparative examples were determined by acetylation. The specific steps are as follows: S1: Weigh each test sample correctly into an Erlenmeyer flask and add the acetylation reagent correctly using a burette.

[0128] S2: After shaking until the sample dissolves, install an air cooler and heat in a constant temperature water bath (98±2℃) for 1 hour. Shake the mixing flask approximately every 20 minutes.

[0129] S3: After removing the product from the constant temperature water bath and allowing it to cool, add 1ml of water from the top of the air cooling tube to mix and decompose the acetic anhydride.

[0130] S4: To further achieve complete decomposition, heat the Erlenmeyer flask in a constant temperature water bath for 20 minutes. After heating for 10 minutes, shake the Erlenmeyer flask to mix.

[0131] S5: After removing the flask from the constant temperature water bath and allowing it to cool, add 10 ml of ethanol (95%) from the top of the air cooler tube while shaking it to rinse the air cooler tube and the inner wall of the flask.

[0132] S6: Remove the air cooler tube, add a few drops of 1% phenolphthalein solution as an indicator, and titrate with 0.5 mol / L potassium hydroxide ethanol solution. The endpoint is when the pale red indicator lasts for about 30 seconds.

[0133] This experiment was conducted under the same conditions in an empty environment.

[0134] The calculation formula is as follows: OHV: Hydroxyl value (KOH mg / g) B: The volume (ml) of 0.5 mol / L potassium hydroxide ethanol solution required for the empty test titration. A: The volume (ml) of 0.5 mol / L potassium hydroxide ethanol solution required for the titration of the sample. f: The f value for 0.5 mol / L sodium hydroxide S: Mass of the sample (g) AV: Acid value of the sample (KOH mg / g) The acid value of the sample should only be determined and the result corrected on specially designated occasions.

[0135] The average molecular weight of each test sample is calculated based on the obtained hydroxyl value, and the average molar addition of EO and PO is calculated based on the difference between the molecular weight of each straight-chain or branched alkanol.

[0136] 2. Time-of-flight mass spectrometry: The compounds prepared in Example 1 were characterized using matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS, instrument model BRUKERmicroflex LRF). A sample solution with a mass concentration of 0.1 mg / mL was prepared using sodium trifluoroacetate as the solvent and subjected to MALDI-TOF-MS. The resulting MALDI-TOF-MS spectra were obtained and analyzed using flexAnalysis software. The results are as follows: Figure 5 and Figure 6 As shown.

[0137] Mass spectrum analysis revealed that the obtained epoxide derivatives exhibited a broad molecular weight distribution. A strong peak was observed at m / z 2136.363, corresponding to the target molecule [M+Na]. + (Theoretical value 2135.760) Obvious characteristic fragment peaks were observed at m / z 1196.698, 1255.101, 1430.365, 1491.228, 1725.679, etc., confirming that it is consistent with the specific structural fragment fragmentation mode of the compound prepared in Example 1.

[0138] Performance testing: 1. HLB values ​​and weight-average molecular weights of the epoxide derivatives prepared in each example and comparative example.

[0139] The book *Fundamentals and Applications of Organic Concept Maps* describes how organic concept maps represent the covalently bonded portion of an organic compound, i.e., the nonpolar portion, as organic property. The degree of organic property is differentiated based on the number of carbon atoms, and this is expressed numerically as the organic property value (hereinafter referred to as the OV value). The electrostatically bonded portion of an organic compound, i.e., the polar portion, is represented as inorganic property, and this is expressed numerically based on the degree of polarity as the inorganic property value (hereinafter referred to as the IV value) (see, for example, Yoshio Koda, *Fundamentals and Applications of Organic Concept Maps*, Chapter 1, Section 1, Organic Concept Maps, p. 5, published in 1984).

[0140] IOB value: The ratio of inorganic value to organic value (IV / OV = IOB) is called the organic-inorganic balance value. For example, the "organic value" of each carbon atom in a molecule is 20; the "inorganic value" of each ether bond is 20. The first ether bond in polyoxyethylene has an "inorganic value" of 20, and from the second bond onwards, the "inorganic value" of each ether bond is 75. When polyoxyethylene is interrupted by other substances, the "inorganic value" of the ether bond needs to be recalculated according to 20. The "inorganic value" of each hydroxyl group is 100. The organic value of branched compounds should be calculated by subtracting 10 (refer to Yoshio Koda, *Fundamentals and Applications of Organic Concept Maps*, Chapter 1, Section 1, Organic Concept Maps, pp. 16-18, published in 1984).

[0141] Each atom or functional group in a molecule has its corresponding "inorganic value" and "organic value". The IOB value of an organic compound can be calculated by dividing the "inorganic value" and "organic value" of all atoms and functional groups in the compound. In addition, Oda et al. proposed HLB≈IOB×10 using Fujita's organic concept map (see Yoshio Koda, "Fundamentals and Applications of Organic Concept Maps", Chapter 3, Section 1, Applications in Surfactants, pp. 99-103, published in 1984).

[0142] Based on the above references, the HLB values ​​of the epoxide derivatives prepared in this invention were calculated.

[0143] The weight-average molecular weight was obtained according to GB / T 21863-2008 "Gel permeation chromatography (GPC) using tetrahydrofuran as eluent". The weight-average molecular weight was determined using the apparatus described below and under the conditions described below.

[0144] Equipment: HLC-8320 GPC (manufactured by Higashi Sou Co., Ltd.) Chromatographic columns: TSKgel SuperMultiporeHZ-M (2 columns), TSKgel SuperHZ2000, TSKgel SuperHZ1000 (manufactured by Higashi Sou Co., Ltd.); Column temperature: 40℃; Eluent: Tetrahydrofuran; Elution buffer flow rate: 0.3 mL / min; Sample solution filtration: A disposable filter membrane with a pore size of 0.45μm made of polytetrafluoroethylene is used; Injection volume: 10 μL; Analysis software: EcoSEC (TOHOS); Detectors: RI, UV; Standard sample: Polyethylene glycol sample; Concentration: 0.5% tetrahydrofuran solution; Collection time: 10-32 mins.

[0145] The HLB values ​​and weight-average molecular weights of the epoxide derivatives prepared in each example and comparative example are shown in Table 1.

[0146] Table 1 2. The low-temperature flowability, water solubility, and safety of the epoxy alkyl derivatives prepared in each example and comparative example, as well as the commercially available product SOLUBULE GS-01, were evaluated.

[0147] 2.1 Low-temperature fluidity evaluation Weigh a certain amount of sample (epoxide derivatives prepared in each example and comparative example or commercially available product GS-01) into a beaker, then place the beaker in a cooling device to slowly cool it down, cooling it down by 1°C every 2 minutes. Observe the fluidity of the sample and record the temperature at which it no longer flows as the solidification temperature.

[0148] The evaluation criteria for low-temperature fluidity are as follows: ◎: Solidification temperature <0℃, excellent low-temperature fluidity; △: Solidification temperature is 0-20℃, with good low-temperature fluidity; ×: Solidification temperature > 20℃, poor low-temperature fluidity.

[0149] 2.2 Water solubility evaluation At room temperature, a certain amount of sample (epoxide derivatives prepared in each example and comparative example or commercially available product GS-01) was added to water and stirred for 5 minutes at 450 rpm to obtain a 10% sample solution. After standing for 30 minutes, the state of each sample solution was observed.

[0150] The evaluation criteria for water solubility are as follows: ◎Clear and transparent: The material is colorless and transparent, and the black and white checkered background can be clearly seen; ○ Slight turbidity: The material is slightly turbid, and the black and white checkered background can be clearly seen; △Moderate turbidity: The material has a certain degree of turbidity, and the black and white checkered background can be vaguely seen; × Severe turbidity or layering: The material is severely turbid, and the black and white checkered background cannot be seen; or the material is layered.

[0151] 2.3 Safety Evaluation In vitro assessment of eye irritation was conducted according to SN / T2329—2009 "Eye Irritation / Corrosivity of Cosmetics - Chicken Embryo Villi Allantoic Membrane Test".

[0152] The safety evaluation criteria are as follows: ◎Non-irritating: ES ≤ 6; Mild irritation: 6 <ES≤ 12 ; △ Moderate irritation: 12 <ES≤ 16 ; ×Strongly irritating / corrosive: 16 <ES。

[0153] The evaluation results of low-temperature fluidity, water solubility and safety are shown in Table 2.

[0154] Table 2 As shown in Table 1, the epoxy alkyl derivatives prepared in the various embodiments of the present invention possess good low-temperature fluidity (solidification temperature below 20°C), water solubility (clear and transparent), and safety (non-irritating). Further optimization by using C12-C18 straight-chain alkyl groups, C9-C24 secondary-chain alkyl groups, or other C12-C24 branched alkyl groups significantly improves the low-temperature fluidity of the epoxy alkyl derivatives (the solidification temperatures of formulas I-1 to I-9 are all below 0°C). However, the epoxy alkyl derivatives prepared in Comparative Examples 2-4 fail to simultaneously achieve low-temperature fluidity, water solubility, and safety. The commercially available product GS-01 also exhibits significant water solubility deficiencies. Only the epoxy alkyl derivative prepared in Comparative Example 1 meets the aforementioned requirements.

[0155] 3. The solubilizing properties of the epoxy alkyl derivatives prepared in each example and comparative example, as well as the commercially available product SOLUBULE GS-01, were evaluated. Test method: S1: First, mix 5 g of butanediol with 2.1 g of each epoxy alkyl derivative or GS-01, heat to 80 ℃ to dissolve, then cool to 50 ℃, add 0.3 g of essential oil (limonene, purchased from Aipu Fragrance) and stir well; S2: Take 92.6 g of water and heat it to 25℃; S3: Slowly pour the mixed solution formed in step S1 into the water heated in step S2 while stirring. After the addition is complete, stir at 450 rpm for 10 minutes and observe the transparency.

[0156] Evaluation criteria for solubility: ◎Clear and transparent: The material is colorless and transparent, and the black and white checkered background can be clearly seen; ○ Slight turbidity: The material has a slight bluish tint, and the black and white checkered background is clearly visible; △Moderate turbidity: The material is cloudy with a bluish tinge, and the black and white checkered background can be vaguely seen; × Severe turbidity: The material is cloudy white, and the black and white grid background cannot be seen; or the material is layered.

[0157] The results of the solubilization evaluation are shown in Table 3. The photographs of the epoxide derivatives I-1, I-3, II-1, and II-3 are shown below. Figure 1 As shown.

[0158] Table 3 From Table 3 and Figure 1 The solubility results show that the epoxy alkane derivatives prepared in Examples 1, 2, 4, 5, 6, 8, and 10 exhibit excellent solubility, with all solutions being clear and transparent. The epoxy alkane derivative prepared in Example 9 shows slightly lower solubility, with a slightly turbid solution (indicating that epoxy alkane derivatives prepared using straight-chain or branched alkanols with more carbon atoms have superior solubility). The epoxy alkane derivatives prepared in Examples 3 and 7 show poor solubility, with severely turbid solutions. The epoxy alkane derivatives prepared in Comparative Examples 1, 2, and 4 show poor solubility, while the epoxy alkane derivative prepared in Comparative Example 3 shows excellent solubility. These results indicate that when C4-C32 straight-chain or branched alkanols preferentially incorporate into the PO block and end with an EO block (i.e., in Formula I, a and f are 0, and b and e are not 0), the solubility can be significantly improved. Furthermore, when the R group is preferably a straight-chain alkyl group of C12 to C18, a secondary-chain alkyl group of C10 to C24, or other branched-chain alkyl groups of C12 to C24, the solubility can be further improved.

[0159] 4. The surface tension of the epoxy alkane derivatives prepared in Example 1 was tested. Surface tension was tested using a high-performance automatic surface tension meter according to the method in GB / T 22237-2008. The instrument automatically mixed a high-concentration surfactant solution with a solvent (pure water) and gradually diluted it, while simultaneously measuring the surface tension in real time at each concentration point. Finally, a complete curve of surface tension changing with concentration was obtained, thereby accurately determining the critical micelle concentration (CMC).

[0160] The results of the critical micelle concentration (CMC) and surface tension test at CMC are shown in Table 4.

[0161] Table 4 5. The cleaning performance of the epoxy alkyl derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3, as well as the commercially available product SOLUBULE GS-01, was tested. Test method: S1: Making the soiled cloth: Cut pure cotton white cloth (purchased from Zuozhixun pure cotton white cloth) into a certain size (e.g., 10). Set aside 10cm); Mix 2% carbon black (purchased from Prwmier binchotan white carbon powder) with 98% sebum (purchased from Phygene Artificial Sebum), heat to melt, and prepare a stain solution. Then, use a brush to apply 1g of the stain solution evenly to a white cotton cloth. Let it stand to dry, and weigh it after it dries (this is the initial weight of the soiled cloth). S2: Preparation of washing solution: The epoxy alkyl derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3, as well as the commercially available product SOLUBULE GS-01, were added to deionized water and stirred at 450 rpm for 10 min at room temperature to prepare 1 L of 0.25% surfactant aqueous solution (i.e., washing solution). S3: Stain removal power test machine washing and rinsing: Add 1L of prepared detergent to a small washing machine (purchased from Xiaomi brand), and use 1L of added deionized water as a blank control. Under room temperature conditions, put in the dyed soiled cloth, set the speed to 1000rpm, and wash for 15 minutes. S4: Post-processing: Remove the soiled cloth, put it in an oven to dry for 30 minutes and weigh it (this is the weight of the soiled cloth after cleaning). S5: Gravimetric evaluation: The dirt removal rate is calculated using the following formula.

[0162] Dirt removal rate = (Initial soiled cloth weight - Soiled cloth weight after washing) / Dirt coating amount × 100% The results of the fouling removal rate evaluated using the gravimetric method are as follows: Figure 1 As shown. This method primarily evaluates its effectiveness in clearing sebum. (The text abruptly ends here.) Figure 1 The results show that the alkyl oxide derivatives prepared in the examples have significantly better dirt removal rates than the alkyl oxide derivatives prepared in the comparative examples and GS-01; in particular, the alkyl oxide derivative prepared in Example 2 has the best effect, with a dirt removal rate of 90.10%. Compared with the alkyl oxide derivative prepared in Comparative Example 3, the alkyl oxide derivative prepared in Example 1, by replacing the large EO and PO blocks with a structure using multiple sets of small EO-PO block units, can significantly improve the dirt removal rate and achieve better cleaning results.

[0163] S6: Whiteness Value Evaluation: Take photos of the original pure white cotton cloth, the soiled cloth before cleaning (after step S1), and the soiled cloth after cleaning (after step S4). Use ImageJ software to measure the average whiteness value of the photos. In digital images, for an 8-bit grayscale image, "white" corresponds to a high grayscale value (255 is pure white, and "black" corresponds to 0 is pure black).

[0164] S6.1: Open the image in ImageJ software and convert it to an 8-bit grayscale image; S6.2: Using the same selection tool and selection area size, measure each piece of fabric (original pure cotton white fabric, soiled fabric before cleaning, and soiled fabric after cleaning) separately, and record the average whiteness value (Mean value) of the measurement area. S6.3: Substitute the obtained results into the following formula to calculate the dirt removal rate.

[0165] Dirt removal rate = (Whiteness value of soiled cloth after washing - Whiteness value of soiled cloth before washing) / (Whiteness value of original pure cotton white cloth - Whiteness value of soiled cloth before washing) × 100% Photos of soiled cloths before and after cleaning with various detergents are shown below. Figure 2 As shown, the dirt removal rate results obtained by evaluating the whiteness value method are as follows: Figure 3 As shown. This method mainly evaluates the removal effect on carbon black. (The text abruptly ends here.) Figure 2 and Figure 3 The results show that the alkyl oxide derivatives prepared in Examples 1 and 2 have significantly better dirt removal rates than the alkyl oxide derivatives prepared in the comparative examples and GS-01; in particular, the alkyl oxide derivative prepared in Example 2 has the best effect, with a dirt removal rate of 73.11%, indicating that it has a very good effect on removing carbon black. Compared with the alkyl oxide derivative prepared in Comparative Example 3, the alkyl oxide derivative prepared in Example 1 improves the dirt removal rate and achieves a better cleaning effect on carbon black by replacing the large EO and PO blocks with a structure using multiple sets of small EO-PO block units. The comparison of the effects of the alkyl oxide derivatives prepared in Examples 1-3 and Comparative Examples 1 and 3 shows that when C4-C32 straight-chain or branched alkanols preferentially enter the PO block and end with the EO block (i.e., in Formula I, a and f are 0, and b and e are not 0), the cleaning effect on carbon black can be significantly improved.

[0166] This invention has many specific applications, and the above description is only a preferred embodiment. It should be noted that the above embodiments are for illustrative purposes only and are not intended to limit the scope of protection of this invention. For those skilled in the art, several improvements can be made without departing from the principle of this invention, and these improvements should also be considered within the scope of protection of this invention.

Claims

1. An epoxy alkane derivative, characterized in that, The epoxide derivatives have the chemical structure shown in formula (I): RO-(EO) a -(PO) b -[(IS) c -(PO) d ] n - (IS) e -(PO) f -HER) Wherein, R represents a straight-chain or branched alkyl group of C4 to C32, and R is connected to O through any one of its carbon atoms; EO is vinyl oxide, and PO is propylene oxide; The aforementioned [(EO)] c -(PO) d ] n The total block unit represents n (EO)-(PO) blocks connected together, where n ranges from 2 to 16. c and d represent the total average number of moles of EO and PO in the total block unit, where c ranges from 1 to 10 and d ranges from 1 to 2.

5. In each (EO)-(PO) block, the average number of moles of EO may be the same or different, and the average number of moles of PO may be the same or different. The values ​​a, b, e, and f represent the average number of moles, with a and e each ranging from 0 to 10, and b and f each ranging from 0 to 30.

2. The epoxy alkane derivative according to claim 1, characterized in that, In the chemical structure shown in formula (I), a and f take values ​​of 0, b and e take values ​​other than 0, c takes values ​​of 2 to 7, and d takes values ​​of 1 to 2.

5.

3. The epoxy alkane derivative according to claim 2, characterized in that, In the chemical structure shown in formula (I), a and f take values ​​of 0, b takes values ​​of 3 to 15, and e takes values ​​of 4 to 7.

4. The epoxy alkane derivative according to claim 1, characterized in that, In the chemical structure shown in formula (I), a takes the value of 1 to 10; b takes the value of 1 to 30; e takes the value of 0; and f takes the value of 1 to 30.

5. The epoxy alkane derivative according to claim 4, characterized in that, In the chemical structure shown in formula (I), a takes the value of 8; b takes the value of 1 to 2; e takes the value of 0; and f takes the value of 9 to 12.

6. The epoxy alkane derivative according to any one of claims 1-5, characterized in that, In the chemical structure shown in formula (I), R represents a straight-chain alkyl group of C4 to C18 or a branched alkyl group of C4 to C32; The C4-C32 branched alkyl groups include C4-C32 secondary alkyl groups and other C4-C32 branched alkyl groups.

7. The epoxy alkane derivative according to claim 6, characterized in that, The R represents a straight-chain alkyl group of C12 to C18, a secondary-chain alkyl group of C9 to C24, or other branched alkyl groups of C12 to C24.

8. The epoxy alkane derivative according to claim 1, characterized in that, The weight-average molecular weight of the epoxide derivative is 1000-5000; preferably, it is 1500-3000.

9. A method for preparing an epoxide derivative according to any one of claims 1-8, characterized in that, Includes the following steps: Under catalytic conditions, straight-chain or branched alkanols of C4 to C32 are subjected to addition reactions with ethylene oxide and propylene oxide in the order of adducts to obtain the alkyl oxide derivatives.

10. Use of an epoxide derivative according to any one of claims 1-8 as a surfactant.

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