Preparation method of isononyl alcohol extended multi-branched chain alcohol polyether and surfactant

Abstract

The invention discloses a preparation method of isononyl alcohol extension multi-branch chain alcohol polyether and a surfactant, and belongs to the technical field of chemical synthesis. The method comprises the following steps: taking isononyl alcohol as an initial raw material, and carrying out alkoxylation reaction on the isononyl alcohol and epoxypropane or epoxybutane to generate an isononyl alcohol alkoxylate mixture; the isononyl alcohol alkoxylate mixture is separated and purified, and a high-purity multi-branch chain alcohol intermediate is obtained; and carrying out ethoxylation reaction on the multi-branched chain alcohol intermediate serving as a raw material and ethylene oxide to obtain a multi-branched chain alcohol polyether product. According to the preparation method of the isononyl alcohol extended multi-branch chain alcohol polyether and the surfactant, the preparation process is simple and efficient, the atom utilization rate is extremely high, and the preparation method is suitable for industrial large-scale production and has wide application prospects and economic benefits.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of isononyl alcohol extended multi-branched alcohol polyether and a surfactant. Background Art

[0002] Fatty alcohol polyoxyethylene ether (AEO) is a non-ionic surfactant that is widely used in the market, especially in detergents, emulsifiers, dispersants, etc. Its chemical structure is characterized by a straight-chain fatty alcohol with a carbon number of 12 to 14 as the hydrophobic end raw material, with an appropriate amount of polyoxyethylene chain. This structure gives it a moderate hydrophobic alkyl chain length, and although it has no branches, it can still provide strong surface activity. However, with the development of technology and the increase in demand, researchers have found that branched surfactants are superior to straight-chain surfactants in many properties.

[0003] Specifically, branched surfactants can not only significantly reduce surface tension, but also improve water solubility and wetting properties, while also having excellent defoaming effects. These characteristics make branched surfactants have greater potential and advantages in many industrial applications. However, how to synthesize branched nonionic surfactants with moderate hydrophobic alkyl chain length has become an important topic in current technology research and development.

[0004] At present, many research teams have tried to synthesize branched surfactants using isooctyl alcohol as a raw material by grafting hydrophobic groups. These methods generally involve first reacting isooctyl alcohol with an alkoxy group to generate a mixture of grafted hydrophobic groups, and then further reacting with ethylene oxide (EO) to generate a polyether product. However, this method has significant limitations. First, the number of branches in the isooctyl alcohol polyether product is small, and a sufficient branched structure cannot be formed; second, these products are complex in structure, which increases the difficulty of analysis and evaluation. These problems limit the existing technology in terms of product consistency, performance stability and industrial application.

[0005] Therefore, it is necessary to provide a new solution to the above technical problems. Summary of the invention

[0006] The object of the present invention is to provide a preparation method of isononyl alcohol extended multi-branched alcohol polyether and a surfactant, wherein the method has low synthesis process cost and high atom utilization rate.

[0007] To achieve the above purpose, the technical solution provided by the present invention is as follows:

[0008] In a first aspect, the present invention provides a method for preparing isononyl alcohol extended multi-branched alcohol polyether, which comprises:

[0009] S101: using isononyl alcohol as a starting material, and carrying out an alkoxylation reaction with propylene oxide or butylene oxide to generate an isononyl alcohol alkoxylate mixture;

[0010] S102: separating and purifying the isononanol alkoxylate mixture to obtain a high-purity multi-branched alcohol intermediate;

[0011] S103: using the multi-branched alcohol intermediate as a raw material, and carrying out an ethoxylation reaction with ethylene oxide to obtain a multi-branched alcohol polyether product.

[0012] In one or more embodiments, in step S101, the addition number of propylene oxide or butylene oxide during the alkoxylation reaction is regulated by adjusting the ratio of isononanol to propylene oxide or butylene oxide.

[0013] In one or more embodiments, in step S101, the alkoxylation reaction equation of isononyl alcohol and propylene oxide includes:

[0014]

[0015] Wherein, x is a positive integer.

[0016] In one or more embodiments, in step S101, the alkoxylation reaction equation of isononanol and butylene oxide includes:

[0017]

[0018] Wherein, y is a positive integer.

[0019] In one or more embodiments, in step S101, the catalyst for the alkoxylation reaction is an alkali metal compound, and the mass ratio of isononyl alcohol to the catalyst is 1000:3 to 1000:5.

[0020] In one or more embodiments, in step S103, the reaction temperature of the ethoxylation reaction is 130-220° C., the reaction pressure is 0.2-0.6 MPa, and the reaction time is 1-12 h.

[0021] In one or more embodiments, in step S103, the catalyst for the ethoxylation reaction is an alkali metal compound, and the mass ratio of the multi-branched alcohol intermediate to the catalyst is 1000:3 to 1000:5.

[0022] In one or more embodiments, in step S103, the equation for the ethoxylation reaction of the multi-branched alcohol intermediate with ethylene oxide includes:

[0023]

[0024] Wherein, x and y are positive integers, and n=1 to 30.

[0025] In one or more embodiments, it is characterized in that the method further comprises: adding acetic acid to the multi-branched alcohol polyether product, reacting for a predetermined time, filtering to remove salt, and rotary evaporating to obtain high-purity multi-branched alcohol polyether.

[0026] In a second aspect, the present invention provides a surfactant, which includes the multi-branched alcohol polyether prepared by the above-mentioned preparation method.

[0027] Compared with the prior art, the preparation method of isononyl alcohol extended multi-branched alcohol polyether and surfactant provided by the present invention obtain a high-purity multi-branched alcohol intermediate by regulating the addition number of propylene oxide or butylene oxide and combining separation and purification technology; the multi-branched structure significantly improves the surface activity of the final product, making it excellent in reducing surface tension, enhancing water solubility and wettability; the multi-branched alcohol polyether generated by ethoxylation reaction has an adjustable hydrophilic-lipophilic balance value to meet different application requirements; in addition, the method of the present invention is simple and efficient, has extremely high atomic utilization, is suitable for industrial large-scale production, and has broad application prospects and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the prior art descriptions are briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 This is a flow chart of a method for preparing isononyl alcohol extended multi-branched alcohol polyether in one embodiment of the present invention;

[0030] Figure 2 The figure is a schematic diagram of the process of preparing the isononyl alcohol extended multi-branched alcohol polyether according to one embodiment of the present invention;

[0031] Figure 3 This is an infrared analysis chart of the high-purity multi-branched PO1 alcohol prepared in Example 1 of the present invention;

[0032] Figure 4 This is a static surface tension diagram of the multi-branched PO1 alcohol polyether prepared in Example 1 of the present invention;

[0033] Figure 5 This is an infrared analysis chart of the high-purity multi-branched BO1 alcohol prepared in Example 2 of the present invention;

[0034] Figure 6 This is a static surface tension diagram of the multi-branched BO1 alcohol polyether prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0035] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0036] It should be noted that, unless otherwise indicated, all numbers used in the specification and claims to represent feature sizes, quantities and physical properties should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.2, 1.4, 1.55, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0037] The invention is proposed based on the in-depth analysis and improvement needs of the existing non-ionic surfactant technology. Fatty alcohol polyoxyethylene ether (AEO) is a widely used non-ionic surfactant. Although it is relatively excellent in performance, its linear structure limits its potential for further performance improvement. Through research on the prior art, the inventors found that branched surfactants have significant advantages in reducing surface tension, improving water solubility and wettability, and improving defoaming performance. However, the branched surfactants based on isooctyl alcohol on the market still have some shortcomings in the preparation process, including a small number of branches, complex product distribution and other problems, which poses challenges to product quality control and performance stability.

[0038] Isononanol can be considered as a hydrophobic end branching raw material because of its rich methyl side chain in its molecular structure, but it has the disadvantage of insufficient alkyl chain length. Extending the hydrophobic tail chain by grafting hydrophobic groups (PO or BO) is an effective synthetic strategy.

[0039] In this context, the present invention proposes a novel method for preparing isononyl alcohol extended multi-branched alcohol polyether. The method rationally designs a synthetic route, utilizes isononyl alcohol, a raw material with abundant methyl branches, introduces propylene oxide (PO) or butylene oxide (BO) for alkoxylation reaction, and then separates, purifies and ethoxylates to finally obtain a multi-branched alcohol polyether nonionic surfactant. This method can not only accurately control the number of branches to obtain a high-purity multi-branched intermediate, but also further improve the hydrophilicity and application effect of the product through subsequent ethoxylation reaction.

[0040] The inventors analyzed the defects in the prior art and found that the traditional method for synthesizing branched surfactants has problems such as complex reaction steps, high product mixing, and difficulty in achieving high-purity separation. Therefore, the present invention mainly innovates and improves the technical implementation ideas in the following aspects:

[0041] 1. Using isononyl alcohol as the starting material, utilizing its unique molecular structure characteristics, introducing propylene oxide or butylene oxide to carry out alkoxylation reaction to form a multi-branched structure.

[0042] 2. Optimize the reaction conditions and catalyst system to generate a mixture of isononanol alkoxylates through alkoxylation, and then obtain a high-purity multi-branched intermediate through a sophisticated separation and purification process.

[0043] 3. Ethoxylation reaction is carried out on the basis of multi-branched intermediates to further enhance the hydrophilicity of the product, and the high purity and stability of the product are ensured through post-treatment process.

[0044] Please refer to Figure 1 and Figure 2 As shown, Figure 1 The flowchart of the preparation method of isononyl alcohol extended multi-branched alcohol polyether in one embodiment of the present invention is shown in FIG. Figure 2 The process diagram of the preparation method of isononanol extended multi-branched alcohol polyether in one embodiment of the present invention is shown in FIG. The preparation method of isononanol extended multi-branched alcohol polyether specifically comprises the following steps:

[0045] S101: using isononyl alcohol as a starting material, and carrying out an alkoxylation reaction with propylene oxide or butylene oxide to generate an isononyl alcohol alkoxylate mixture.

[0046] In step S101, isononanol is used as a starting material and undergoes an alkoxylation reaction with propylene oxide (PO) or butylene oxide (BO) to generate an isononanol alkoxylate mixture. The core of this step is to combine isononanol molecules with propylene oxide or butylene oxide through a chemical reaction to form an intermediate with a multi-branched structure.

[0047] A specific embodiment may include mixing isononanol with a catalyst such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) to form a reaction system. Then, propylene oxide or butylene oxide is gradually added to the reaction system under controlled temperature and pressure conditions (e.g., 140-200° C., 0.5-1 MPa). By regulating the amount of propylene oxide or butylene oxide added, the addition number of the alkoxylate can be accurately controlled, thereby adjusting the composition and properties of the generated isononanol alkoxylate mixture.

[0048] For example, in a specific embodiment, isononanol and potassium hydroxide can be mixed in a certain ratio (e.g., 1000:4), and then propylene oxide is gradually added at a reaction temperature of 160° C. to react with isononanol for 2 to 5 hours to generate a multi-branched isononanol propoxylate mixture. After the reaction is completed, propoxylates of different chain lengths, such as PO1, PO2, PO3, etc., are separated by reduced pressure distillation.

[0049] The main purpose of this step is to give the isononanol molecule a multi-branched structure by introducing propylene oxide or butylene oxide. This multi-branched structure not only increases the steric hindrance between molecules and reduces surface tension, but also significantly improves its water solubility and wetting properties. In addition, the high efficiency and controllability of the alkoxylation reaction ensure that the generated isononanol alkoxylate mixture has uniform properties and high purity, providing high-quality intermediates for subsequent separation and purification and ethoxylation reactions.

[0050] Specifically, in step S101, the addition number of propylene oxide or butylene oxide during the alkoxylation reaction is regulated by adjusting the ratio of isononanol to propylene oxide or butylene oxide. By adjusting the ratio of the reactants, the length and number of the branches in the generated isononanol alkoxylate can be accurately controlled, thereby achieving the regulation of the product molecular chain.

[0051] Alkoxylation reaction refers to the chemical reaction between isononanol and propylene oxide or butylene oxide under the action of a catalyst. By adjusting the molar ratio of isononanol to propylene oxide or butylene oxide, the addition number of the alkoxylate, that is, the number of times propylene oxide or butylene oxide is attached to the isononanol molecule, can be controlled. The number of additions directly affects the branched structure of the product and its final performance.

[0052] For example, in a specific embodiment, if the molar ratio of isononanol to propylene oxide is set to 1:1.5, an alkoxylate mixture with isononanol PO1 as the main component may be generated. If the molar ratio is adjusted to 1:2.5, an alkoxylate mixture with isononanol PO2 as the main component is generated. The same principle also applies to butylene oxide. By adjusting the ratio of isononanol to butylene oxide, a butoxylate mixture with different addition numbers can be generated.

[0053] The purpose of controlling the addition number of propylene oxide or butylene oxide is to obtain isononanol alkoxylates with specific branched structures. These branched structures play a key role in the subsequent ethoxylation reaction and the performance of the final product. Specifically, the multi-branched structure can significantly reduce surface tension, improve water solubility and wetting properties, and enhance the defoaming effect. In addition, by precisely controlling the addition number, it is possible to ensure that the generated alkoxylates have uniform properties, reducing the complexity of the subsequent separation and purification process.

[0054] In step S101, the alkoxylation reaction equation of isononyl alcohol and propylene oxide includes:

[0055]

[0056] Wherein, x is a positive integer.

[0057] Specifically, isononyl propoxylated PO 1.5 The reaction can obtain a mixture with a higher PO1 content:

[0058] A mixture of propylene oxide and isononanol with a molar ratio of 1.5 is used as the starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and a mixture of isononanol propoxylates with a multi-branched structure is obtained after the reaction, a=0,1,2,3... The main components are isononanol PO1 and a small amount of isononanol PO2, isononanol PO3, and isononanol.

[0059] Isononyl alcohol propoxylated PO 1.5 The reaction equation is:

[0060]

[0061] Isononyl alcohol propoxylated PO 2.5 The reaction can obtain a mixture with a higher PO2 content:

[0062] A mixture of propylene oxide and isononanol with a molar ratio of 2.5 is used as the starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and a mixture of isononanol propoxylates with a multi-branched structure is obtained after the reaction, b=0,1,2,3,4... The main components are isononanol PO2 and a small amount of isononanol PO1, isononanol PO3, isononanol PO4, and isononanol.

[0063] Isononyl alcohol propoxylated PO 2.5 The reaction equation is:

[0064]

[0065] Isononyl alcohol propoxylated PO 3.5 The reaction can obtain a mixture with a higher PO3 content:

[0066] A mixture of propylene oxide and isononanol with a molar ratio of 3.5 is used as the starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and a mixture of isononanol propoxylates with a multi-branched structure is obtained after the reaction, c=0,1,2,3,4,5... The main components are isononanol PO3 and a small amount of isononanol PO1, isononanol PO2, isononanol PO4, isononanol PO5 and isononanol.

[0067] Isononyl alcohol propoxylated PO 3.5 The reaction equation is:

[0068]

[0069] Isononyl alcohol propoxylated PO 4.5 ,PO 5.5 ...and so on.

[0070] In step S101, the alkoxylation reaction equation of isononyl alcohol and butylene oxide includes:

[0071]

[0072] Wherein, y is a positive integer.

[0073] Specifically, isononyl butoxylated BO 1.5 The reaction can obtain a mixture with a higher BO1 content:

[0074] A mixture of butylene oxide and isononanol with a molar ratio of 1.5 is used as the starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and after the reaction, a mixture of isononanol butoxylates with a multi-branched structure is obtained, d=0, 1, 2, 3... The main components are isononanol BO1 and a small amount of isononanol BO2, isononanol BO3, and isononanol.

[0075] Isononyl alcohol butoxylated BO 1.5 The reaction equation is:

[0076]

[0077] Isononyl alcohol butoxylated BO 2.5 The reaction can obtain a mixture with a higher BO2 content:

[0078] A mixture of butylene oxide and isononanol with a molar ratio of 2.5 is used as a starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and a mixture of isononanol butoxylates with a multi-branched structure is obtained after the reaction, e=0,1,2,3,4... The main components are isononanol BO2 and a small amount of isononanol BO1, isononanol BO3, isononanol BO4, and isononanol.

[0079] Isononyl alcohol butoxylated BO 2.5 The reaction equation is:

[0080]

[0081] Isononyl alcohol butoxylated BO 3.5 The reaction can obtain a mixture with a higher BO3 content:

[0082] A mixture of butylene oxide and isononanol with a molar ratio of 3.5 is used as the starting material, the temperature of the reaction system is reduced to below 5°C, and the reaction system is ensured to be oxygen-free by nitrogen purging. Under the action of a catalyst, the reaction temperature is controlled at 140-200°C, the reaction time is 2-5 hours, and a mixture of isononanol butoxylates with a multi-branched structure is obtained after the reaction, with f=0, 1, 2, 3, 4, 5... The main components are isononanol BO3 and a small amount of isononanol BO1, isononanol BO2, isononanol BO4, isononanol BO5 and isononanol.

[0083] Isononyl alcohol butoxylated BO 3.5 The reaction equation is:

[0084]

[0085] Isononyl alcohol butoxylated BO 4.5 , BO 5.5 ...and so on.

[0086] Preferably, in step S101, the catalyst for the alkoxylation reaction is an alkali metal compound, and the mass ratio of isononyl alcohol to the catalyst is 1000:3 to 1000:5. For example, the catalyst may be a potassium-containing compound or a sodium-containing compound, wherein the potassium-containing compound may be potassium hydroxide, potassium methoxide, potassium carbonate, potassium tert-butoxide, potassium oxalate, etc.; and the sodium-containing compound may be sodium hydroxide, sodium methoxide, sodium carbonate, sodium acetate, sodium tert-butoxide, sodium oxalate, etc.

[0087] The reason for using alkali metal compounds as catalysts is that these catalysts can provide an efficient alkaline environment, which is conducive to the ring-opening reaction of propylene oxide or butylene oxide, so that it can undergo an addition reaction with isononyl alcohol molecules to generate alkoxylates. For example, potassium hydroxide, as a strong base, can effectively initiate and accelerate the reaction of epoxides with alcohol compounds to generate alkoxylates with multi-branched structures.

[0088] S102: separating and purifying the isononanol alkoxylate mixture to obtain a high-purity multi-branched alcohol intermediate.

[0089] Step S102 involves separating and purifying the generated isononanol alkoxylate mixture to obtain a high-purity multi-branched alcohol intermediate. The main purpose of this step is to effectively separate alkoxylates with different addition numbers through fine separation technology, thereby ensuring the high purity and specific properties of each intermediate, and providing high-quality raw materials for subsequent ethoxylation reactions.

[0090] The specific method for implementing this step generally includes vacuum distillation technology. Vacuum distillation is a separation process carried out under conditions below normal pressure. It utilizes the difference in boiling points of different compounds to improve separation efficiency while reducing the distillation temperature. For example, in the present invention, the isononanol propoxylate mixture can be separated by vacuum distillation step by step. In each stage of distillation, by accurately controlling the temperature and pressure, high-purity intermediates such as multi-branched PO1, PO2, PO3 can be obtained respectively.

[0091] Specifically, the isononanol propoxylate mixture can be placed in a vacuum distillation tower, and the distillation temperature is first set at 80-100°C and the pressure is controlled at 500Pa. In this stage, the unreacted isononanol can be mainly separated. Next, the distillation temperature is increased to 100-120°C, and the multi-branched PO1 can be separated at the same pressure. Further increasing the temperature to 120-140°C, the multi-branched PO2 can be separated. In this way, the temperature is gradually increased, and the multi-branched PO3 is finally separated at 140-160°C. This separation method ensures the high purity and precise separation of each intermediate.

[0092] For details, please refer to Figure 2 As shown, isononyl alcohol propoxylated PO 1.5 The method of obtaining pure PO1 after vacuum distillation of the mixture generated by the reaction includes: the mixture passes through a vacuum distillation tower 1 at 80-100°C and 500Pa to obtain isononyl alcohol, and then passes through a vacuum distillation tower 2 at 100-120°C and 500Pa to obtain high-purity multi-branched PO1. The structural formula of PO1 is:

[0093]

[0094] Isononyl alcohol propoxylated PO 2.5 The method of obtaining pure PO2 after vacuum distillation of the mixture generated by the reaction includes: the mixture passes through a vacuum distillation tower 1 at 80-100°C and 500Pa to obtain isononyl alcohol, then passes through a vacuum distillation tower 2 at 100-120°C and 500Pa to obtain multi-branched PO1, and then passes through a vacuum distillation tower 3 at 120-140°C and 500Pa to obtain high-purity multi-branched PO2. The structural formula of PO2 is:

[0095]

[0096] Isononyl alcohol propoxylated PO 3.5 The method of obtaining pure PO3 after vacuum distillation of the mixture generated by the reaction includes: the mixture passes through a vacuum distillation tower 1 at 80-100°C and 500Pa to obtain isononyl alcohol, then passes through a vacuum distillation tower 2 at 100-120°C and 500Pa to obtain multi-branched PO1, then passes through a vacuum distillation tower 3 at 120-140°C and 500Pa to obtain multi-branched PO2, and finally passes through a vacuum distillation tower 4 at 140-160°C and 500Pa to obtain high-purity PO3. The structural formula of PO3 is:

[0097]

[0098] Separation and purification of pure substances PO4, PO5... and so on.

[0099] Isononyl alcohol butoxylated BO 1.5 The method of obtaining pure BO1 after vacuum distillation of the reaction mixture includes: the mixture passes through a vacuum distillation tower 1 at 95-115°C and 500Pa to obtain isononyl alcohol, and then passes through a vacuum distillation tower 2 at 115-135°C and 500Pa to obtain high-purity multi-branched BO1. The structural formula of BO1 is:

[0100]

[0101] Isononyl alcohol butoxylated BO 2.5 The method of obtaining pure BO2 after vacuum distillation of the mixture generated by the reaction includes: the mixture passes through a vacuum distillation tower 1 at 95-115°C and 500Pa to obtain isononyl alcohol, then passes through a vacuum distillation tower 2 at 115-135°C and 500Pa to obtain multi-branched BO1, and then passes through a vacuum distillation tower 3 at 135-155°C and 500Pa to obtain high-purity multi-branched BO2. The structural formula of BO2 is:

[0102]

[0103] Isononyl alcohol butoxylated BO 3.5The method of obtaining pure BO3 after vacuum distillation of the mixture generated by the reaction includes: the mixture passes through a vacuum distillation tower 1 at 95-115°C and 500Pa to obtain isononyl alcohol, then passes through a vacuum distillation tower 2 at 115-135°C and 500Pa to obtain multi-branched BO1, and then passes through a vacuum distillation tower 3 at 135-155°C and 500Pa to obtain multi-branched BO2. Finally, it passes through a vacuum distillation tower 4 at 155-175°C and 500Pa to obtain high-purity BO3. The structural formula of BO3 is:

[0104]

[0105] BO4, BO5 separation and purification of pure substances... and so on.

[0106] S103: using the multi-branched alcohol intermediate as a raw material, and carrying out an ethoxylation reaction with ethylene oxide to obtain a multi-branched alcohol polyether product.

[0107] The core of step S103 is to use the multi-branched alcohol intermediate obtained in the previous step to carry out an ethoxylation reaction with ethylene oxide (EO) (ethylene oxide can be introduced intermittently through a solenoid valve), and finally generate a multi-branched alcohol polyether product. Ethoxylation is a process in which ethylene oxide molecules are connected to multi-branched alcohol molecules through ether bonds, thereby forming polyoxyethylene ether chains, which not only improves the hydrophilicity of the product, but also enhances its surface activity.

[0108] In a specific embodiment of implementing this step, the multi-branched alcohol intermediate (such as multi-branched PO1, PO2, etc.) is first mixed with a certain amount of catalyst, and the commonly used catalyst is an alkali metal compound, such as potassium hydroxide (KOH) or sodium hydroxide (NaOH). In the reaction system, ethylene oxide is intermittently introduced and reacted under controlled temperature and pressure. For example, the reaction temperature can be set between 130 and 220° C., the pressure is controlled at 0.2 to 0.6 MPa, and the reaction time is 1 to 12 hours. Through the optimization of these conditions, the insertion amount of ethylene oxide units can be effectively controlled, thereby adjusting the polymerization degree and properties of the generated multi-branched alcohol polyether.

[0109] Preferably, in step S103, the catalyst for the ethoxylation reaction is an alkali metal compound, and the mass ratio of the multi-branched alcohol intermediate to the catalyst is 1000:3 to 1000:5. For example, the catalyst may be a potassium-containing compound or a sodium-containing compound, wherein the potassium-containing compound may be potassium hydroxide, potassium methoxide, potassium carbonate, potassium tert-butoxide, potassium oxalate, etc.; and the sodium-containing compound may be sodium hydroxide, sodium methoxide, sodium carbonate, sodium acetate, sodium tert-butoxide, sodium oxalate, etc.

[0110] In step S103, the equation for the ethoxylation reaction of the multi-branched alcohol intermediate with ethylene oxide includes:

[0111]

[0112] Wherein, x and y are positive integers, and n=1 to 30.

[0113] Specifically, the reaction equation for the ethoxylation of high-purity multi-branched PO1 is:

[0114]

[0115] The reaction equation for the ethoxylation of high-purity multi-branched PO2 is:

[0116]

[0117] The reaction equation for the ethoxylation of high-purity multi-branched PO3 is:

[0118]

[0119] High-purity multi-branched PO4, PO5...ethoxylation reactions are similar.

[0120] The reaction equation for the ethoxylation of high-purity multi-branched BO1 is:

[0121]

[0122] The reaction equation for the ethoxylation of high-purity multi-branched BO2 is:

[0123]

[0124] The reaction equation for the ethoxylation of high-purity multi-branched BO3 is:

[0125]

[0126] High purity multi-branched BO4, BO5...ethoxylation reaction and so on.

[0127] In an exemplary embodiment, the method further comprises: adding acetic acid to the multi-branched alcohol polyether product, reacting for a predetermined time, filtering to remove salt, and rotary evaporating to obtain a high-purity multi-branched alcohol polyether. The multi-branched alcohol polyether product is treated by adding acetic acid to neutralize the catalyst remaining in the previous reaction. The core of this step is to react the catalyst with acetic acid to generate salts through a chemical reaction, thereby improving the purity and stability of the product.

[0128] The specific implementation method can include adding the equimolar amount of acetic acid determined in advance to the multi-branched alcohol polyether product, so that it reacts completely with the residual catalyst. After the reaction is completed, the generated salts are removed from the product by a filtering step. This step can adopt a conventional filtering method, such as using a vacuum filtration device, to ensure that the solid salts are separated from the liquid product. In order to further improve the purity of the product, it is also necessary to carry out rotary evaporation (referred to as rotary evaporation) processing. Rotary evaporation is a distillation process carried out under reduced pressure, which can effectively remove the residual solvent and other low-boiling impurities in the solution, thereby obtaining a highly purified multi-branched alcohol polyether product.

[0129] The present invention provides a surfactant, which comprises the multi-branched alcohol polyether prepared by the above-mentioned preparation method.

[0130] The present invention will be further described below in conjunction with specific embodiments.

[0131] Example 1

[0132] Weigh 82.47g (0.56mol) of isononanol and 0.24g (0.3wt.% of the mass of isononanol) of KOH and put them into a 250ml reactor. Then, turn on the low-temperature circulating water bath to reduce the reactor temperature to below 5°C, purge the reactor three times with nitrogen from a nitrogen cylinder, then add 48.31g (0.832mol) of propylene oxide, stir for 20min and heat to 160°C, regulate the product distribution by regulating the addition number of propylene oxide, and age for 1h after the reaction to obtain 128.83g of a crude product. Gas chromatography measured that isononanol PO1 accounted for 45.34%, isononanol PO2 accounted for 22.91%, isononanol PO3 accounted for 7.61% and isononanol accounted for 15.02% in the product.

[0133] The crude product is distilled in a vacuum distillation tower 1 at 80-100°C and 500Pa to obtain isononyl alcohol, and then distilled in a vacuum distillation tower 2 at 100-120°C and 500Pa to obtain high-purity multi-branched PO1 alcohol.

[0134] After vacuum distillation tower 2, high-purity multi-branched PO1 alcohol was obtained for infrared analysis. The analysis results are as follows Figure 3 As shown. Figure 3 It can be seen that C9P1-OH has a wave number of 2953cm -1 and 2865cm -1 The nearby peaks are typical stretching vibrations of saturated carbon-hydrogen bonds (-CH3, -CH2), at 1465 cm -1 and 1368cm -1 The nearby peaks belong to the bending vibration of saturated carbon-hydrogen bonds at 1110 cm -1 The ether bond stretching vibration peak appears at 1054 cm -1The carbon-oxygen stretching vibration peak corresponding to C9-OH disappeared, indicating that PO was successfully inserted between the carbon-oxygen bonds to form an ether bond.

[0135] Take the aforementioned high-purity multi-branched PO1 alcohol 70.00g (0.35mol), catalyst KOH 0.21g (0.3wt.% of the mass of multi-branched PO1 alcohol) and add it to a 250mL stainless steel reactor equipped with mechanical stirring, and seal the reactor. Set the stirring rate to 600RPM, heat to 160℃ to start the reaction, add 92.50g of ethylene oxide through a solenoid valve, and the reaction time is 9h. After the reaction is completed, maintain 160℃ aging for 1h, then cool to 90℃, vacuumize at a pressure of -0.08MPa for 30min to remove residual ethylene oxide, then release the vacuum and continue to cool to 40℃, you can get 162.41g of multi-branched PO1 alcohol polyoxyethylene ether, and the residual alcohol is 0 as measured. Figure 4 The static surface tension diagram of the multi-branched PO1 alcohol polyether obtained in Example 1 is shown.

[0136] The multi-branched PO1 alcohol polyether synthesized in Example 1 was prepared into a surfactant aqueous solution with a concentration of 2 mmol / L. The instrument used was a German KRUSS K100C surface tension tester, which tested the surface tension by using a platinum plate in contact with the surface of an aqueous solution containing a certain concentration of surfactant based on the Wilhelmy Plate method, and the test temperature was controlled to 25°C ± 0.5°C using a circulating water bath from Ulabo Technology.

[0137] When the instrument starts testing, it first measures the surface tension of pure water. While keeping the volume of the measured solution constant, it continuously injects an equal volume of surfactant solution into the test container and accurately draws out the corresponding volume of solution. In this way, the concentration of the surfactant solution continuously changes from dilute to concentrated, and the surface tension of the solution at different concentrations can be obtained. At the end of the test, the relationship curve between surface tension and concentration can be obtained (such as Figure 4 As shown in Figure 2), it can be determined that the critical micelle concentration (CMC) of the surfactant is 2.20 mmol / L and the corresponding surface tension (γ CMC ) is 27.95 mN / m, which indicates that the multi-branched PO1 alcohol polyether synthesized in Example 1 has typical surfactant properties and can effectively reduce the surface tension of water.

[0138] Example 2

[0139] Weigh 82.47g (0.56mol) of isononanol and 0.24g (0.3wt.% of the mass of isononanol) of KOH and put them into a 250ml reactor. Then, turn on the low-temperature circulating water bath to reduce the reactor temperature to below 5°C, purge the reactor three times with nitrogen from a nitrogen cylinder, then add 59.99g (0.832mol) of butylene oxide, stir for 20min and heat to 160°C, regulate the product distribution by regulating the addition number of butylene oxide, and age for 1h after the reaction to obtain 140.30g of a crude product. Gas chromatography measured that isononanol BO1 accounted for 55.30%, isononanol BO2 accounted for 23.87%, isononanol BO3 accounted for 6.15% and isononanol accounted for 8.81% in the product.

[0140] The crude product is distilled in a vacuum distillation tower 1 at 95-115°C and 500Pa to obtain isononyl alcohol, and then distilled in a vacuum distillation tower 2 at 115-135°C and 500Pa to obtain high-purity multi-branched BO1 alcohol.

[0141] The high-purity multi-branched BO1 alcohol obtained after the vacuum distillation tower 2 was subjected to infrared analysis. The analysis results are as follows: Figure 5 As shown. Figure 5 It can be seen that C9B1-OH has a wave number of 2953cm -1 and 2865cm -1 The nearby peaks are typical stretching vibrations of saturated carbon-hydrogen bonds (-CH3, -CH2), at 1465 cm -1 and 1368cm -1 The nearby peaks belong to the bending vibration of saturated carbon-hydrogen bonds at 1110 cm -1 The ether bond stretching vibration peak appears at 1054 cm -1 The carbon-oxygen stretching vibration peak corresponding to C9-OH disappeared, indicating that BO was successfully inserted between the carbon-oxygen bonds to form an ether bond.

[0142] Take the aforementioned high-purity multi-branched BO1 alcohol 80.00g (0.37mol), catalyst KOH 0.24g (0.3wt.% of the mass of multi-branched BO1 alcohol) and add it to a 250mL stainless steel reactor equipped with mechanical stirring, and seal the reactor. Set the stirring rate to 600RPM, heat to 160°C to start the reaction, add 97.79g of ethylene oxide through a solenoid valve, and the reaction time is 12h. After the reaction is completed, maintain 160°C for aging for 1h, then cool to 90°C, vacuumize at a pressure of -0.08MPa for 30min to remove residual ethylene oxide, then release the vacuum and continue to cool to 40°C, you can get 177.82g of multi-branched BO1 alcohol polyoxyethylene ether, the residual alcohol is measured to be 0. Figure 6 The static surface tension diagram of the multi-branched BO1 alcohol polyether obtained in Example 2 is shown.

[0143] The multi-branched BO1 alcohol polyether synthesized in Example 2 is prepared into a surfactant aqueous solution with a concentration of 2mmol / L. The instrument used is a German KRUSS K100C surface tension tester, which tests the surface tension by using a platinum plate to contact the surface of an aqueous solution containing a certain concentration of surfactant based on the Wilhelmy Plate method. The test temperature is controlled to 25°C ± 0.5°C using a circulating water bath of Ulabo Technology. When the instrument starts testing, it first measures the surface tension of pure water, continuously injects an equal volume of surfactant solution into the test container while keeping the volume of the measured solution constant, and accurately draws out the corresponding volume of solution, so that the concentration of the surfactant solution continuously changes from dilute to concentrated, and the surface tension of the solution at different concentrations can be obtained accordingly. At the end of the test, the relationship curve between the surface tension and the concentration can be obtained (such as Figure 6 shown).

[0144] In summary, the preparation method of isononyl alcohol extended multi-branched alcohol polyether and surfactant provided by the present invention obtain a high-purity multi-branched alcohol intermediate by regulating the addition number of propylene oxide or butylene oxide and combining separation and purification technology; this multi-branched structure significantly improves the surface activity of the final product, making it excellent in reducing surface tension, enhancing water solubility and wettability; the multi-branched alcohol polyether generated by ethoxylation reaction has an adjustable hydrophilic-lipophilic balance value to meet different application requirements; in addition, the method of the present invention is simple and efficient, has extremely high atomic utilization, is suitable for industrial large-scale production, and has broad application prospects and economic benefits.

[0145] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

[0146] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing isononyl alcohol extended multi-branched alcohol polyether, characterized in that: include: S101: using isononyl alcohol as a starting material, and carrying out an alkoxylation reaction with propylene oxide or butylene oxide to generate an isononyl alcohol alkoxylate mixture; S102: separating and purifying the isononanol alkoxylate mixture to obtain a high-purity multi-branched alcohol intermediate; S103: using the multi-branched alcohol intermediate as a raw material, and carrying out an ethoxylation reaction with ethylene oxide to obtain a multi-branched alcohol polyether product.

2. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S101, the addition number of propylene oxide or butylene oxide during the alkoxylation reaction is regulated by the ratio of isononyl alcohol to propylene oxide or butylene oxide.

3. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S101, the alkoxylation reaction equation of isononyl alcohol and propylene oxide includes: Wherein, x is a positive integer.

4. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S101, the alkoxylation reaction equation of isononyl alcohol and butylene oxide includes: Wherein, y is a positive integer.

5. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S101, the catalyst for the alkoxylation reaction is an alkali metal compound, and the mass ratio of isononyl alcohol to the catalyst is 1000:3 to 1000:

5.

6. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S103, the reaction temperature of the ethoxylation reaction is 130-220°C, the reaction pressure is 0.2-0.6 MPa, and the reaction time is 1-12 hours.

7. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S103, the catalyst for the ethoxylation reaction is an alkali metal compound, and the mass ratio of the multi-branched alcohol intermediate to the catalyst is 1000:3 to 1000:

5.

8. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: In step S103, the equation for the ethoxylation reaction of the multi-branched alcohol intermediate with ethylene oxide includes: Wherein, x and y are positive integers, and n=1 to 30.

9. The method for preparing isononyl alcohol extended multi-branched alcohol polyether according to claim 1, characterized in that: The method further comprises: Acetic acid is added to the multi-branched alcohol polyether product, and after reacting for a predetermined time, the product is filtered to remove salt, and then rotary evaporated to obtain high-purity multi-branched alcohol polyether.

10. A surfactant, characterized in that The invention comprises a multi-branched alcohol polyether prepared by the preparation method as described in any one of claims 1 to 9.

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