Catalyst for synthesis of fatty amine polyoxyalkylene ether and use thereof

Abstract

The present application relates to the catalyst for the synthesis of fatty amine polyoxyalkylene ether, mainly the product colority problem of the existing fatty amine polyoxyethylene ether production method, technical scheme as follows: the catalyst for the synthesis of fatty amine polyoxyalkylene ether, including the following components: (a) metallocene;(b) cocatalyst;The weight ratio of cocatalyst and metallocene is 1-10;Wherein the cocatalyst includes the boron compound shown in formula (1): wherein, P1-P 15 are independently selected from hydrogen atom or halogen atom: formula (1).

Description

Technical Field

[0001] This invention relates to catalysts for the synthesis of fatty amine polyoxyalkylene ethers and their applications. Background Technology

[0002] Fatty amine polyoxyethylene ethers are important amine ethoxylates that possess both nonionic and cationic surfactant properties, and are widely used in many fields such as textile leveling, daily chemical washing, metal corrosion inhibition, and pesticide emulsification.

[0003] Currently, the industrial synthesis of amine ethoxylates generally uses strong alkaline catalysts such as sodium hydroxide, potassium hydroxide, and sodium alkoxide. These catalysts have a relatively fast catalytic rate, but they have obvious drawbacks: the alkaline system is very prone to side reactions such as oxidation and deterioration of aliphatic amines, polyether chain scission, and isomerization, generating a large number of colored impurities. Ultimately, this results in a high color of the finished product, with a yellowish or dark appearance, which seriously restricts its use in high-value-added fields such as high-end daily chemicals and light-colored textile auxiliaries. Summary of the Invention

[0004] One of the technical problems to be solved by the present invention is that the products obtained by the existing production methods of fatty amine polyoxyethylene ethers have high color. The present invention provides a catalyst for the synthesis of fatty amine polyoxyalkylene ethers, which produces products with low color when used in the synthesis of fatty amine polyoxyethylene ethers.

[0005] The catalyst used for the synthesis of fatty amine polyoxyalkylene ethers comprises the following components:

[0006] (a) Metallocene;

[0007] (b) Co-catalyst;

[0008] The weight ratio of the co-catalyst to the metallocene is 1 to 10; for example, but not limited to, weight ratios of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc. For comparison, in specific embodiments, the weight ratio of the co-catalyst to the metallocene is generally 9.

[0009] The cocatalyst comprises a boron compound represented by formula (1):

[0010] Equation (1);

[0011] Among them, P1~P 15 The atom is independently selected from hydrogen or halogen atoms; preferably, the halogen atom is fluorine.

[0012] When the catalyst described above is used in the synthesis of fatty amine polyoxyalkylene ethers, the resulting fatty amine polyoxyalkylene ethers have a significantly lower color than those obtained by conventional methods. The presence of the additives promotes the effect of metallocene in reducing the color of the product.

[0013] In the above technical solution, the co-catalyst preferably further includes alkylaluminoxane. Regarding color reduction, the boron compound and the alkylaluminoxane have a synergistic effect; preferably, the weight ratio of the alkylaluminoxane to the boron compound is 1 to 10, for example, but not limited to 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, etc., more preferably 2 to 5.

[0014] For comparison only, the boron compound used in the specific embodiments of the present invention is tris(pentafluorophenyl)borane, CAS number 1109-15-5.

[0015] In the above technical solution, the co-catalyst is preferred, characterized in that the alkyl group in the alkylaluminoxane is selected from at least one of the alkyl groups from C1 to C8.

[0016] In the above technical solution, the preferred metallocene is a complex of a group IVB transition metal element, and the ligand contains at least one cyclopentadiene anion ligand (Cp) or a cyclopentadiene derivative anion ligand.

[0017] The transition metal is Ti, Zr, or Hf.

[0018] By way of example only, the metallocene is selected from at least one of the following groups: titanium dichlorocerocene (molecular formula Cp₂TiCl₂), zirconium dichlorocerocene (molecular formula Cp₂ZrCl₂), and hafnium dichlorocerocene (molecular formula Cp₂HfCl₂). For comparative purposes only, the metallocene used in the specific embodiment is zirconium dichlorocerocene, CAS number 1291-32-3.

[0019] In a specific implementation, the trialkylaluminum used is triisobutylaluminum, with CAS number 100-99-2.

[0020] The second technical problem to be solved by the present invention is to provide the application of the above-mentioned catalyst.

[0021] To solve the second technical problem mentioned above, the technical solution of the present invention is as follows: the application of the catalyst described in any one of the technical solutions to the first technical problem mentioned above in the production of aliphatic amine polyoxyalkylene ethers by epoxy compound polymerization using aliphatic amines as initiators.

[0022] The key technology of this invention is the selection of catalyst components. As for the specific process conditions used in the synthesis of fatty amine polyoxyalkylene ethers, those skilled in the art can make reasonable choices without having to put in creative effort.

[0023] For example, but not limited to, the specific process conditions for using the catalyst of the present invention in the synthesis of fatty amine polyoxyalkylene ethers are:

[0024] A method for synthesizing aliphatic amine polyoxyalkylene ethers involves using an aliphatic amine containing nitrogen-hydrogen bonds as a starting agent and undergoing a polymerization reaction of an epoxide compound in the presence of a catalyst to obtain aliphatic amine polyoxyalkylene ethers.

[0025] For example only, when the epoxy compound is ethylene oxide, the fatty amine polyoxyalkylene ether is specifically a fatty amine polyoxyethylene ether (commonly known as fatty amine polyoxyethylene ether); when the epoxy compound is 1,2-epoxypropane, the fatty amine polyoxyalkylene ether is specifically a fatty amine polyoxy-1,2-propylene ether (commonly known as fatty amine polyoxypropylene ether) propylene ether. For comparative purposes only, the epoxy compound used in the specific embodiments of the present invention is ethylene oxide.

[0026] In the above technical solutions, there are no particular restrictions on the amount of catalyst used. Those skilled in the art can choose a reasonable amount based on factors such as effect and cost. Within a certain range, the larger the amount, the better the effect. However, if the amount is too large, the effect will not increase proportionally, and the proportion of the catalyst in the product cost will increase with the amount used. As a suggestion only, the amount of catalyst used is 0.08% to 1% of the mass of the aliphatic primary amine, for example, 0.10%, 0.20%, 0.30%, 0.40%, 0.45%, 0.50%, 0.55%, 0.60%, 0.70%, 0.80%, etc.

[0027] In the above technical solution, the preferred aliphatic amine conforms to RNH2, where R is an aliphatic hydrocarbon group with 8 to 20 carbon atoms. For example, but not limited to, R having 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, etc. The aliphatic hydrocarbon group can be alkyl or olefinic. It can be a straight-chain hydrocarbon group or a branched hydrocarbon group. For comparison only, the specific embodiments of the present invention all use n-octadecylamine.

[0028] In the above technical solution, the preferred reaction temperature is 110~170℃, such as, but not limited to, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, and 150℃. More preferably, it is 120~150℃.

[0029] In the above technical solution, the preferred reaction pressure is 0~0.5 MPa using a gauge manometer. For example, but not limited to, 0.05 MPa, 0.1 MPa, 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.5 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, etc., and more preferably 0~0.4 MPa.

[0030] In the above technical solution, the preferred total molar ratio of epoxy compound to aliphatic amine is 5 to 20. For example, but not limited to, the total molar ratio of epoxy compound to aliphatic amine is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., and more preferably 8 to 18.

[0031] Regarding the preparation method of the catalyst used in this invention, it is sufficient to mix the required components in any order to achieve comparable technical effects. The components can be mixed before being added to the polymerization reaction system or mixed in situ within the polymerization reaction system; there are no particular limitations, and comparable technical effects can be achieved in both cases. However, to solve the second technical problem mentioned above, it is recommended to mix the components before adding them to the polymerization reaction system, i.e., the catalyst preparation method includes:

[0032] The catalyst is obtained by adding a co-catalyst to a metallocene and mixing it, specifically by sequentially adding the required amounts of trialkylaluminum, boron compound, and alkylaluminoxane to the metallocene and mixing them thoroughly. The embodiments in the specific implementation details of this invention all employ this catalyst preparation method.

[0033] In a specific embodiment of the present invention, the color of the product is measured using the method of GB / T 22295-2008 ("Test Method for Color of Transparent Liquids (Gardner Colorimetric)").

[0034] The present invention will be illustrated below with specific examples of its implementation. Detailed Implementation

[0035]

Comparative Example 1

[0036] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of potassium hydroxide were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0037] Analysis and testing showed that the color (Gardner color) value of the fatty amine polyoxyethylene ether product was 11.

[0038] [Comparative Example 2]

[0039] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of zirconium dichloroethylene were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0040] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 8. － .

[0041] [Comparative Example 3]

[0042] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of triisobutylaluminum were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0043] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 9. ＋ .

[0044] [Comparative Example 4]

[0045] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of methylaluminoxane were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0046] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 8. ＋ .

[0047] [Comparative Example 5]

[0048] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of tris(pentafluorophenyl)borane were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0049] Analysis and testing showed that the color (Gardner color) value of the fatty amine polyoxyethylene ether product was 8.

[0050]

Example 1

[0051] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g of zirconium dichloroethylene and 3.6 g of triisobutylaluminum) were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0052] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 7. ＋ .

[0053]

Example 2

[0054] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g of zirconium dichloroethylene and 3.6 g of methylaluminoxane) were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0055] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 6. － .

[0056]

Example 3

[0057] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g of zirconium dichloroethylene and 3.6 g of tris(pentafluorophenyl)borane) were added to a 2L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90°C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140°C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140°C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60°C to obtain the octadecylamine polyoxyethylene ether product.

[0058] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 7. － .

[0059]

Example 4

[0060] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g zirconium dichloroethylene, 2.4 g methylaluminoxane, and 1.2 g tris(pentafluorophenyl)borane) were added to a 2 L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90 °C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140 °C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had entered, the feed was stopped. The product was aged at 140 °C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60 °C to obtain the octadecylamine polyoxyethylene ether product.

[0061] Analysis and testing showed that the colorimetric (Gardner colorimetric) value of the fatty amine polyoxyethylene ether product was 5. ＋ .

[0062]

Example 5

[0063] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g zirconium dichloroethylene, 3.0 g methylaluminoxane, and 0.6 g tris(pentafluorophenyl)borane) were added to a 2 L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90 °C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140 °C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140 °C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60 °C to obtain the octadecylamine polyoxyethylene ether product.

[0064] Analysis and testing showed that the color (Gardner color) value of the fatty amine polyoxyethylene ether product was 2.

[0065]

Example 6

[0066] 800.0 g (3.0 mol) of octadecylamine and 4.0 g of catalyst (catalyst composition: 0.4 g zirconium dichloroethylene, 3.0 g methylaluminoxane, and 0.6 g tris(pentafluorophenyl)borane) were added to a 2 L reactor (equipped with a stirrer, an electric heating jacket, and an internal water-cooling coil), and the reactor was sealed. The reactor was purged with nitrogen three times, the stirrer was turned on, and the temperature was raised to 90 °C. Vacuum treatment was carried out at -0.09 MPa for 60 min, then the temperature was raised to 140 °C, ethylene oxide was introduced, and this temperature was maintained. The reaction pressure was maintained at 0.3 MPa by controlling the ethylene oxide feed rate. When a total of 1034 g (30.0 mol) of ethylene oxide had been introduced, the feed was stopped. The product was aged at 140 °C until the pressure no longer dropped (indicating that the aging reaction was complete), and vacuum treatment was carried out at -0.09 MPa for 30 min. Then the temperature was lowered to 60 °C to obtain the octadecylamine polyoxyethylene ether product.

[0067] Analysis and testing showed that the color (Gardner color) value of the fatty amine polyoxyethylene ether product was 4.

Claims

1. A catalyst for the synthesis of fatty amine polyoxyalkylene ethers, comprising the following components: (a) Metallocene; (b) Co-catalyst; The weight ratio of the co-catalyst to the metallocene is 1~10; The cocatalyst comprises a boron compound represented by formula (1): Equation (1); in, P1~P 15 The atom is independently selected from hydrogen or halogen atoms; preferably, the halogen atom is fluorine.

2. The co-catalyst according to claim 1, characterized in that: The cocatalyst includes alkylaluminoxane.

3. The co-catalyst according to claim 2, characterized in that: The weight ratio of alkylaluminoxane to the boron compound is 1 to 10.

4. The co-catalyst according to claim 3, characterized in that: The weight ratio of alkylaluminoxane to the boron compound is 2 to 5.

5. The co-catalyst according to claim 1, characterized in that... The alkyl group in alkylaluminoxane is selected from at least one of the C1 to C8 alkyl groups.

6. The cocatalyst according to claim 1, characterized in that the metallocene is a complex of a group IVB transition metal element, and the ligand contains at least one cyclopentadiene anionic ligand or a cyclopentadiene derivative anionic ligand.

7. The use of the catalyst according to any one of claims 1 to 6 in obtaining aliphatic amine polyoxyalkylene ethers by epoxy compound polymerization using aliphatic amines as initiators.

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