Preparation method of polyether amine for emulsifier

Abstract

The invention discloses a preparation method of polyether amine for an emulsifier, and belongs to the technical field of synthesis of organic high-molecular compounds. The preparation method comprises the following steps: firstly, by taking methanol as an initiator and sodium methoxide as a catalyst, introducing epoxide in sections to obtain methanol polyether; liquid ammonia, hydrogen and the prepared methanol polyether are introduced into a tubular reactor with a reductive amination catalyst for a hydrogenation amination reaction, and methanol polyether amine is prepared. Wherein the segmented introduction of the epoxide is as follows: ethylene oxide is introduced in the first stage, a mixture of ethylene oxide and epoxypropane is introduced in the second stage, and epoxypropane is introduced in the third stage for blocking. The polyether structure with excellent emulsifying performance is obtained by designing different addition modes and sequences of EO and PO, the emulsifying performance of polyether amine is greatly improved, and the process is simple and easy to operate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic polymer compound synthesis, and particularly relates to a preparation method of polyether amine for emulsifier. BACKGROUND

[0002] Polyether amine (PEA) is a kind of polymer with polyether structure as a main chain and amine group as a terminal active functional group. The polyether amine is aminated polyether by converting hydroxyl groups of polyethylene glycol, polypropylene glycol or ethylene glycol / propylene glycol copolymer into amine groups. By selecting different polyoxyalkyl structures, the reactivity, toughness, viscosity and hydrophilicity of the polyether amine can be adjusted, and the amine group provides the possibility of reaction of the polyether amine with various compounds. The special molecular structure endows the polyether amine with excellent comprehensive performance. The commercialized polyether amine includes a series of products with single function, double function, triple function and molecular weight from 230 to 5000. The compound can be widely used in epoxy resin curing agent, wind energy blade curing agent, polyurethane polyurea elastomer, gasoline cleaning agent, water-based coating, textile finishing agent and emulsifier, dispersant and the like.

[0003] The polyether amine becomes a research hotspot of emulsifier due to its non-toxicity, low cost and biodegradability. The polyether amine has various types, and the number and distribution of hydrophilic and hydrophobic segments of polyether amines with different structures are different, resulting in different emulsifying properties of the polyether amines. At present, the existing polyether amine has low emulsifying efficiency and poor emulsifying performance.

[0004] The emulsifying performance of the polyether amine is often affected by the structure and morphology, so it is necessary to finely synthesize and structure design the polyether amine, so that the synthesized polyether amine has excellent emulsifying performance. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, the purpose of the present application is to provide a preparation method of polyether amine for emulsifier, so as to solve the problem of poor emulsifying performance of the existing polyether amine.

[0006] To solve the above problems, the technical scheme adopted by the present application is as follows: A preparation method of polyether amine for emulsifier, comprising the following steps: S1, synthesizing methanol polyether: taking methanol as a starter, sodium methoxide as a catalyst, and sequentially feeding in epoxide to obtain methanol polyether; wherein the sequentially feeding in of the epoxide is as follows: feeding in ethylene oxide in the first stage, feeding in a mixture of ethylene oxide and propylene oxide in the second stage, and feeding in propylene oxide for end-capping in the third stage; S2, synthesizing methanol polyether amine: feeding in liquid ammonia, hydrogen and the methanol polyether prepared in step S1 into a tubular reactor with a reduction amination catalyst to perform a hydrogenation amination reaction, so as to obtain the methanol polyether amine.

[0007] As a preferred embodiment of the present application, the molar ratio between the first stage of ethylene oxide and methanol in step S1 is 3-8:1; the molar ratio between the second stage of ethylene oxide, propylene oxide and methanol is 50-60:4-8:1; the molar ratio between the third stage of propylene oxide and methanol in step S1 is 1-5:1.

[0008] As a preferred embodiment of the present application, the reaction temperature of the first stage of adding epoxide in step S1 is 110-160℃, the relative pressure is ≤0.3MPa, and the aging time is 1-3h; the reaction temperature of the second stage is 110-140℃, the relative pressure is ≤0.3MPa, and the aging time is 1-4h; the reaction temperature of the third stage is 110-140℃, the relative pressure is ≤0.3MPa, and the aging time is 1-5h.

[0009] As a preferred embodiment of the present application, the amount of sodium methoxide in step S1 is 0.1-0.6% of the mass of methanol.

[0010] As a preferred embodiment of the present application, the molar ratio between the liquid ammonia and the methanol polyether in step S2 is 8-15:1; the molar ratio between the hydrogen and the methanol polyether is 20-50:1; and the mass space velocity of the methanol polyether is 0.08-1.50Kg / Kg.CAT.h.

[0011] As a preferred embodiment of the present application, the reducing amination catalyst in step S2 is a nickel-palladium supported catalyst, and the support of the nickel-palladium supported catalyst is a mixture of alumina and silica.

[0012] Further preferably, the loading amount of nickel is 10-25wt% of the nickel-palladium supported catalyst, preferably 12-15wt%; the loading amount of palladium is 0.1-2wt% of the nickel-palladium supported catalyst, preferably 0.5-1wt%; the content of the support is 73-89.9wt% of the nickel-palladium supported catalyst, preferably 84-87.5wt%; and the mass ratio of alumina to silica in the support is 1-10:1, preferably 3-7:1.

[0013] As a preferred embodiment of the present application, the preparation method of the reducing amination catalyst is as follows: A1, uniformly mixing spherical Al(OH)3 and SiO2 particles, grinding and sieving to obtain a mixture of 100-200 mesh, drying the mixture at 100-150°C for 20-30h, then calcining at 1000-1100°C for 20-30h, and obtaining a white powder after cooling, which is shaped to obtain a spherical carrier with γ-Al2O3 / SiO2 particles adhered to the surface, the diameter of the spherical carrier being 1-8mm, preferably 1-5mm; placing the carrier in dilute ammonia water with a concentration of 1-10%, until the adsorption amount of the dilute ammonia water is 1-15% of the weight of the carrier; A2, adding nickel nitrate and palladium nitrate to deionized water to prepare a metal salt solution, immersing the carrier prepared in step A1 in the metal salt solution, drying after sufficient adsorption and equilibrium, and calcining at 360-420°C for 4-8h; after cooling, the carrier loaded with nickel and palladium is reduced in a hydrogen atmosphere to obtain the reduced amination catalyst.

[0014] As a preferred embodiment of the present application, the temperature of the reduction in step A2 is 220-370°C, and the hydrogen flow rate is 0.1-5ml / KG.CAT.min.

[0015] As a preferred embodiment of the present application, the reaction temperature of the hydroamination reaction in step S2 is 130-190°C, and the reaction pressure is 10-16MPa.

[0016] Compared with the prior art, the present application has the following advantages: (1) The present application designs the structure of the methanol polyether by three-stage feeding of epoxide, the first stage of feeding of EO can enhance water solubility, so that the polyether amine can more easily diffuse in the aqueous phase, the second stage of feeding of a mixture of EO and PO can adjust the HLB value by adjusting the ratio between EO and PO, so that the HLB value can match the target emulsifier, and the third stage of feeding of PO can perform end-capping. The present application first determines the total ratio of EOPO by the HLB value, and then designs the different addition modes and sequences of EO and PO to obtain a polyether structure with excellent emulsifying performance.

[0017] (2) In the synthesis of the methanol polyether, the present application uses sodium methoxide as the catalyst, without the need for dehydration or dealcoholization treatment of the raw materials, effectively simplifying the process and improving the production efficiency.

[0018] (3) In the synthesis of the methanol polyether amine, the present application uses a nickel-palladium supported catalyst as the reduction amination catalyst, the carrier of the catalyst is pretreated with a small amount of ammonia water before loading the metal salt, which can make the metal salt in the form of nanometer adsorbed on the carrier during the impregnation and co-precipitation process, the loading process is more efficient, and the adhesion is more firm, which is particularly suitable for preparing methanol-based high-molecular, high-viscosity polyether amines. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 GPC chart of the polyether amine prepared in Example 1 and Example 2 of the present application; Figure 2 GPC chart of the polyether amine prepared in Comparative Example 1 of the present application; Figure 3 GPC chart of the polyether amine prepared in Comparative Example 2 of the present application; Figure 4 GPC chart of the polyether amine prepared in Comparative Example 3 of the present application; Figure 5 GPC chart of the polyether amine prepared in Comparative Example 4 of the present application. DETAILED DESCRIPTION

[0020] The present application will be further described in detail below in combination with the accompanying drawings and specific embodiments.

[0021] The polyether amine for emulsifier involved in the present application is mainly used as an emulsifier with excellent emulsifying performance, and is designed by adding different epoxides in stages to realize the polyether structure, and the preparation method specifically includes the following steps: S1, synthesizing methanol polyether: taking methanol as a starter and sodium methoxide as a catalyst, and adding epoxides in stages to obtain methanol polyether; wherein, the epoxides are added in stages as follows: in the first stage, adding ethylene oxide, in the second stage, adding a mixture of ethylene oxide and propylene oxide, and in the third stage, adding propylene oxide for end-capping.

[0022] In step S1, sodium methoxide is used as a catalyst for the polymerization stage, and after mixing methanol with sodium methoxide, there is no need for dehydration, which effectively simplifies the process; preferably, the amount of sodium methoxide is 0.1-0.6% of the mass of methanol.

[0023] By adding different epoxides in three stages, the methanol polyether structure with excellent emulsifying performance can be obtained through structure design. Further, by respectively controlling the proportions of epoxides in the three stages, methanol polyethers with different structures can be obtained. Specifically, the structural formula of the methanol polyether is CH3Oa(EO)(mEOnPO)b(PO), the molar ratio between the ethylene oxide added in the first stage and methanol is controlled to be 3-8:1, which can ensure that the coefficient a in CH3Oa(EO)(mEOnPO)b(PO) is 3-8; the molar ratio between the ethylene oxide and propylene oxide added in the second stage and methanol is controlled to be 50-60:4-8:1, which can ensure that the coefficient m in CH3Oa(EO)(mEOnPO)b(PO) is 50-60 and the coefficient n is 4-8; the molar ratio between the propylene oxide added in the third stage and methanol is controlled to be 1-5:1, which can ensure that the coefficient b in CH3Oa(EO)(mEOnPO)b(PO) is 1-5.

[0024] Specifically, the reaction conditions of each stage of the polymerization reaction in step S1 are as follows: the reaction temperature of the first stage of adding epoxide is 110-160℃, the relative pressure is ≤0.3 MPa, and the aging time is 1-3 h; the reaction temperature of the second stage of adding epoxide is 110-140℃, the relative pressure is ≤0.3 MPa, and the aging time is 1-4 h; the reaction temperature of the third stage of adding epoxide is 110-140℃, the relative pressure is ≤0.3 MPa, and the aging time is 1-5 h.

[0025] S2, synthesis of methanol polyether amine: liquid ammonia, hydrogen and the methanol polyether prepared in step S1 are introduced into a tubular reactor with a reduction amination catalyst to perform a hydrogenation amination reaction, the reaction temperature is 130-190℃, and the reaction pressure is 10-16 MPa, to prepare methanol polyether amine.

[0026] In step S2, the molar ratio of liquid ammonia to methanol polyether is 8-15:1; the molar ratio of hydrogen to methanol polyether is 20-50:1, and the mass space velocity of methanol polyether is 0.08-1.50 Kg / Kg.CAT.h.

[0027] The reduction amination catalyst in step S2 is a nickel-palladium supported catalyst, and the carrier of the nickel-palladium supported catalyst is a mixture of alumina (γ-Al2O3) and silicon dioxide. Specifically, the loading amount of nickel is 10-25 wt% of the nickel-palladium supported catalyst, preferably 12-15 wt%; the loading amount of palladium is 0.1-2 wt% of the nickel-palladium supported catalyst, preferably 0.5-1 wt%; the content of the carrier is 73-89.9 wt% of the nickel-palladium supported catalyst, preferably 84-87.5 wt%; and the mass ratio of alumina to silicon dioxide in the carrier is 1-10:1, preferably 3-7:1.

[0028] The carrier of the nickel-palladium supported catalyst is pretreated with ammonia water, and then a certain amount of metal nickel salt and metal palladium salt is loaded to obtain the catalyst. The carrier is composed of alumina and silicon dioxide by compounding through pressing or the like, and the carrier with high specific surface area and three-dimensionally connected double-helical pore structure suitable for loading metal can be prepared by adjusting the ratio between alumina and silicon dioxide; and the metal salt is adsorbed on the carrier in nanometer form by pretreating the carrier with ammonia water, and the adhesion is more firm, which can greatly improve the service life of the catalyst.

[0029] The preparation method of the reduction amination catalyst is specifically as follows: A1, the spherical Al(OH)3 and SiO2 particles are mixed in a mortar, ground and sieved to obtain a mixture of 100-200 mesh, which is transferred to a crucible, dried at 100-150°C for 20-30h, and then calcined at 1000-1100°C for 20-30h to obtain a white powder. The white powder is shaped by pressing to obtain a spherical carrier with γ-Al2O3 / SiO2 particles attached to the surface, the diameter of the spherical carrier being 1-8mm, preferably 1-5mm. The carrier is placed in dilute ammonia water with a concentration of 1-10%, until the adsorption amount of the dilute ammonia water is 1-15% of the weight of the carrier; A2, the nickel nitrate and palladium nitrate are added to deionized water to prepare a metal salt solution, the carrier prepared in step A1 is immersed in the metal salt solution, dried after sufficient adsorption and equilibrium, and calcined in a muffle furnace at 360-420°C for 4-8h. After cooling, the carrier loaded with nickel and palladium is reduced in a hydrogen atmosphere at 220-370°C, and the hydrogen flow rate is 0.1-5ml / K Kg.CAT.h, to obtain a reduced amination catalyst.

[0030] Example 1 The present embodiment provides a preparation method of a supported reduced amination catalyst and a method for preparing a polyether amine emulsifier using the supported reduced amination catalyst.

[0031] A preparation method of a supported reduced amination catalyst, specifically comprising the following steps: A1, 1223g of spherical Al(OH)3 and 200g of SiO2 particles are mixed in a mortar, ground and sieved to obtain a mixture of 100-200 mesh, which is transferred to a crucible, dried at 110°C for 14h, and then calcined in air at 1050°C at a heating rate of 3°C / min (the heating rate refers to the rate at which the temperature is raised from room temperature to the final temperature per minute) for 20h. The white powder is granulated and shaped to obtain a spherical carrier with γ-Al2O3 / SiO2 particles attached to the surface and a diameter of 4mm, about 1000g. The 1000g of Al2O3 / SiO2 spherical carrier is placed in 90g of ammonia solution with a concentration of 5%, stirred and absorbed for about 1h, and then used.

[0032] A2、According to the content of the catalyst, the above carrier is immersed in an aqueous solution containing Ni(NO3)3·6H2O and Pb(NO3)3 by using an equal volume impregnation method, and is dried in an oven at 110°C after sufficient adsorption and equilibrium. After drying, it is calcined in a muffle furnace at 360°C for 10h. After cooling, the carrier loaded with nickel and palladium is reduced in a hydrogen atmosphere at 300°C, and the hydrogen flow rate is 0.3ml / KG catalyst·min. Thus, a reduced amination catalyst with a Ni content of 13wt% and a Pb content of 0.52wt% is obtained, which is named CAT-M01.

[0033] A method for preparing a polyether amine for an emulsifier, comprising the following steps: S1, adding the epoxide in three steps: the first step is to add ethylene oxide, the second step is to add a mixture of ethylene oxide and propylene oxide, and the third step is to add propylene oxide: Into a 1.5L reactor, 160g of methanol (methanol water content ≤0.10%, 5mol), 0.48g of CH3ONa were sequentially added, vacuumed and replaced with nitrogen at room temperature, and the nitrogen pressure was ≥0.2MPa. Then vacuumed to -0.090MPa. Then slowly heated to 130°C, and 880g (20mol) of ethylene oxide was introduced, and the polymerization reaction was carried out at a relative pressure ≤0.3MPa, and the aging time was 2 hours. The obtained polyether was transferred to a 20L reactor, vacuumed and replaced with nitrogen, and the nitrogen pressure was ≥0.2MPa. Then vacuumed to -0.090MPa. Then slowly heated to 120°C, and 12320g (280mol) of a mixture of ethylene oxide and 1450g (25mol) of propylene oxide was introduced, and the polymerization reaction was carried out at 120°C and a relative pressure ≤0.3MPa, and the aging time was 3 hours. Then continue to introduce propylene oxide 580g (10mol) at this temperature, and the polymerization reaction was carried out at 120°C and a relative pressure ≤0.3MPa, and the aging time was 2 hours. After cooling, adsorption post-treatment was carried out to obtain methanol polyether M-01, and the structure of the obtained methanol polyether M-01 is CH3O4EO(56EO5PO)2PO.

[0034] S2, the polyether is hydrogenated and aminated to prepare a polyether amine, which is evaluated by using a continuous fixed bed process. The reduction amination catalyst CAT-M01 is reduced in a hydrogen stream (at normal pressure) at 250°C for 24h before use. The temperature in the reactor is naturally increased to 150°C, and the pressure is increased to 13.0MPa. After the system is stable, a mixed liquid with a molar ratio of NH3 / M-01=12 is pumped into the reactor, and the hydrogen gas is introduced at a molar amount of 1 times that of M-01. After a period of time, the polyether amine product is obtained by filtration and vacuum distillation, and is recorded as MA-01. According to chemical analysis, the reaction conversion rate is 99.8%, the primary amine selectivity is 99.0%, and the total amine value of the polyether amine MA-01 is 18.5mgKOH / g.

[0035] Example 2 This example provides a method for preparing polyether amine for emulsifier by using supported reductive amination catalyst, which is different from example 1 in step S1, and the difference is as follows: S1, adding the epoxide in three steps, the order of addition is first adding ethylene oxide, second adding a mixture of ethylene oxide and propylene oxide, and third adding propylene oxide: Into a 1.5L reactor, 160g of methanol (methanol water content ≤0.10%, 5mol), 0.48g of CH3ONa were sequentially added, vacuum was replaced by nitrogen at room temperature, and the nitrogen pressure was charged to ≥0.2MPa, and then vacuumed to -0.090MPa. Then slowly heated to 130℃, and 1100g (25mol) of ethylene oxide was introduced, and the polymerization reaction was carried out at a relative pressure of ≤0.3MPa, and the aging time was 2 hours. The obtained polyether was transferred to a 20L reactor, vacuum was replaced by nitrogen, nitrogen pressure was charged to ≥0.2MPa, and then vacuumed to -0.090MPa. Then slowly heated to 120℃, and 11440g (260mol) of a mixture of ethylene oxide and 1740g (30mol) of propylene oxide was introduced, and the polymerization reaction was carried out at 120℃ and a relative pressure of ≤0.3MPa, and the aging time was 3 hours. Then 725g (12.5mol) of propylene oxide was continuously introduced at this temperature, and the polymerization reaction was carried out at 120℃ and a relative pressure of ≤0.3MPa, and the aging time was 2 hours. After cooling, adsorption post-treatment was carried out to obtain polyether M-02, and the structure of the obtained methanol polyether is: CH3O5EO(52EO6PO)2.5PO.

[0036] The synthesis of polyether amine was carried out according to the step S2 of example 1, and the obtained polyether amine was denoted as MA-02. According to chemical analysis, the reaction conversion rate was 99.5%, the primary amine selectivity was 99.0%, and the total amine value of polyether amine MA-02 was 18.5mgKOH / g.

[0037] Comparative Example 1 This comparative example provides a method for preparing polyether amine for emulsifier by using supported reductive amination catalyst, which is different from example 1 in step S1, and the difference is as follows: S1, adding the epoxide in three steps, the order of addition is first adding ethylene oxide, second adding a mixture of ethylene oxide and propylene oxide, and third adding propylene oxide: Into a 20L reactor, 160g of methanol (methanol water content ≤0.10%, 5mol), 0.48g of CH3ONa were sequentially added, at room temperature, vacuum replacement with nitrogen, nitrogen pressure to ≥0.2MPa, then vacuum to -0.090MPa. Then slowly heated to 130℃, directly into 880g of ethylene oxide (20mol), 12320g of ethylene oxide and 1450g of propylene oxide mixture (280mol, 25mol), and 580g of propylene oxide (10mol), under the relative pressure ≤0.3MPa, the polymerization reaction was carried out, the aging time was 3 hours. After cooling, the adsorption post-treatment was carried out to obtain the polyether M-03, and the structure of the obtained methanol polyether was: CH3O(60EO7PO).

[0038] The synthesis of polyether amine was carried out according to the procedure of step S2 of example 1, and the obtained polyether amine was denoted as MA-03. According to chemical analysis, the reaction conversion rate was 97.0%, the primary amine selectivity was 98.0%, and the total amine value of the polyether amine MA-03 was 18.1mgKOH / g.

[0039] Comparative example 2 This comparative example provides a method for preparing polyether amine for emulsifier by using supported reduction amination catalyst. The difference between this comparative example and example 1 is that the step S1 is different, and the specific difference is as follows: S1, the epoxy material is added in two steps, the first step is to add ethylene oxide, the mixture of ethylene oxide and propylene oxide, and the second step is to add propylene oxide: Into a 20L reactor, 160g of methanol (methanol water content ≤0.10%, 5mol), 0.48g of CH3ONa were sequentially added, at room temperature, vacuum replacement with nitrogen, nitrogen pressure to ≥0.2MPa, then vacuum to -0.090MPa. Then slowly heated to 130℃, directly into 880g of ethylene oxide (20mol), 12320g of ethylene oxide and 1450g of propylene oxide mixture (280mol, 25mol), and 580g of propylene oxide (10mol), under the relative pressure ≤0.3MPa, the polymerization reaction was carried out, the aging time was 3 hours. After cooling, the adsorption post-treatment was carried out to obtain the polyether M-03, and the structure of the obtained methanol polyether was: CH3O(60EO7PO).

[0040] The synthesis of polyether amine was carried out according to the procedure of step S2 of example 1, and the obtained polyether amine was denoted as MA-03. According to chemical analysis, the reaction conversion rate was 97.0%, the primary amine selectivity was 98.0%, and the total amine value of the polyether amine MA-03 was 18.1mgKOH / g.

[0041] Comparative example 3 This comparative example provides a method for preparing polyether amine for emulsifier using supported reductive amination catalyst. The difference between this comparative example and Example 1 is that the step S1 is different, and the difference is as follows: S1, the epoxy material is added in two steps, the first step is to add ethylene oxide, and the second step is to add a mixture of ethylene oxide and propylene oxide and propylene oxide: 160 g of methanol (methanol water content ≤0.10%, 5 mol), 0.48 g of CH3ONa are sequentially added into a 1.5 L reaction kettle, vacuum replacement with nitrogen is carried out at room temperature, the nitrogen pressure is charged to ≥0.2 MPa, and then vacuum is extracted to -0.090 MPa. Then slowly heat to 130°C, the first step is to pass in 1100 g (25 mol) of ethylene oxide, and the polymerization reaction is carried out at a relative pressure ≤0.3 MPa, and the aging time is 2 hours. The obtained polyether is transferred to a 20 L reaction kettle, vacuum replacement with nitrogen is carried out, the nitrogen pressure is charged to ≥0.2 MPa, and then vacuum is extracted to -0.090 MPa. The second step is to slowly heat to 120°C, and then pass in 11440 g (260 mol) of a mixture of ethylene oxide and propylene oxide and propylene oxide 725 g (12.5 mol) of propylene oxide, and the polymerization reaction is carried out at 120°C and a relative pressure ≤0.3 MPa, and the aging time is 2 hours. After cooling, adsorption post-treatment is carried out to obtain polyether M-05, and the obtained methanol polyether structure is: CH3O (5EO) (52PEO8.5PO).

[0042] The synthesis of polyether amine is carried out according to the step S2 of Example 1, and the obtained polyether amine is denoted as MA-05. According to chemical analysis, the reaction conversion rate is 98.2%, the primary amine selectivity is 98.6%, and the total amine value of polyether amine MA-05 is 18.3 mgKOH / g.

[0043] Comparative Example 4 This comparative example provides a method for preparing polyether amine for emulsifier using supported reductive amination catalyst. The difference between this comparative example and Example 1 is that the step S1 is different, and the difference is as follows: S1, in three steps, first step, a mixture of ethylene oxide and propylene oxide is added, second step, propylene oxide is added, third step, ethylene oxide is added: 160 g of methanol (methanol water content ≤0.10%, 5 mol), 0.48 g of CH3ONa are sequentially added to a 20 L reaction kettle, vacuum is extracted and replaced with nitrogen at room temperature, nitrogen is pressurized to ≥0.2 MPa, and then vacuum is extracted to -0.090 MPa. Then slowly warm up to 130°C, and then 11440 g (260 mol) of a mixture of ethylene oxide and 1740 g (30 mol) of propylene oxide are introduced, and the polymerization reaction is carried out at a relative pressure of ≤0.3 MPa, and the aging time is 3 hours. Then continue to introduce propylene oxide 725 g (12.5 mol) at this temperature, and the polymerization reaction is carried out at 120°C and a relative pressure of ≤0.3 MPa, and the aging time is 2 hours. Finally, continue to introduce ethylene oxide 1100 g (25 mol) at this temperature, and the polymerization reaction is carried out at 120°C and a relative pressure of ≤0.3 MPa, and the aging time is 2 hours. After cooling, adsorption post-treatment is carried out to obtain polyether M-06, and the structure of the obtained methanol polyether M-06 is: CH3O(52EO6PO)2.5PO5EO.

[0044] The synthesis of polyether amine is carried out according to the procedure of step S2 of Example 1, and the obtained polyether amine is denoted as MA-06. According to chemical analysis, the reaction conversion rate is 97.5%, the primary amine selectivity is 97.0%, and the total amine value of polyether amine MA-06 is 18.0 mgKOH / g.

[0045] Comparative Example 5 This comparative example provides a preparation method of a supported reductive amination catalyst and a method for preparing a polyether amine for emulsifier by using the supported reductive amination catalyst.

[0046] A preparation method of a supported reductive amination catalyst, specifically comprising the following steps: A1, 1223 g of spherical Al(OH)3 and 200 g of SiO2 particles are mixed in a mortar, and after grinding and sieving to obtain a mixture of 100-200 mesh, the mixture is transferred to a crucible, dried at 110°C for 14 h, and then calcined in air at 1050°C for 20 h at a heating rate of 3°C / min (the heating rate refers to the rate at which the temperature is raised from room temperature to the final temperature per minute). After granulation and molding, about 1000 g of spherical carrier with a diameter of 4 mm is obtained, and γ-Al2O3 / SiO2 particles are attached to the surface.

[0047] A2, according to the content of the catalyst composition, using equal volume impregnation method is immersed in the above spherical carrier containing Ni(NO3)3·6H2O, Pb(NO3)3 aqueous solution, adsorption equilibrium after drying in the oven at 110℃, after drying in the muffle furnace at 360℃ for 10h;After cooling, get, the carrier loaded with nickel and palladium is reduced in hydrogen atmosphere at 300℃, the hydrogen flow is 0.3ml / KG catalyst·min, namely the reduction amination catalyst with Ni content of 13wt%, Pb content of 0.52wt%, named CAT-M02.

[0048] A preparation method of polyether amine for emulsifier, which is different from example 1 in that the reduction amination catalyst in step S2 is replaced by catalyst CAT-M02, and other steps are the same as example 1.

[0049] The prepared polyether amine product is analyzed by chemical analysis, the reaction conversion rate is 96.5%, the primary amine selectivity is 96.0%, and the total amine value of polyether amine is 17.5mgKOH / g. Compared with the MA-01 product of example 1, the conversion rate and primary amine selectivity are reduced, which shows that the preparation method of catalyst CAT-M01 in example 1 is more suitable for amination of polyether with this structure.

[0050] Comparative example 6 The present comparative example provides a preparation method of polyether amine for emulsifier, which is different from example 2 in that the reduction amination catalyst in step S2 is replaced by catalyst CAT-M02, and other steps are the same as example 2.

[0051] The prepared polyether amine product is analyzed by chemical analysis, the reaction conversion rate is 96.7%, the primary amine selectivity is 96.2%, and the total amine value of polyether amine is 17.7mgKOH / g. Compared with the MA-01 product of example 1, the conversion rate and primary amine selectivity are reduced, which shows that the preparation method of catalyst CAT-M01 in example 1 is more suitable for amination of polyether with this structure.

[0052] Application example In order to verify the emulsifying performance of the polyether amine for emulsifier prepared by the present application, the polyether amine products prepared in examples 1-2 and comparative examples 1-4 are respectively made into emulsion explosive emulsion matrix according to the same method, and the limit emulsification performance of the emulsifier is tested, and the specific experimental method is as follows: The proportion of the fixed composite oil phase material in the emulsion explosive emulsion matrix is adjusted to 5-50% of the normal amount, the proportion of the water phase component and the oil phase component in the emulsion explosive emulsion matrix is fixed, and the emulsification of the emulsion matrix is observed under the same operating conditions. The limit emulsification experiment formula is shown in table 1.

[0053] Table 1: Emulsion explosive emulsion base formula

[0054] The preparation process parameters of the emulsion explosive emulsion base are as follows: water phase temperature: 90-95℃, oil phase temperature: 45-50℃, stirring speed: 1100r / min. The emulsion base preparation operation method: heat the oil phase and the water phase to the predetermined temperature, start the stirrer and set the speed to 1100r / min, add the water phase into the oil phase for emulsification within 1min, continue to stir at 1100r / min for 1min for fine emulsification, and after fine emulsification, place the emulsion base in a clean transparent plastic cup and wait for testing. As a comparative example, repeat the above operation to prepare the emulsion base using emulsifier Span-80, and observe and test the appearance state and performance characteristics of the two emulsion bases.

[0055] Prepare emulsion explosive emulsion bases with the addition amount of emulsifier being 0.15%, 0.20% and 0.30% respectively, observe the appearance of the emulsion bases, and evaluate the limiting emulsification performance of the emulsifiers. The experimental phenomena are shown in Table 2.

[0056] Table 2: Comparison of emulsion effect of emulsion explosive emulsion base

[0057] As shown in Table 1, MA-01 and MA-02 structural polyether amines have good emulsification performance, which shows that the emulsification performance of the products after amination of CH3O4EO(56EO5PO)2PO and CH3O5EO(52EO6PO)2.5PO structures is better.

[0058] From the above experimental results, it can be seen that the emulsification performance of the emulsion bases prepared by adding the emulsifier in the order of methanol, ethylene oxide and propylene oxide is better than that of the emulsion bases prepared by adding the emulsifier in the order of ethylene oxide, methanol and propylene oxide. Figures 1-5 It can be seen that, compared with Comparative Examples 1-4, although the molecular composition of each product is obtained by amination of methanol, ethylene oxide and propylene oxide polyether, the molecular weight of each product is almost the same, but due to the difference in the addition order and method of the emulsifier, the structure is different, and the application emulsification performance is different.

[0059] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the scope of protection of the present application. Any non-essential changes and substitutions made by those skilled in the art based on the present application are within the scope of protection of the present application.

Claims

1. A method for preparing a polyetheramine for emulsifier, characterized in that: The following steps are involved: S1. Synthesis of methanol polyether: using methanol as an initiator and sodium methoxide as a catalyst, introducing epoxide in stages to obtain methanol polyether; wherein the epoxide is introduced in stages as follows: ethylene oxide is introduced in the first stage, a mixture of ethylene oxide and propylene oxide is introduced in the second stage, and propylene oxide is introduced in the third stage for end-capping; S2. Synthesis of methanol polyetheramine: Liquid ammonia, hydrogen and the methanol polyether prepared in step S1 are introduced into a tubular reactor containing a reductive amination catalyst to carry out a hydrogenation amination reaction to prepare the methanol polyetheramine.

2. The method for preparing a polyetheramine for emulsifier according to claim 1, wherein: The molar ratio of ethylene oxide to methanol introduced in the first stage in step S1 is 3-8:1; the molar ratio of ethylene oxide and propylene oxide to methanol introduced in the second stage is 50-60:4-8:1; the molar ratio of propylene oxide to methanol introduced in the third stage in step S1 is 1-5:

1.

3. The method for preparing the polyetheramine for emulsifier according to claim 1 or 2, characterized in that: The reaction temperature of the first stage of adding epoxide in step S1 is 110-160° C., relative pressure ≤0.3 MPa, and aging time is 1-3 h; the reaction temperature of the second stage is 110-140° C., relative pressure ≤0.3 MPa, and aging time is 1-4 h; and the reaction temperature of the third stage is 110-140° C., relative pressure ≤0.3 MPa, and aging time is 1-5 h.

4. The method for preparing a polyetheramine for emulsifier according to claim 1 or 2, characterized in that: The amount of sodium methoxide used in step S1 is 0.1-0.6% of the mass of methanol.

5. The method for preparing the polyetheramine for emulsifier according to claim 1 or 2, characterized in that: In step S2, the molar ratio of liquid ammonia to methanol polyether is 8-15:1; the molar ratio of hydrogen to methanol polyether is 20-50:1; and the mass space velocity of the methanol polyether is 0.08-1.50 Kg / Kg.CAT.h.

6. The method for preparing a polyetheramine for emulsifier according to claim 1 or 2, characterized in that: The reductive amination catalyst in step S2 is a nickel-palladium supported catalyst, and the carrier of the nickel-palladium supported catalyst is a mixture of aluminum oxide and silicon dioxide.

7. The method for preparing a polyetheramine for emulsifier according to claim 6, wherein: The nickel loading is 10-25 wt % of the nickel-palladium loaded catalyst, the palladium loading is 0.1-2 wt % of the nickel-palladium loaded catalyst, the carrier content is 73-89.9 wt % of the nickel-palladium loaded catalyst; and the mass ratio of alumina to silica in the carrier is 1-10:

1.

8. The method for preparing the polyetheramine for emulsifier according to claim 6 or 7, characterized in that: The preparation method of the reductive amination catalyst is as follows: A1. Spherical Al(OH)3 and SiO2 particles are uniformly mixed, ground, and sieved to obtain a mixture of 100-200 mesh. The mixture is dried at 100-150°C for 20-30 hours, and then calcined at 1000-1100°C for 20-30 hours. After cooling, a white powder is obtained. The white powder is processed and molded to obtain a spherical carrier with a diameter of 1-8 mm and γ-Al2O3 / SiO2 particles attached to the surface. The carrier is placed in a dilute ammonia solution with a concentration of 1-10% until the adsorption amount of the dilute ammonia solution is 1-15% of the carrier weight. A2, nickel nitrate and palladium nitrate are added to deionized water to prepare a metal salt solution, the support prepared in step A1 is immersed in the metal salt solution, dried after sufficient adsorption equilibrium, and calcined at 360-420° C. for 4-8 hours; after cooling, the support loaded with nickel and palladium is reduced under a hydrogen atmosphere to obtain the reductive amination catalyst.

9. The method for preparing a polyetheramine for emulsifier according to claim 8, wherein: The reduction temperature in step A2 is 220-370° C., and the hydrogen flow rate is 0.1-5 ml / KG.CAT.min.

10. The method for preparing a polyetheramine for emulsifier according to claim 1 or 2, characterized in that: The reaction temperature of the hydroamination reaction in step S2 is 130-190° C., and the reaction pressure is 10-16 MPa.

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