A polyetheramine modified polyamine block polymer dispersant and its preparation method and application

Abstract

The invention provides a polyetheramine polyamine block polymer dispersant and a preparation method and application thereof. The structural formula of the dispersant is:; or:; wherein x=2-3, y=2-4, polyther is a block polyether of ethylene oxide and / or propylene oxide; R is a structure with a carboxyl group after the anhydride ring is opened; the dispersant of the invention can efficiently disperse infinite ultrafine powders and has an excellent dispersing effect; the preparation method of the dispersant provided by the invention is simple and efficient, the reaction conditions are mild, the reactant utilization rate can reach 100%, and the solvent consumption is small and easy to remove, which meets the requirements of green chemistry and is easy to realize industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of dispersants, and in particular to a polyetheramine modified polyamine block polymer dispersant and a preparation method and application thereof. Background Art

[0002] In the production of chemical products such as coatings, inks, and composite materials, the dispersion of pigments and fillers in the manufacturing process of coatings and inks refers to the secondary agglomerates of pigments and fillers being wetted, crushed, and dispersed in the color-developing agent under the action of mechanical force to obtain a dispersed suspension. Among them, the size of the pigments and fillers has an important influence on the gloss, hue, fullness, surface tension, etc. of the final product. In terms of the current industry development needs, inorganic ultrafine powders (also known as nanopowders) have significant advantages as pigments and fillers. Inorganic ultrafine powders, such as nano titanium dioxide, transparent iron oxide, nano aluminum silver paste, etc., have extremely high specific surface areas and polar particle sizes. Compared with conventional granular materials, they have a series of excellent physical and chemical properties, but too small a particle size will inevitably lead to easy agglomeration in coatings and other systems, and the use of high-efficiency dispersants is an effective means to prevent their aggregation and sedimentation.

[0003] According to the chemical structure, dispersants can be divided into anionic dispersants, cationic dispersants, nonionic dispersants, polymer dispersants and other types. Many studies have shown that polymer dispersants can overcome the limitations of poor dispersion effects of traditional dispersants, and have a considerable effect on wetting and stability in the dispersion process, which has greatly improved and has become a new generation of high-efficiency dispersants. Polymer dispersants maintain the performance of pigment particles in the medium through the anchoring force and steric hindrance between ultrafine powders. The anchoring force is provided by the anchoring group part, including electrostatic force, hydrogen bonding, conjugation, van der Waals force, etc., and the steric hindrance is provided by the solvation chain part, including electrostatic repulsion, steric hindrance, etc. Commonly used anchoring groups include carboxyl, amine, amide, ester, sulfonic acid, hydroxyl, etc. The solvation chain varies according to the solvent of the dispersion system, such as polyether, acrylate, etc.

[0004] For dispersants of inorganic ultrafine powders, since they are required to have a strong and stable anchoring effect and a highly efficient solvation chain dispersion effect, existing work reports use nitrogen-rich groups such as polyethylene polyamine as anchoring segments and modified copolymer systems such as polyethers as solvation chain segments. However, the key is to effectively chemically bond the two into a polymer dispersant and adjust the molecular chain configuration to the optimal block mode. However, there are not many related synthetic preparation methods and research, and the mechanism is not mature.

[0005] Therefore, it is of great practical significance to develop efficient dispersants for dispersing inorganic ultrafine powders in the fields of coatings, inks and composite materials. Summary of the invention

[0006] Based on this, one of the purposes of the present invention is to provide a polyetheramine modified polyamine block polymer dispersant that can be used to efficiently disperse inorganic ultrafine powders. The dispersant has an anchoring structure of polyamine and carboxyl groups and a solvation chain of copolymers such as polyether, and has an excellent dispersing effect on inorganic ultrafine powders.

[0007] Based on the above purpose, the technical solution of the present invention is as follows:

[0008] A polyetheramine modified polyamine block polymer dispersant, the structural formula of which is as follows:

[0009] ;

[0010] Wherein, x=2~3, y=2~4; polyther is a block polyether of ethylene oxide and / or propylene oxide; R is a carboxyl group-bearing portion after ring-opening of different acid anhydrides, which varies depending on the specific selected acid anhydride.

[0011] The second object of the present invention is to provide a method for preparing the above-mentioned polyetheramine modified polyamine block polymer powder for efficiently dispersing inorganic ultrafine powder, the method comprising the following steps:

[0012] S1, dissolving the terminal hydroxyl acrylate in a solvent, adding a first catalyst and a polyetheramine, controlling the molar ratio of the primary amine group of the polyetheramine to the terminal hydroxyl acrylate to be 1:1, and performing an amine-ene addition reaction under heat preservation to obtain a first product;

[0013] S2, adding an anhydride monomer with a double bond and a second catalyst to the first product, and controlling the molar ratio of the anhydride monomer with a double bond to the first product to be 1:1, and performing an anhydride ring-opening reaction while keeping the temperature to obtain a second product;

[0014] S3, adding polyethylene polyamine and a third catalyst to the second product, and controlling the molar ratio of the polyethylene polyamine to the second product to be 1:1, and performing an amine-ene addition reaction at a temperature-insulated state; after the reaction is completed, removing the solvent under reduced pressure, and then adding water to obtain the modified polyetheramine-modified anhydride copolymer.

[0015] In some embodiments, in step S1, the terminal hydroxyl acrylate is at least one of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), and hydroxypropyl methacrylate (HPMA);

[0016] In some embodiments, in step S1, the polyetheramine is a monoamino-terminated block polyether of ethylene oxide / propylene oxide (EO / PO), and its number average molecular weight is preferably 1000-2500 g / mol; more preferably, the molecular weight is 1500 g / mol, 2000 g / mol, and 2500 g / mol, respectively denoted as PEA1500, EP2000, and PEA2500.

[0017] In some embodiments, in step S1, the solvent is a high boiling point ether solvent, preferably one of propylene glycol monomethyl ether (PM), propylene glycol monobutyl ether (PGM), and propylene glycol acetate (PMA), and the added amount is 5-50 wt.% of the solid reactant mass in step S1;

[0018] In some embodiments, in step S1 and step S3, the first catalyst and the third catalyst are cerium ammonium nitrate (CAN) and / or zirconium acetylacetonate (Zr(AcAc)), respectively, and the added amounts are preferably 0.1-5 wt.%, more preferably 0.1-2 wt.% of the solid mass of the current step.

[0019] In some embodiments, in step S1, the reaction temperature is 50-90° C., the reaction time is 8-20 h, and the reaction is carried out in a nitrogen environment.

[0020] In some embodiments, in step S2, the anhydride monomer with a double bond is one of maleic anhydride (MA) and nadic anhydride (NA).

[0021] In some embodiments, in step S2, the catalyst is a strong acid or strong base catalyst, preferably one of dodecylbenzoic acid (DBSA), p-toluenesulfonic acid (TsOH), potassium methoxide (MK), and sodium methoxide (MN), and the added amount is preferably 0.1~5 wt.% of the solid mass of the current step, and more preferably 0.1~1 wt.%.

[0022] In some embodiments, in step S2, the reaction temperature is 100-150° C., the reaction time is 2-6 h, and the reaction is carried out in a nitrogen environment.

[0023] In some embodiments, in step S3, the polyethylene polyamine is one of diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA).

[0024] In some embodiments, in step S3, the reaction temperature is 50-90° C., the reaction time is 8-20 h, and the reaction is carried out in a nitrogen environment; after the solvent is removed under reduced pressure, the amount of distilled water added is preferably 0.5-2 times the mass of the solid content of the product, that is, the solid content of the obtained product is 30-60%.

[0025] It should be noted that, in the present application, EO / PO refers to EO and / or PO, and the specific structure can be determined according to the reactants.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The dispersant provided by the present invention uses the amino group of the block polyamine and the carboxylic acid heel formed by the ring opening of the acid anhydride as the anchoring group, uses the EO / PO polyether part of the polyetheramine as the solvation chain part, and uses the hydroxyl acrylate as the bridging part to connect the polyetheramine block part with the acid anhydride and the polyamine part together, uses the high-polarity polyethylene polyamine and the carboxyl group as the anchoring group of the inorganic ultrafine powder, and electrostatically adsorbs on the surface of the inorganic ultrafine powder, and then uses the EO / PO copolymerized polyether as the solvation chain to regulate the steric hindrance and the ionic electrostatic repulsion, promotes the dispersion of the inorganic ultrafine powder particles, and can achieve efficient dispersion of the inorganic ultrafine powder and show excellent dispersion effect.

[0028] The invention provides a method for preparing a polyetheramine modified polyamine polymer dispersant. The method comprises the following steps: controlling the molar ratio of polyetheramine to hydroxyl acrylate to be 1:1, combining them together by an amine-ene addition reaction; then the hydroxyl groups of the obtained product are ring-opened at high temperature to obtain anhydride molecules with double bonds; finally, the primary amines of polyethylene polyamine and the double bonds remaining in the anhydride molecules are subjected to an amine-ene addition reaction again, and strictly controlling the molar ratio of polyethylene polyamine to the intermediate product to be 1:1, so that the polyetheramine solvated chain blocks are connected with the anhydride and polyamine anchoring structure parts, so that the obtained dispersant has high-efficiency dispersing performance for inorganic ultrafine powders and excellent dispersing effect.

[0029] In addition, the preparation method of the present invention is simple and efficient, the reaction conditions are mild, the reactant utilization rate reaches 100%, and the solvent usage is small and easy to remove, which effectively reduces carbon emissions, meets the requirements of green chemistry, and is easy to realize industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the infrared test image of the dispersant obtained in Example 1. DETAILED DESCRIPTION

[0031] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions 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 are within the scope of protection of the present invention. Example

[0032] A polyetheramine modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation method of which comprises the following steps:

[0033] S1, add 11.6 g HEA (0.1 mol) and 32 g PM solvent into a four-necked flask, then add 0.32 g CAN (0.2 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 60 °C, add 150 g PEA1500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 60 °C for 15 h to obtain the intermediate product R1;

[0034] S2, add 0.34 g (0.2 wt.%) of DBSA catalyst to the intermediate product R1, raise the temperature to 120 °C, add 9.8 g of MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 5 hours to obtain the intermediate product R2;

[0035] S3. Cool the intermediate product R2 to 70 °C, add 0.19 g (0.1 wt.%) of CAN catalyst, and add 14.6 g of TETA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 70 °C for 10 h, remove the solvent in vacuo until the solid content is ≥98%, then add 186 g of distilled water to dilute to a solid content of 50 wt.%, and finally obtain a dark red viscous dispersant product.

[0036] The obtained product was tested by infrared spectroscopy. Figure 1 As shown, characteristic peaks of polyether, acrylate, carboxyl, amino, etc. can be seen in the infrared spectrum. This indicates that the product is the target product required by the present invention, and its molecular formula is:

[0037]

[0038] Among them, x=2, y=3. Example

[0039] A polyetheramine modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0040] S1. Add 13 g HPA (0.1 mol) and 26 g PMA solvent into a four-necked flask, then add 0.26 g Cr(AcAc) (0.1 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 80 °C, add 250 g PEA2500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 80 °C for 12 h to obtain the intermediate product R1;

[0041] S2, add 0.27 g (0.1 wt.%) of TsOH catalyst to the intermediate product R1, raise the temperature to 150 °C, add 9.8 g MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 3 hours to obtain the intermediate product R2;

[0042] S3, cool the intermediate product R2 to 60 ℃, add 0.28 g (0.1 wt.%) of Cr(AcAc) catalyst, add 10.3 g of DETA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 60 ℃ for 15 hours, remove the solvent in vacuo until the solid content is ≥98%, then add 424 g of distilled water to dilute to a solid content of 40 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0043]

[0044] Among them, x=3, y=2. Example

[0045] A polyetheramine modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0046] S1. Add 13 g HEMA (0.1 mol) and 65 g PGM solvent into a four-necked flask, then add 0.81 g Cr(AcAc) (0.5 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 50 °C, add 150 g PEA1500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 50 °C for 20 h to obtain the intermediate product R1;

[0047] S2, add 1.07 g (0.6 wt.%) of MK catalyst to the intermediate product R1, raise the temperature to 110 °C, add 16.4 g NA (0.1 mol) dropwise and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 4 hours to obtain the intermediate product R2;

[0048] S3, cool the intermediate product R2 to 90 ℃, add 0.59 g (0.3 wt.%) of Cr(AcAc) catalyst, add 18.9 g TEPA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 90 ℃ for 8 hours, remove the solvent in vacuo until the solid content is ≥98%, then add 132 g of distilled water to dilute to a solid content of 60 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0049]

[0050] Among them, x=2, y=4. Example

[0051] A polyetheramine-modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0052] S1, add 14.4 g HPMA (0.1 mol) and 80 g PM solvent into a four-necked flask, then add 3.21 g CAN (1.5 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 70 °C, add 200 g PEA2000 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 70 °C for 12 h to obtain the intermediate product R1;

[0053] S2, add 1.34 g (0.6 wt.%) of MN catalyst to the intermediate product R1, raise the temperature to 100 °C, add 9.8 g MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 100 °C for 6 hours to obtain the intermediate product R2;

[0054] S3, cool the intermediate product R2 to 80 ℃, add 2.91 g (1.2 wt.%) of CAN catalyst, add 18.9 g TEPA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 80 ℃ for 10 hours, remove the solvent in vacuo until the solid content is ≥98%, then add 567 g of distilled water to dilute to a solid content of 30 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0055]

[0056] Among them, x=3, y=4. Example

[0057] A polyetheramine-modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0058] S1, add 11.6 g HEA (0.1 mol) and 25 g PM solvent into a four-necked flask, then add 1.04 g CAN (0.4 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 60 °C, add 250 g PEA2500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 60 °C for 9 h to obtain the intermediate product R1;

[0059] S2, add 1.90 g (0.7 wt.%) of DBSA catalyst to the intermediate product R1, raise the temperature to 140 °C, add 9.8 g MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 140 °C for 3 hours to obtain the intermediate product R2;

[0060] S3, cool the intermediate product R2 to 70 ℃, add 0.29 g (0.1 wt.%) of CAN catalyst, add 14.6 g TETA (1.6 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 70 ℃ for 14 h, remove the solvent in vacuo until the solid content is ≥98%, then add 429 g of distilled water to dilute to a solid content of 40 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0061]

[0062] Among them, x=2, y=3. Example

[0063] A polyetheramine-modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0064] S1. Add 13 g HPA (0.1 mol) and 60 g PGM solvent into a four-necked flask, then add 1.70 g Cr(AcAc) (0.8 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 90 °C, add 200 g PEA2000 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 90 °C for 16 h to obtain the intermediate product R1;

[0065] S2, add 1.15 g (0.5 wt.%) of TsOH catalyst to the intermediate product R1, raise the temperature to 150 °C, add 16.4 g NA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 2 hours to obtain the intermediate product R2;

[0066] S3, cool the intermediate product R2 to 60 ℃, add 3.6 g (1.5 wt.%) of Cr(AcAc) catalyst, add 10.3 g of DETA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 60 ℃ for 12 h, remove the solvent in vacuo until the solid content is ≥98%, then add 560 g of distilled water to dilute to a solid content of 30 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0067]

[0068] Among them, x=3, y=2. Example

[0069] A polyetheramine modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0070] S1. Add 13 g HEMA (0.1 mol) (0.1 mol) and 50 g PGM solvent into a four-necked flask, then add 1.58 g Cr(AcAc) (0.6 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 60 °C, add 250 g PEA2500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 60 °C for 20 h to obtain the intermediate product R1;

[0071] S2, add 0.84 g (0.3 wt.%) of MK catalyst to the intermediate product R1, raise the temperature to 110 °C, add 16.4 g NA (0.1 mol) dropwise and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 4 hours to obtain the intermediate product R2;

[0072] S3, cool the intermediate product R2 to 70 ℃, add 4.17 g (1.4 wt.%) of Cr(AcAc) catalyst, add 18.9 g TEPA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 70 ℃ for 16 hours, remove the solvent in vacuo until the solid content is ≥98%, then add 186 g of distilled water to dilute to a solid content of 40 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0073]

[0074] Among them, x=2, y=4. Example

[0075] A polyetheramine modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0076] S1, add 14.4 g HPMA (0.1 mol) (0.1 mol) and 60 g PM solvent into a four-necked flask, then add 1.15 g CAN (0.7 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 60 °C, add 150 g PEA1500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 60 °C for 18 h to obtain the intermediate product R1;

[0077] S2, add 0.18 g (1 wt.%) of MN catalyst to the intermediate product R1, raise the temperature to 120 °C, add 16.4 g NA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 5 hours to obtain the intermediate product R2;

[0078] S3, cool the intermediate product R2 to 80 ℃, add 1.8 g (0.9 wt.%) of CAN catalyst, add 18.9 g TEPA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 80 ℃ for 16 hours, remove the solvent in vacuo until the solid content is ≥98%, then add 134 g of distilled water to dilute to a solid content of 60 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0079]

[0080] Among them, x=3, y=4. Example

[0081] A polyetheramine-modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0082] S1. Add 11.6 g HEA (0.1 mol) and 100 g PMA solvent into a four-necked flask, then add 1.26 g Cr(AcAc) (0.5 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 70 °C, add 200 g PEA2000 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 70 °C for 10 h to obtain the intermediate product R1;

[0083] S2, add 0.66 g (0.3 wt.%) of DBSA catalyst to the intermediate product R1, raise the temperature to 120 °C, add 9.8 g MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 3 hours to obtain the intermediate product R2;

[0084] S3. Cool the reaction solution of the intermediate product R2 to 90°C, add 4.63 g (2 wt.%) of Cr(AcAc) catalyst, and add 10.3 g of DETA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 90°C for 10 hours, remove the solvent in vacuo until the solid content is ≥98%, and then add 539 g of distilled water to dilute to a solid content of 30 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0085]

[0086] Among them, x=2, y=2. Example

[0087] A polyetheramine-modified polyamine block polymer dispersant for efficiently dispersing inorganic ultrafine powders, the preparation of which comprises the following steps:

[0088] S1. Add 13 g HPA (0.1 mol) and 30 g PMA solvent into a four-necked flask, then add 1.30 g CAN (0.8 wt.%), introduce nitrogen and all the following steps are carried out under nitrogen environment, heat to 80 °C, add 150 g PEA1500 (0.1 mol) dropwise, and control the addition to be completed within 1 hour; continue the reaction at 80 °C for 18 h to obtain the intermediate product R1;

[0089] S2, add 0.17 g (0.1 wt.%) of TsOH catalyst to the intermediate product R1, raise the temperature to 140 °C, add 9.8 g MA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 120 °C for 6 hours to obtain the intermediate product R2;

[0090] S3, cool the intermediate product R2 to 90 ℃, add 2.99 g (1.6 wt.%) of CAN catalyst, add 14.6 g TETA (0.1 mol) dropwise, and control the addition to be completed within 0.5 hours; continue the reaction at 90 ℃ for 14 h, remove the solvent in vacuo until the solid content is ≥98%, then add 125 g of distilled water to dilute to a solid content of 60 wt.%, and finally obtain a dark red viscous dispersant product. Its molecular formula is:

[0091]

[0092] Among them, x=3, y=3.

[0093] Examples 1, 3, 5, 7, 9 and commercially available dispersant samples were mixed in the ratios shown in Table 1 to prepare slurries. The obtained slurries were tested. The test results are shown in Table 2.

[0094] Table 1 Slurry ratio

[0095]

[0096] Table 2 Performance test results of slurries prepared with dispersants from different embodiments

[0097]

[0098] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0099] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the present invention. The present invention has been described in detail with reference to the preferred embodiments. Those skilled in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention without departing from the purpose and scope of the technical solutions should be included in the scope of the claims of the present invention.

Claims

1. A polyetheramine modified polyamine block polymer dispersant, characterized in that: Its structural formula is as follows: ； or: ； Wherein, x=2~3, y=2~4, polyther is a block polyether of ethylene oxide and / or propylene oxide; and R is a structure with a carboxyl group after the anhydride ring is opened.

2. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 1, characterized in that: The following steps are involved: S1, dissolving the terminal hydroxyl acrylate in a solvent, adding a first catalyst and a polyetheramine, controlling the molar ratio of the primary amine group of the polyetheramine to the terminal hydroxyl acrylate to be 1:1, and performing an amine-ene addition reaction under heat preservation to obtain a first product; S2, adding an anhydride monomer with a double bond and a second catalyst to the first product, and controlling the molar ratio of the anhydride monomer with a double bond to the first product to be 1:1, and performing an anhydride ring-opening reaction while keeping the temperature to obtain a second product; S3, adding polyethylene polyamine and a third catalyst to the second product, and controlling the molar ratio of the polyethylene polyamine to the second product to be 1:1, and performing an amine-ene addition reaction at a temperature-insulated state; after the reaction is completed, removing the solvent under reduced pressure, and then adding water to obtain the modified polyetheramine-modified anhydride copolymer.

3. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S1, the terminal hydroxyl acrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

4. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: The polyetheramine is a monoamino-terminated block polyether of ethylene oxide / propylene oxide, and its number average molecular weight is 1000-2500 g / mol.

5. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S1, the solvent is a high boiling point ether solvent, and the amount of the solvent added is 5-50 wt.% of the solid reactant mass.

6. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S1 and step S3, the first catalyst and the third catalyst are respectively ammonium cerium nitrate and / or zirconium acetylacetonate, and the added amount is 0.1-5 wt.% of the mass of the solid reactant in the current step.

7. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S2, the acid anhydride monomer with a double bond is one of maleic anhydride and nadic anhydride.

8. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S2, the second catalyst is at least one of dodecylbenzoic acid, p-toluenesulfonic acid, potassium methoxide, and sodium methoxide; and / or, the amount of the second catalyst added is 0.1-5 wt.% of the solid mass of the current step.

9. The method for preparing the polyetheramine modified polyamine block polymer dispersant according to claim 2, characterized in that: In step S3, the polyethylene polyamine is at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

10. Use of the polyether-modified polyamine block polymer dispersant according to claim 1 or the polyether-modified polyamine block polymer dispersant obtained by the preparation method according to any one of claims 2 to 9 in dispersing inorganic ultrafine powders.

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