Hyperdispersant and preparation method thereof

Abstract

The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of a hyperdispersant, which comprises the following steps: (1) sequentially adding fatty acid, triethanolamine, a catalyst and an assistant into a reaction kettle, replacing air in the reaction kettle with nitrogen with the concentration of more than or equal to 99.9%, continuously stirring and heating, vacuumizing the reaction kettle when the temperature is 120-200 DEG C, and carrying out esterification reaction, the reaction pressure is-0.1 to 0.2 MPa, and the reaction time is 1 to 12 hours; and (2) after the esterification reaction is completed, settling for 1-6 hours to obtain a product, namely the hyperdispersant. Meanwhile, the invention discloses the hyperdispersant obtained by the method. According to the hyperdispersant and the preparation method thereof disclosed by the invention, the triethanolamine fatty acid ester and the triethanolamine fatty acid ester quaternary ammonium salt are prepared from fatty acid with low carbon atoms, so that the application range of the hyperdispersant is wider.

Description

Technical Field

[0001] The invention relates to the technical field of fine chemicals, in particular to a hyperdispersant and a preparation method thereof. Background Art

[0002] At present, triethanolamine is used as the matrix to prepare triethanolamine fatty acid ester or triethanolamine fatty acid ester quaternary ammonium salt, which are C 16 ~C 18 Saturated or unsaturated fatty acids can only be used as softeners in the textile, leather, papermaking and other industries, and have great application limitations. Summary of the invention

[0003] In order to solve the above technical deficiencies, the present invention provides a hyperdispersant and a preparation method thereof, which realizes the preparation of triethanolamine fatty acid ester and triethanolamine fatty acid ester quaternary ammonium salt by using low-carbon fatty acid, thereby expanding the application range.

[0004] The present invention discloses a hyperdispersant, the structural formula of which is shown in Formula 1 or Formula 2:

[0005] The general formula 1 is:

[0006]

[0007] In general formula 1: R1 is N or N + When the target product is triethanolamine fatty acid ester, R1 is N; when the target product is triethanolamine fatty acid ester quaternary ammonium salt, R1 is N + ;

[0008] R2, R3, and R4 are fatty acid groups and hydrogen groups, and the number of hydrogen groups is 0, 1, and 2;

[0009] General formula 2 is:

[0010]

[0011] In general formula 2: R5, R6, and R7 are methyl groups and hydrogen groups, and the number of hydrogen groups is 0, 1, and 2;

[0012] R8, R9, R 10 C1~C 20 One or more of hydrogen groups, ester groups, and hydroxyl groups, the number of hydrogen groups is 0, 1, or 2, the number of hydroxyl groups is 0, 1, or 2, and the number of ester groups is 1, 2, or 3;

[0013] R2, R3, and R4 are fatty acid groups, and the fatty acid groups are C6 to C 18 One or more of monobasic or dibasic straight-chain fatty acids, isomeric fatty acids, cycloalkane acids, and heterocyclic acids. 18It may be any one of C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18, preferably C6 to C15. The same applies below.

[0014] Preferably, the fatty acid of the fatty acid group is one or more of Formula 2 to Formula 7; wherein,

[0015] Formula 2:

[0016]

[0017] Formula 3:

[0018]

[0019] Formula 4:

[0020]

[0021] Formula 5:

[0022]

[0023] Formula 6:

[0024]

[0025] Formula 7:

[0026]

[0027] R8, R9, R 10 When it is an ester group, the ester-forming fatty acid group of the ester group is C6~C 18 One or more of monobasic or dibasic straight-chain fatty acids, isomeric fatty acids, cycloalkane acids, and heterocyclic acids.

[0028] Preferably, the fatty acid forming the ester fatty acid group of the ester group is one or more of Formulas 2 to 10; wherein,

[0029] Formula 2:

[0030]

[0031] Formula 3:

[0032]

[0033] Formula 4:

[0034]

[0035] Formula 5:

[0036]

[0037] Formula 6:

[0038]

[0039] Formula 7:

[0040]

[0041] Formula 8:

[0042]

[0043] Formula 9:

[0044]

[0045] Formula 10:

[0046]

[0047] A method for preparing a hyperdispersant comprises the following steps:

[0048] (1) fatty acid, precursor, catalyst and auxiliary agent are sequentially put into a reaction kettle, the air in the reaction kettle is replaced by nitrogen, the nitrogen concentration is required to be ≥99.9%, stirring is continued and the temperature is raised, and when the temperature is 120-200° C., the reaction kettle is evacuated to carry out esterification reaction, the reaction pressure is -0.1-0.2 MPa, and the reaction time is 1-12 h; wherein the precursor is one or more of triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine;

[0049] (2) After the esterification reaction is completed, the reaction is allowed to settle for 1 to 6 hours, and the resulting product is one or more of triethanolamine mono-fatty acid ester, triethanolamine di-fatty acid ester, triethanolamine tri-fatty acid ester, monoisopropanolamine fatty acid ester, diisopropanolamine mono-fatty acid ester, diisopropanolamine di-fatty acid ester, triisopropanolamine mono-fatty acid ester, triisopropanolamine di-fatty acid ester, and triisopropanolamine tri-fatty acid ester;

[0050] The catalyst is one or more of sodium methoxide, phosphorous acid, phosphorus pentoxide, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and sulfuric acid;

[0051] If the selected catalyst is phosphorus pentoxide, the esterification product needs to be filtered. If the catalyst is sulfuric acid or the esterification product contains large particles of salt-forming substances, the crude esterification product needs to be centrifuged to remove the salt-forming substances to ensure the quality of the final product.

[0052] The auxiliary agents are solvents, stabilizers and co-catalysts;

[0053] The molar ratio of fatty acid to matrix is ​​0.8-3.2:1, the mass ratio of catalyst and stabilizer to total reactants is 1-8:30-100:10000, the molar ratio of co-catalyst to catalyst is 0.5-5:1, and the volume ratio of solvent to fatty acid is 20-50:1.

[0054] The solvent is one or more of ethanol, petroleum ether and polyethylene glycol, the co-catalyst is one or two of crown ether and polyethylene glycol, the stabilizer is one or more of phenothiazine, hydroquinone and anthraquinone, wherein the molecular weight of polyethylene glycol is 200-600.

[0055] Another form: after step (2), the method further comprises the following steps:

[0056] (3) the esterified product obtained in step (2) is put back into the reaction kettle after settling, a quaternizing agent is added, and the reaction is carried out at a pressure of -0.1 to 0.05 MPa and 40 to 90° C. for 1 to 8 hours to obtain triethanolamine fatty acid ester quaternary ammonium salt;

[0057] The quaternizing agent is one or more of epichlorohydrin, dimethyl sulfate, methyl chloride, and sodium chloroacetate;

[0058] The molar ratio of the esterification product to the quaternizing agent is 1:0.8-4.

[0059] When the formula 5 is used as an initiator, it can be used as a rust inhibitor, a dispersant and a special oil additive.

[0060] When the compound of formula 6 is used as an initiator, it can be used as a bactericidal / bacteriostatic agent.

[0061] The compounds of formula 2, formula 3, formula 4 and formula 7 can be used as initiators and as chemical or pharmaceutical intermediates.

[0062] The hyperdispersant of the general formula 2 can be used as a component of cement grinding aids and can also be used as a grease additive.

[0063] In step (1), the mixed gas extracted during the vacuum is separated by a primary organic separation device, and the heavy component is recovered as a raw material and returned to the reactor to continue to participate in the reaction, or it can enter the raw material recovery equipment for standby use; the light component containing auxiliary agents and water enters the secondary organic separation equipment for separation, the auxiliary agents are recovered and reused, and the waste gas and wastewater enter the corresponding treatment system for treatment.

[0064] The primary organic separation device and the secondary organic separation device are both existing known equipment.

[0065] The primary organic separation device is equipped with a packed absorption tower and an oil-water phase separator, which can recover the ethanolamines or low-boiling volatile fatty acids released during the reaction to the reaction system, ensuring the accuracy of the reaction measurement. The wastewater treatment system is equipped with a water reuse diversion facility to improve the utilization rate of water resources and reduce the discharge of three wastes. The secondary organic separation equipment is equipped with a cascade-arranged membrane separator and a molecular distiller. Among them, the membrane separator is used to separate additives with a boiling point lower than water; the molecular distiller is used to separate additives with a boiling point higher than water and easy-to-crystallize raw materials. The separated additives can be reused, reducing the raw material cost of the process.

[0066] The hyperdispersant and the preparation method thereof obtained by the invention adopt low-carbon atom fatty acids to prepare triethanolamine fatty acid ester, triisopropanolamine fatty acid ester and triethanolamine fatty acid ester quaternary ammonium salt and triisopropanolamine fatty acid ester quaternary ammonium salt, so that the application range of the hyperdispersant is wider. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0068] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation mode, structure, characteristics and effects of the present invention are described in detail below in combination with the accompanying drawings and preferred embodiments.

[0069] Embodiment 1:

[0070] The present invention discloses a method for preparing a hyperdispersant. 400g of triethanolamine, 660g of isopropyl benzoic acid, 32g of p-toluenesulfonic acid and 50ml of ethanol are put into a 2L reactor, and the mixture is continuously stirred after nitrogen replacement, heated to 130°C, vacuumed and reacted. The reaction pressure is controlled to be -0.05MPa, the reaction temperature is 150°C, the solvent ethanol is separated and recovered through secondary organic matter, and the reaction is carried out for 6h to obtain a hyperdispersant according to the present invention, which is recorded as TFE-1. The structure of TFE-1 is general formula 1, wherein R1 is N, at least one of R2, R3 and R4 is formula 7, and the rest are hydrogen groups.

[0071] Embodiment 2:

[0072] 1120g of TFE-1 was put into a 2L reactor, the temperature was controlled at 50°C, the pressure was -0.05MPa, 300g of methyl chloride was gradually added to the reactor, the addition was completed within 4 hours, and the aging was continued for 1 to 2 hours to obtain a superdispersant according to the present invention, which was recorded as TFA-1. The structural formula of TFA-1 is general formula 1, R1 is N + , the structures of R2, R3, and R4 are the same as those of TFE-1.

[0073] TFA-1 is used as an antibacterial agent. In the compounding of conventional polycarboxylic acid-based high-performance water-reducing agent (solid content 40%), the recommended dosage is 0.02% to 0.05%.

[0074] Example 3

[0075] Put 500g triisopropanolamine and 5.2g p-toluenesulfonic acid into a 2L reactor, replace with nitrogen, and heat to 120°C. Mix 526g malic acid with 350ml ethanol, dissolve and put into a 1.5L dropping tank, and add malic acid ethanol solution into the reactor through a peristaltic pump. Control the reaction pressure to -0.1MPa and the reaction temperature to 50°C. The solvent ethanol is separated and recovered through secondary organic matter. React for 6h to obtain a hyperdispersant described in the present invention, which is recorded as TPE-1. The structure of TPE-1 is general formula 2, R8, R9, R 10 At least one of them is Formula 9.

[0076] TPE-1 can be used with triisopropanolamine as a cement grinding aid component. The mass ratio of TPE-1 to triisopropanolamine, lignin sulfonate / alkyl sulfonate, and water is 10:15:25:30. The recommended addition amount of the compound grinding aid during cement grinding is 0.03-0.1% of the total weight of cement.

[0077] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simplified modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A hyperdispersant, characterized in that: Its structural formula is shown in general formula 1 or general formula 2: The general formula 1 is: In general formula 1: R1 is N or N + When the target product is triethanolamine fatty acid ester, R1 is N; when the target product is triethanolamine fatty acid ester quaternary ammonium salt, R1 is N + ; R2, R3, and R4 are fatty acid groups and hydrogen groups, and the number of hydrogen groups is 0, 1, and 2; General formula 2 is: In general formula 2: R5, R6, and R7 are methyl groups and hydrogen groups, and the number of hydrogen groups is 0, 1, and 2; R8, R9, R 10 C1~C 20 One or more of hydrogen groups, ester groups, and hydroxyl groups, the number of hydrogen groups is 0, 1, or 2, the number of hydroxyl groups is 0, 1, or 2, and the number of ester groups is 1, 2, or 3.

2. A hyperdispersant according to claim 1, characterized in that: R2, R3, and R4 are fatty acid groups, and the fatty acid groups are C6 to C 18 One or more of monobasic or dibasic straight-chain fatty acids, isomeric fatty acids, cycloalkane acids, and heterocyclic acids.

3. A hyperdispersant according to claim 2, characterized in that: The fatty acid of the fatty acid group is one or more of Formula 2 to Formula 7; wherein, Formula 2: Formula 3: Formula 4: Formula 5: Formula 6: Formula 7:

4. A hyperdispersant according to claim 1, characterized in that: R8, R9, R 10 When it is an ester group, the ester-forming fatty acid group of the ester group is C6~C 18 One or more of monobasic or dibasic straight-chain fatty acids, isomeric fatty acids, cycloalkane acids, and heterocyclic acids.

5. A hyperdispersant according to claim 4, characterized in that: The fatty acid of the ester-forming fatty acid group of the ester group is one or more of Formulas 2 to 10; wherein, Formula 2: Formula 3: Formula 4: Formula 5: Formula 6: Formula 7: Formula 8: Formula 9: Formula 10:

6. A method for preparing a hyperdispersant, characterized in that: The following steps are involved: (1) fatty acid, precursor, catalyst and auxiliary agent are sequentially put into a reaction kettle, the air in the reaction kettle is replaced by nitrogen, the nitrogen concentration is required to be ≥99.9%, stirring is continued and the temperature is raised, and when the temperature is 120-200° C., the reaction kettle is evacuated to carry out esterification reaction, the reaction pressure is -0.1-0.2 MPa, and the reaction time is 1-12 h; wherein the precursor is one or more of triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine; (2) After the esterification reaction is completed, the reaction is allowed to settle for 1 to 6 hours, and the resulting product is one or more of triethanolamine mono-fatty acid ester, triethanolamine di-fatty acid ester, triethanolamine tri-fatty acid ester, monoisopropanolamine fatty acid ester, diisopropanolamine mono-fatty acid ester, diisopropanolamine di-fatty acid ester, triisopropanolamine mono-fatty acid ester, triisopropanolamine di-fatty acid ester, and triisopropanolamine tri-fatty acid ester; The catalyst is one or more of sodium methoxide, phosphorous acid, phosphorus pentoxide, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and sulfuric acid; The auxiliary agents are solvents, stabilizers and co-catalysts; The molar ratio of fatty acid to matrix is ​​0.8-3.2:1, the mass ratio of catalyst and stabilizer to total reactants is 1-8:30-100:10000, the molar ratio of co-catalyst to catalyst is 0.5-5:1, and the volume ratio of solvent to fatty acid is 20-50:

1.

7. A method for preparing a hyperdispersant according to claim 5, characterized in that: The solvent is one or more of ethanol, petroleum ether and polyethylene glycol, the co-catalyst is one or two of crown ether and polyethylene glycol, the stabilizer is one or more of phenothiazine, hydroquinone and anthraquinone, wherein the molecular weight of polyethylene glycol is 200-600.

8. A method for preparing a hyperdispersant according to claim 5, characterized in that: The following steps are also included: (3) the esterified product obtained in step (2) is put back into the reaction kettle after settling, a quaternizing agent is added, and the reaction is carried out at a pressure of -0.1 to 0.05 MPa and 40 to 90° C. for 1 to 8 hours to obtain triethanolamine fatty acid ester quaternary ammonium salt; The quaternizing agent is one or more of epichlorohydrin, dimethyl sulfate, methyl chloride, and sodium chloroacetate; The molar ratio of the esterification product to the quaternizing agent is 1:0.8-4.

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