Water-soluble dispersant, manufacturing process therefor and its use

Abstract

Water-soluble dispersant comprising a polyether-modified polymer A and an amide polymer B; wherein raw materials for the production of the polyether-modified polymer A comprise a vinylbenzene monomer, an allyl succinic anhydride, an active polyether macromonomer and a monohydric alkyl alcohol, wherein the amide polymer B comprises a homopolymer of vinylpyrrolidone and / or a copolymer of vinylpyrrolidone.

Description

Technical field

[0001] Exemplary embodiments of the present application belong to the technical field of dye additives, such as a water-soluble dispersant, a manufacturing process for it and its use. background

[0002] Dispersing agents are surfactants with opposing lipophilic and hydrophilic properties in their molecules, which can uniformly disperse solid and liquid particles of inorganic and organic pigments that are difficult to dissolve in liquids, while simultaneously acting as amphiphilic reagents that can prevent sedimentation and agglomeration of the particles to form a stable suspension.

[0003] Dispersible dyes have a small molecular structure and contain no water-soluble groups, only polar groups. They are extremely sparingly soluble in water and require dispersants to form a homogeneous dispersion for use.

[0004] Conventional dispersion dyes require the addition of a large number of lignin salts, naphthalenesulfonate salts, and other dispersing additives during dispersion. These dispersing additives are needed in large quantities during dispersion, comprising 70 to 150% of the dye content. The resulting liquid dye dispersion has a short stabilization time and cannot achieve long-term preservation. Furthermore, the high concentration of dispersing agents leads to a large amount of organic matter in the printing and dyeing wastewater, causing treatment difficulties, environmental hazards, and other problems.

[0005] US patent 2015 / 0166780 A1 discloses a dispersion composition, a curable composition, a transparent film, a microlens, and a solid-state imaging device, each utilizing the dispersion composition; and a polymer compound. CN 113 527 572 A discloses an aqueous thickening dispersion agent, an aqueous binder, and a manufacturing process for a lithium-ion battery. CN 108 911 561 A discloses a polycarboxylic acid settling inhibitor utilizing polyethers with a molecular weight of 2200 and a process for its preparation.

[0006] CN 1 14 644 762 A discloses a multiply modified lignin dye dispersant and a manufacturing process for it. Industrial alkali lignin is used as a raw material, and under alkaline conditions, sulfonated reagent 1 and sulfonated reagent 2 are used as a sulfonated reagent system to simultaneously introduce sulfone groups at various positions, thereby significantly increasing the content of hydrophilic sulfone groups. The blocking reagent is then optionally added to reduce the proportion of residual hydroxyl groups while simultaneously increasing the molecular mass.The multiply modified lignosulfonate can be used as a dye dispersant and processed into a disperse dye system with good dispersibility and excellent high-temperature stability without milling. This system exhibits very low staining and a low reduction rate for azo dyes, while simultaneously significantly improving the dyeing rate and substantially reducing production costs in the printing and dyeing industries. However, the dispersant in this application requires a high additive content when used for dye dispersion.

[0007] Therefore, it is expected that a water-soluble dispersant for dye dispersion will be developed in this area. Summary

[0008] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0009] Exemplary embodiments of the present application provide a water-soluble dispersant, a method for its preparation, and a use thereof. Compared to a conventional small-molecule dye dispersant with a single anchoring group and wetting group, the water-soluble dispersant provided in the present application contains aromatic, carboxylic ester, and carboxyl pigment affinity groups, and it has good wetting properties, excellent anti-settling, anti-floocing, anti-flooding, and anti-buoyancy properties, strong structural modification, is a rich source of raw materials, and is suitable for a wide variety of pigment dispersion applications.The water-soluble dispersant presented in the present application can control the microscopic electrostatic repulsion effect, the ability to adsorb at multiple sites, the chain solvation effect and the steric hindrance of the dispersant by controlling the ratio of the monomers of the polymer unit, the degree of polymerization of the polymer and the regulation of the structure, number and distribution density of the functional groups, thus ensuring the performance of the dispersant such as wettability as well as anti-settling and anti-flocculation properties.

[0010] In comparison to a conventional dye dispersant, the water-soluble dispersant presented in the present application can not only reduce the amount of dispersant additives, decrease wear and tear on processing equipment and energy consumption and reduce environmental pollution, but it can also disperse and stabilize the slurry uniformly, thus significantly improving the performance of the end use of the dispersed system.

[0011] From a first point of view, embodiments of the present application provide a water-soluble dispersant, and the water-soluble dispersant comprises a polyether-modified polymer A and an amide polymer B.

[0012] The raw materials for the production of the polyether-modified polymer A include a vinylbenzene monomer, an allyl succinic anhydride, an active polyether macromonomer and a monohydric alkyl alcohol.

[0013] The amide polymer B comprises a homopolymer of vinylpyrrolidone and / or a copolymer of vinylpyrrolidone.

[0014] In the present application, the water-soluble dispersant is obtained by compounding the polyether-modified polymer A and the amide polymer B, wherein the prepolymerization product of the polyether-modified polymer A is obtained by polymerization of the vinylbenzene monomer, the allyl succinic anhydride, and the active polyether macromonomer under the initiation of a peroxide initiator by a radical bulk polymerization process, and the anhydride group in the prepolymerization product is subjected to esterification and ring opening with the monohydric alkyl alcohol under the action of an acid catalyst to form the carboxylic ester and the carboxyl groups in order to obtain the polyether-modified polymer A; wherein the polyether-modified polymer A is a polymer with a comb-like structure containing a variety of characteristic functional groups.wherein the active polyether macromonomer provides a hydrophilic segment of the side chain, and wherein the conjugative effect of the benzene ring group contained in the vinylbenzene monomer provides affinity anchoring of the dye group, wherein the anhydride group, which undergoes ring opening and esterification by the monohydric alkyl alcohol, simultaneously provides the functional carboxylic acid ester group with an affinity for pigments and the ionized carboxyl group with a wettability and an electrostatic repulsion effect exerted on the dye particles. The composite system of the polyether-modified polymer A and the polar amide polymer B ensures a greater diversification of the types of functional groups in the water-soluble dispersant system and it improves the wetting and protective effect of the dispersant on the disperse dye particles, thus increasing the milling performance of the disperse dye.The proportion of dye particles in the dispersion and the dispersion stability are improved.

[0015] The active polyether macromonomer is preferably produced by the following manufacturing process: The reaction involves adding polyetheramine and allyl succinic anhydride to a reactor, and carrying out heat preservation until no more water is distilled off during the reaction to obtain the active polyether macromonomer.

[0016] Preferably, the polyetheramine is a mono-primary aminopolyether produced by self-polymerization of an ethylene oxide or by copolymerization of an ethylene oxide and a propylene oxide using a monohydric alcohol as an initiator, wherein the terminal hydroxyl group is replaced by an amino group.

[0017] Preferably, the polyetheramine has a weight-average molecular mass of 500 to 2500 g / mol, such as 500 g / mol, 800 g / mol, 1000 g / mol, 1300 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2300 g / mol or 2500 g / mol.

[0018] Preferably, the polyetheramine comprises one or a combination of at least two of a JEFFAMINE M-2070, a JEFFAMINE M-1000 or a JEFFAMINE M-600.

[0019] Preferably, the molar ratio of the polyetheramine to the allyl succinic anhydride is (0.5 to 1.5) to 1, for example 0.5 to 1, 1 to 1 or 1.5 to 1, and particularly preferably 1 to 1. It should be noted that the allyl succinic anhydride here comprises only the allyl succinic anhydride used in the preparation of the active polyether macromonomer and not the allyl succinic anhydride used directly in the preparation of the polyether-modified polymer A.

[0020] Preferably, the temperature is heated to 120 to 160 °C, for example to 120 °C, 130 °C, 140 °C, 150 °C or 160 °C.

[0021] Preferably, heat retention is carried out over a period of 2 to 6 hours, such as 2, 3, 4, 5 or 6 hours.

[0022] Preferably, the active polyether macromonomer is produced under a protective gas atmosphere.

[0023] Preferably, the active polyether macromonomer has a structure that is represented in the following formula I: where R1 is a hydrogen atom or a methyl group, R2 is a methyl group, an ethyl group, a propyl group or a butyl group, m is an integer from 10 to 60, such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60, and n is an integer from 0 to 15, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15.

[0024] Preferably, the vinylbenzene monomer comprises one or a combination of at least two styrene, β-methylstyrene, allylbenzene, 3-methylstyrene, 2-methylstyrene or 2-isopropenyltoluene.

[0025] Preferably, the monohydric alkyl alcohol comprises one or a combination of at least two of a methanol, an ethanol, a propanol, an n-butanol, an isopropanol, an isobutanol or a tert-butanol.

[0026] Preferably, the mass ratio of the vinylbenzene monomer to the allyl succinic anhydride to the active polyether macromonomer is (2 to 10) to (5 to 20) to (30 to 80), such as 2 to 5 to 30, 10 to 20 to 80, or 5 to 10 to 50. It should be noted that the allyl succinic anhydride here comprises only the allyl succinic anhydride used directly in the preparation of the polyether-modified polymer A, and not the allyl succinic anhydride used in the preparation of the active polyether macromonomer.

[0027] Preferably, the molar ratio of the monohydric alkyl alcohol to the allyl succinic anhydride is (0.1 to 1) to 1, such as 0.1 to 1, 0.2 to 1, 0.3 to 1, 0.4 to 1, 0.5 to 1, 0.6 to 1, 0.7 to 1, 0.8 to 1, 0.9 to 1 or 1 to 1, and particularly preferably 1 to 1. It should be noted that the allyl succinic anhydride referred to here comprises only the allyl succinic anhydride used directly in the preparation of the polyether-modified polymer A, and not the allyl succinic anhydride used in the preparation of the active polyether macromonomer.

[0028] Preferably, the raw materials for the production of the polyether-modified polymer A further comprise an initiator and a catalyst.

[0029] Preferably, the initiator comprises one or a combination of at least two of a benzoyl peroxide, a tert-butyl peroxybenzoate, a methyl ethyl ketone peroxide, a dicumyl peroxide, a di-tert-butyl peroxide or a 2,2-bis(tert-butylperoxy)butane.

[0030] Preferably, the catalyst comprises one or a combination of at least two of a p-toluenesulfonic acid, a sulfuric acid, a propionic acid, a sulfamic acid or a hydrochloric acid.

[0031] Preferably, the raw materials for the production of the polyether-modified polymer A have the following components, based on weight: Vinylbenzene monomer 4 to 20 pieces; Allyl succinic anhydride 10 to 40 pieces; active polyether macromonomer 60 to 160 pieces; monohydric alkyl alcohol in a molar ratio of the monohydric alkyl alcohol to the allyl succinic anhydride of (0.1 to 1) to 1; initiator 0.5 to 2 parts; and catalyst 1 to 3 pieces.

[0032] Preferably, the amount of vinylbenzene monomer used as a raw material for the production of the polyether-modified polymer A can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts by weight.

[0033] Preferably, the amount of allyl succinic anhydride used as a raw material for the production of the polyether-modified polymer A can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts by weight.

[0034] Preferably, the amount of active polyether macromonomer used as a raw material for the production of the polyether-modified polymer A can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts or 160 parts.

[0035] Preferably, the molar ratio of the monohydric alkyl alcohol to the allyl succinic anhydride as a raw material for the production of the polyether-modified polymer A can be 0.1 to 1, 0.2 to 1, 0.3 to 1, 0.4 to 1, 0.5 to 1, 0.6 to 1, 0.7 to 1, 0.8 to 1, 0.9 to 1 or 1 to 1 in parts by weight.

[0036] Preferably, the amount of initiator used as a raw material for the production of the polyether-modified polymer A can be 0.5 parts, 1 part, 1.5 parts or 2 parts by weight.

[0037] Preferably, the amount of catalyst used as a raw material for the production of the polyether-modified polymer A can be 1 part, 2 parts or 3 parts by weight.

[0038] Preferably, the polyether-modified polymer A has a weight-average molecular mass of 5,000 to 100,000 g / mol, such as 5,000 g / mol, 8,000 g / mol, 10,000 g / mol, 20,000 g / mol, 30,000 g / mol, 40,000 g / mol, 50,000 g / mol, 60,000 g / mol, 70,000 g / mol, 80,000 g / mol, 90,000 g / mol or 100,000 g / mol and particularly preferably of 20,000 to 60,000 g / mol.

[0039] Preferably, the amide polymer B has a weight-average molecular mass of 2,000 to 100,000 g / mol, such as 2,000 g / mol, 5,000 g / mol, 8,000 g / mol, 10,000 g / mol, 20,000 g / mol, 30,000 g / mol, 40,000 g / mol, 50,000 g / mol, 80,000 g / mol or 100,000 g / mol and particularly preferably of 10,000 to 50,000 g / mol.

[0040] Preferably, the amide polymer B comprises one or a combination of at least two of a PVPK25, a PVPK30, a PVPK35 or a copovidone VA64.

[0041] Preferably, the mass ratio of the polyether-modified polymer A and the amide polymer B is (7 to 22) to (4 to 7), such as 7 to 4, 7 to 6, 7 to 7, 15 to 4, 15 to 6, 15 to 7, 22 to 4, 22 to 6 or 22 to 7.

[0042] Preferably, the water-soluble dispersant also comprises deionized water and a pH regulator.

[0043] Preferably, the pH adjuster comprises one or a combination of at least two sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol or N,N-dimethylethanolamine, and particularly preferably it comprises sodium hydroxide and / or potassium hydroxide.

[0044] Preferably, the raw materials for the production of the water-soluble dispersant comprise the following components by weight: polyether-modified polymer A 70 to 220 pieces; Amide polymer B 40 to 70 pieces; deionized water 80 to 200 pieces; and pH adjuster which adjusts the pH value of the system to between 7 and 10.

[0045] Preferably, the amount of polyether-modified polymer A used as a raw material for the production of the water-soluble dispersant can be 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts or 220 parts.

[0046] Preferably, the amount of amide polymer B used as a raw material for the production of the water-soluble dispersant can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts by weight.

[0047] Preferably, the amount of deionized water used as a raw material for the production of the water-soluble dispersant, in parts by weight, can be 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts or 200 parts.

[0048] According to a second point, embodiments of the present application provide a manufacturing process for the water-soluble dispersant as described in the first point, and the manufacturing process comprises the following steps: (1) Adding an active polyether macromonomer in a formulation quantity to a reactor, heating, then adding a vinylbenzene monomer, an allyl succinic anhydride, and an optional initiator and carrying out a reaction under heat preservation, then successively adding a monohydric alkyl alcohol and an optional catalyst, carrying out another reaction under heat preservation, taking samples, and testing every 30 minutes until the difference between the acid values ​​of the system in two adjacent tests is ≤ 2 mg KOH / g, and stopping the reaction to obtain the polyether-modified polymer A; and (2) cooling of the polyether-modified polymer A obtained in step (1), then adding optional deionized water and the amide polymer B, then adding an optional pH regulator and stirring to obtain the water-soluble dispersant.

[0049] Preferably, during heating in step (1), the temperature is increased to 100 to 150 °C, such as 100 °C, 110 °C, 120 °C, 130 °C, 140 °C or 150 °C.

[0050] Preferably, in step (1) for the addition of the vinylbenzene monomer, the allyl succinic anhydride and the optional initiator, these three raw materials are first processed to a mixture and then added dropwise, and a period of dropwise addition is set to 2 to 8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.

[0051] Preferably, the reaction with heat preservation in step (1) is carried out at a temperature of 100 to 150 °C, such as 100 °C, 110 °C, 120 °C, 130 °C, 140 °C or 150 °C, and the reaction under heat preservation is carried out over a period of 1 to 3 h, such as 1 h, 2 h or 3 h.

[0052] Preferably, the other reaction with heat preservation in step (1) is carried out at a temperature of 100 to 150 °C, such as 100 °C, 110 °C, 120 °C, 130 °C, 140 °C or 150 °C, and the other reaction with heat preservation is carried out for a period of 2 to 10 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.

[0053] Preferably, the acidity level in step (1) is measured by titration using neutral ethanol as a solvent and a standard sodium hydroxide solution or a standard potassium hydroxide solution as a neutralizing titrant.

[0054] It should be noted that the difference between the acid values ​​of the system in the two adjacent tests in step (1) refers to the difference between two successive measurements of the acid values ​​of the system, where the result of the large value minus the small value is ≤ 2 mgKOH / g.

[0055] Preferably, both step (1) and step (2) are carried out under a protective gas.

[0056] Preferably, the temperature in step (2) is cooled to 50 to 60 °C, for example to 50 °C, 55 °C or 60 °C.

[0057] According to a third point, embodiments of the present application provide a use of the water-soluble dispersing agent as described in the first point.

[0058] In comparison to the related prior art, the embodiments of the present application have the following advantageous effects:

[0059] In the embodiments of the present application, the vinylbenzene monomer, the allyl succinic anhydride, and the active polyether macromonomer are subjected to radical bulk polymerization and then esterified with the monohydric alkyl alcohol to obtain the polyether-modified polymer A. The polyether-modified polymer A and the amide polymer B are compounded to form a water-soluble dispersant. The types of functional groups in the water-soluble dispersant system are more diverse, which improves the wetting and protective effect of the dispersant on the dispersed dye particles, thus improving the milling efficiency of the dispersed dyes, the proportion of dye particles in the dispersion, and the dispersion stability.

[0060] Further aspects become clear when reading and understanding the detailed description. Detailed description, production example 1

[0061] The manufacturing example yields an active polyether macromonomer, and the manufacturing process comprises the following steps: 200 g of polyetheramine JEFFAMINE M-2070 and 14 g of allyl succinic anhydride (the molar ratio of these two substances was 1 to 1) were placed in a reaction flask, which was protected with N2 and heated to 120 °C and held for 6 hours until no more water had been distilled off in the reaction process, in order to obtain the active polyether macromonomer, which was designated a1. Production example 2

[0062] The manufacturing example yields an active polyether macromonomer, and the manufacturing process comprises the following steps: 200 g of polyetheramine JEFFAMINE M-1000 and 28 g of allyl succinic anhydride (the molar ratio of these two substances was 1 to 1) were placed in a reaction flask protected with N2, heated to 160 °C and held for 2 hours until no more water had been distilled off in the reaction process, in order to obtain the active polyether macromonomer, which was designated a2. Comparative manufacturing example 1

[0063] This comparative manufacturing example differs from manufacturing example 1 only in that the allyl succinic anhydride was replaced by a maleic anhydride with the same molar amount and the resulting polyether is designated as D -a1 was described. Example 1

[0064] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 60 parts by weight of the active polyether macromonomer a1 were weighed out and placed in a reaction flask protected with nitrogen, stirred, and heated to 100 °C. A mixed solution containing 20 parts styrene, 15 parts allyl succinic anhydride, and 0.5 parts benzoyl peroxide was added dropwise, and the dropwise addition was completed within 3 hours. After completion of the dropwise addition, the reaction was held at 100 °C for 1 hour, the flask being kept at an internal temperature of 100 °C. 7.9 parts n-butanol and 1 part p-toluenesulfonic acid were added successively by weight, and the reaction was carried out at a constant temperature for 6 hours, with samples being taken and tested every 30 minutes.The reaction was stopped as soon as the difference between the acid values ​​of the system of the two adjacent tests was ≤ 2 mgKOH / g to obtain a polyether-modified polymer A; and. (2) 90 parts by weight of the polyether-modified polymer A obtained in step (1) were weighed out and placed in a reaction flask protected with N2, cooled to 60 °C and then mixed with 120 parts deionized water and 40 parts PVPK30, then potassium hydroxide was added to adjust the pH of the system to 8.5 and the system was stirred uniformly to obtain the water-soluble dispersant. Example 2

[0065] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 120 parts by weight of the active polyether macromonomer a2 were weighed out and placed in a reaction flask protected with N2, stirred, and heated to 110 °C; a mixed solution containing 4 parts allylbenzene, 20 parts allyl succinic anhydride, and 0.8 parts benzoyl peroxide was added dropwise at a uniform rate, and the dropwise addition was completed within 2 hours, and after completion of the dropwise addition, the reaction was held at 110 °C for 1 hour, the flask being kept at a temperature of 110 °C internally, 3.3 parts by weight of ethanol and 1.2 parts by weight of sulfuric acid were added successively, and the reaction was carried out at a constant temperature for 1 hour, samples being taken and tested every 30 minutes, and until the difference between the acid values ​​of the system of the two adjacent tests was ≤ 2 mg KOH / g, the reaction was stopped to obtain a polyether-modified polymer A; and (2) 130 parts by weight of the polyether-modified polymer A obtained in step (1) were weighed out and placed in a reaction flask protected with N2, cooled to 60 °C and then mixed with 100 parts deionized water and 45 parts PVPK35, then sodium hydroxide was added to adjust the pH of the system to 7.5 and the system was stirred uniformly to obtain the water-soluble dispersant. Example 3

[0066] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 80 parts by weight of the active polyether macromonomer a1 were weighed out and placed in a reaction flask protected with N2, stirred and heated to 125 °C;A mixed solution containing 10 parts 2-methylstyrene, 30 parts allyl succinic anhydride, and 1.8 parts tert-butyl peroxybenzoate was added dropwise at a uniform rate. The dropwise addition was completed within 8 hours. After completion of the dropwise addition, the reaction was held at 125 °C for 2 hours. The flask was kept at a temperature of 125 °C. 6.9 parts methanol and 1.6 parts sulfamic acid by weight were added successively, and the reaction was carried out at a constant temperature for 2 hours. Samples were taken and tested every 30 minutes. When the difference between the acid values ​​of the system in both adjacent tests was ≤ 2 mg KOH / g, the reaction was stopped to obtain a polyether-modified polymer A. (2) 110 parts of the polyether-modified polymer A obtained in step (1) were weighed by weight and placed in a reaction flask protected with N2, cooled to 60 °C, and then 160 parts of deionized water and 60 parts of povidone VA64 were added. Subsequently, potassium hydroxide was added to adjust the pH of the system to 10, and the system was stirred uniformly to obtain the water-soluble dispersant. Example 4

[0067] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 140 parts by weight of the active polyether macromonomer a2 were weighed out and placed in a reaction flask protected with N2, stirred and heated to 145 °C; A mixed solution containing 15 parts styrene, 25 parts allyl succinic anhydride, and 1.5 parts di-tert-butyl peroxide was added dropwise at a uniform rate, and the dropwise addition was completed within 7 h. After completion of the dropwise addition, the reaction was held at 145 °C for 2 h, the flask being kept at a temperature of 145 °C. 10.7 parts isopropanol and 2.6 parts p-toluenesulfonic acid by weight were added successively, and the reaction was carried out at a constant temperature for 8 hours, with samples taken and tested every 30 minutes. The reaction was stopped when the difference between the acid values ​​of the system of the two adjacent tests was ≤ 2 mgKOH / g to obtain a polyether-modified polymer A.and; (2) 160 parts of the polyether-modified polymer A obtained in step (1) were weighed and placed in a reaction flask protected with N2, cooled to 60 °C, and then mixed with 155 parts deionized water and 70 parts PVPK30. Sodium hydroxide was then added to adjust the pH of the system to 8.5, and the system was stirred uniformly to obtain the water-soluble dispersant. Example 5

[0068] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 160 parts by weight of the active polyether macromonomer a1 were weighed out and placed in a reaction flask protected with N2, stirred and heated to 115 °C;A mixed solution containing 17 parts styrene, 35 parts allyl succinic anhydride, and 2 parts benzoyl peroxide was added dropwise at a uniform rate, and the dropwise addition was completed within 5 hours. After completion of the dropwise addition, the reaction was held at 115 °C for 2.5 hours, with the flask maintained at a temperature of 115 °C. 18.5 parts tert-butanol and 2.8 parts hydrochloric acid were added successively by weight, and the reaction was carried out at a constant temperature for 6 hours, with samples taken and tested every 30 minutes. The reaction was stopped until the difference between the acid values ​​of the system in both adjacent tests was ≤ 2 mg KOH / g, in order to obtain a polyether-modified polymer A. (2) 210 parts of the polyether-modified polymer A obtained in step (1) were weighed and placed in a reaction flask protected with N2, cooled to 60 °C, and then mixed with 175 parts deionized water and 50 parts PVPK35. Potassium hydroxide was then added to adjust the pH of the system to 9.5, and the system was stirred uniformly to obtain the water-soluble dispersant. Example 6

[0069] This example provides a water-soluble dispersant, and the manufacturing process includes the following steps: (1) 50 parts of the active polyether macromonomer a1 and 50 parts of the active polyether macromonomer a2 were weighed and placed in a reaction flask protected with N2, stirred and heated to 130 °C; a mixed solution containing 9 parts of 3-methylstyrene, 40 parts of allyl succinic anhydride and 1.2 parts of dicumyl peroxide was added dropwise at a uniform rate, and the dropwise addition was completed within 6 hours.After completion of the dropwise addition, the reaction was held at 130 °C for 3 hours, the flask was kept at a temperature of 130 °C inside, 9.1 parts methanol and 3 parts propionic acid were added successively by weight, and the reaction was carried out at a constant temperature for 4 hours, with samples taken and tested every 30 minutes, and when the difference between the acid values ​​of the system in both adjacent tests was ≤ 2 mgKOH / g, the reaction was stopped to obtain a polyether-modified polymer A; and. (2) 140 parts of the polyether-modified polymer A obtained in step (1) were weighed and placed in a reaction flask protected with N2, cooled to 60 °C, then 200 parts of deionized water and 70 parts of PVPK30 were added, then sodium hydroxide was added to adjust the pH of the system to 7.5, and the system was stirred uniformly to obtain the water-soluble dispersant. Example 7

[0070] This example differs from example 1 only in that the active polyether macromonomer a1 in step (1) was 50 parts by weight. Example 8

[0071] This example differs from example 5 only in that the active polyether macromonomer a1 in step (1) was 170 parts by weight. Comparative example 1

[0072] This comparative example differs from example 1 only in that the active polyether macromonomer a1 in step (1) was replaced by an allyl polyether APEG2400 with equal parts by weight. Comparative example 2

[0073] This comparative example differs from example 1 only in that the vinylbenzene monomer (styrene) in step (1) has been replaced by a sodium p-styrene sulfonate with equal parts by weight. Comparative example 3

[0074] This comparative example differs from example 1 only in that the allyl succinic anhydride in step (1) has been replaced by a maleic anhydride with equal parts by weight. Comparative example 4

[0075] This comparative example differs from example 1 only in that the monohydric alkyl alcohol (n-butanol) in step (1) was replaced by a laurinol with the same molar fraction. Comparative example 5

[0076] This comparative example differs from example 1 only in that the amide polymer B (PVPK30) in step (2) was replaced by a PVPK12 with equal parts by weight. Comparative example 6

[0077] This comparative example differs from example 1 only in that the active polyether macromonomer a1 in step (1) was replaced by the polyether D-a1 with equal parts by weight, which was produced in comparative example 1. Comparative example 7

[0078] A commercially available dispersing agent that is NNO. Test example

[0079] The laboratory grinding process was carried out, the dispersion formulation totaled 200 g, and a dispersing agent, water, and a dispersion dye (Disperse Red 167) were added successively in their respective proportions. After uniform stirring, 400 g of zirconium beads with a particle size of 0.8 to 1 mm were added to the system and sealed in a glass container. The system was then shaken for 15 hours and subsequently filtered to obtain a dye dispersion.

[0080] The dye dispersion produced in the present application has the specific formulation shown in Table 1: Table 1 Dye dispersion DisperseRed 167 (g) Dispersing agent Water (g) product Quantity (g) Test Example 1 54 Example 1 12 134 Test Example 2 54 Example 2 12 134 Test Example 3 54 Example 3 12 134 Test Example 4 54 Example 4 12 134 Test Example 5 54 Example 5 12 134 Test Example 6 54 Example 6 12 134 Test Example 7 54 Example 7 12 134 Test Example 8 54 Example 8 12 134 Test comparison example 1 54 Comparative example 1 12 134 Test comparison example 2 54 Comparative example 2 12 134 Test comparison example 3 54 Comparative example 3 12 134 Test comparison example 4 54 Comparative example 4 12 134 Test comparison example 5 54 Comparative example 5 12 134 Test comparison example 6 54 Comparative example 6 12 134 Test comparison example 7 54 Blank 0 146 Test comparison example 8 54 Comparative example 7 (dispersing agent NNO) 12 134 Test comparison example 9 54 Comparative example 7 (dispersing agent NNO) 54 92 Performance test (1) Viscosity: measured using a rotational viscometer NDJ-1B, Shanghai Changji Geological Instrument Co., Ltd; “-” means that the viscosity is too high to be measured. (2) Particle size: measured using a BT-90 laser particle size analyzer, Dandong Bettersize Instrument Co., Ltd; “\” indicates sedimentation or lack of flowability, and particle size cannot be verified. (3) Storage stability: The dye dispersion was stored at 55 °C for 7 days, the condition of the dye dispersion was observed and the particle size and viscosity were retested. (4) Centrifugal sedimentation rate (%): The dye dispersion was centrifuged at 4000 rpm for 20 minutes, washed with anhydrous ethanol, and fired at 90 °C until its weight was constant, and then weighed precisely to obtain the sedimentation weight; Sedimentation rate = Sedimentation weight ÷ (dye content of the dispersion × sample quantity) × 100 %; “+” means that there is no fluidity and the sedimentation rate cannot be checked.

[0081] The specific test results are listed in Table 2: Table 2 group Viscosity (mpa·s) Particle size D50 (nm) Centrifugal sedimentation rate (%) Initially 55°C / 7d Initially 55°C / 7d Test Example 1 256 270 290 293 4,5 % Test Example 2 245 261 298 303 4,9 % Test Example 3 237 245 325 329 4,2 % Test Example 4 252 261 318 325 3,6 % Test Example 5 264 276 308 316 3,3 % Test Example 6 249 261 331 340 4,0 % Test Example 7 478 1534 476 879 27,5 % Test Example 8 573 - 783 \ 34,2 % Test comparison example 1 345 492 412 573 12,1 % Test comparison example 2 1382 - 1052 \ 45,2 % Test comparison example 3 1415 - 756 \ + Test comparison example 4 375 - 418 \ 10,7 % Test comparison example 5 298 467 354 475 13,5 % Test comparison example 6 - - \ \ + Test comparison example 7 - - \ \ + Test comparison example 8 684 978 545 678 55,6 % Test comparison example 9 478 537 456 489 25,5 %

[0082] As can be seen from the data in Table 2, the water-soluble dispersant in the present application, obtained by combining the polyether-modified polymer A and the amide polymer B, exhibits, provided a small quantity is used, good dispersing effect on the dye dispersion (particle size D50 (initial): 290 to 331 nm), the dye dispersion can meet the viscosity requirements (viscosity (initial): 237 to 264 mPa·s), a low centrifugal sedimentation rate (3.3 to 4.9%), and good dye dispersion stability (showing small changes in viscosity and particle size after 7 days of storage at 55 °C), as well as a long shelf life, which is better than that of commercially available dispersants.

[0083] As can be seen from the comparison of test example 7 and test example 1, the viscosity, particle size, and centrifugal sedimentation rate of the dye dispersion increase considerably when the amount of active polyether macromonomer is too low, and system stability is poor. As can be seen from the comparison of test example 8 and test example 5, the particle size and viscosity of the dye dispersion increase considerably when the amount of active polyether macromonomer is too high, the increase in the corresponding indicators after storage is too large, and the centrifugal sedimentation rate is significantly higher.

[0084] As can be seen from the comparison of test example 1 and comparison test examples 1 to 6, the viscosity, particle size and centrifugal sedimentation rate of the dye dispersion are significantly increased when one of the raw materials for the production of the polyether-modified polymer A (the vinylbenzene monomer, the allyl succinic anhydride, the active and monohydric alkyl alcohol) is replaced by another component or when the amide polymer B is replaced by another component.

[0085] The applicant explains that a water-soluble dispersant, a manufacturing process for it, and a use thereof are illustrated in the present application by the examples above, but that the present application is not limited to the examples above. That is to say, the present application is not necessarily dependent on the implementation of the examples above.

Claims

[1] Water-soluble dispersant comprising a polyether-modified polymer A and an amide polymer B; wherein raw materials for the production of the polyether-modified polymer A comprise a vinylbenzene monomer, an allyl succinic anhydride, an active polyether macromonomer and a monohydric alkyl alcohol, wherein the amide polymer B comprises a homopolymer of vinylpyrrolidone and / or a copolymer of vinylpyrrolidone. [2] Water-soluble dispersant according to claim 1, wherein the active polyether macromonomer is produced by the following manufacturing process: The reaction involves adding polyetheramine and allyl succinic anhydride to a reactor, heating, and carrying out heat conservation until no more water is distilled off during the reaction to obtain the active polyether macromonomer. [3] Water-soluble dispersing agent according to claim 2, wherein the polyetheramine is a mono-primary aminopolyether produced by self-polymerization of ethylene oxide or copolymerization of ethylene oxide and propylene oxide using a monohydric alcohol as an initiator and wherein the terminal hydroxyl group is replaced by an amino group. [4] Water-soluble dispersant according to claim 2 or 3, wherein the polyetheramine has a weight-average molecular weight of 500 to 2500 g / mol, wherein the molar ratio of the polyetheramine to the allyl succinic anhydride is preferably (0.5 to 1.5) to 1 and preferably 1 to 1, where heating is preferably to 120 to 160 °C, where heat retention is preferably carried out for a period of 2 to 6 hours, wherein the active polyether macromonomer is preferably produced under a protective gas atmosphere. [5] Water-soluble dispersant according to any one of claims 1 to 4, wherein the active polyether macromonomer has a structure shown below in formula I: wherein R1 is a hydrogen atom or a methyl group, R2 is a methyl group, an ethyl group, a propyl group or a butyl group, m is an integer from 10 to 60 and n is an integer from 0 to 15. [6] Water-soluble dispersant according to any one of claims 1 to 5, wherein the vinylbenzene monomer comprises one or a combination of at least two styrene, β-methylstyrene, allylbenzene, 3-methylstyrene, 2-methylstyrene or 2-isopropenyltoluene, wherein preferably the monohydric alkyl alcohol comprises one or a combination of at least two of a methanol, an ethanol, a propanol, an n-butanol, an isopropanol, an isobutanol or a tert-butanol, wherein preferably the mass ratio of the vinylbenzene monomer to the allyl succinic anhydride and to the active polyether macromonomer is (2 to 10) to (5 to 20) to (30 to 80), wherein the molar ratio of the monohydric alkyl alcohol to the allyl succinic anhydride is preferably (0.1 to 1) to 1 and preferably 1 to 1. [7] Water-soluble dispersant according to any one of claims 1 to 6, wherein the raw materials for the production of the polyether-modified polymer A further comprise an initiator and a catalyst, wherein preferably the initiator comprises one or a combination of at least two comprising a benzoyl peroxide, a tert-butyl peroxybenzoate, a methyl ethyl ketone peroxide, a dicumyl peroxide, a di-tert-butyl peroxide or a 2,2-bis(tert-butyl-peroxy)butane, wherein preferably the catalyst comprises one or a combination of at least two of a p-toluenesulfonic acid, a sulfuric acid, a propionic acid, a sulfamic acid or a hydrochloric acid, wherein the raw materials for the production of the polyether-modified polymer A preferably comprise the following components by weight: Vinylbenzene monomer 4 to 20 pieces, Allyl succinic anhydride 10 to 40 pieces, active polyether macromonomer 60 to 160 pieces, monohydric alkyl alcohol in a molar ratio of monovalent Alkyl alcohol to allyl succinic anhydride from (0.1 to 1) to 1, initiator 0.5 to 2 parts. and catalyst 1 to 3 pieces. [8] Water-soluble dispersing agent according to any one of claims 1 to 7, wherein the polyether-modified polymer A has a weight average molecular weight of 5,000 to 100,000 g / mol and preferably 20,000 to 60,000 g / mol, wherein the mass ratio of the polyether-modified polymer A to the amide polymer B is preferably (7 to 22) to (4 to 7). [9] Water-soluble dispersant according to any one of claims 1 to 8, wherein the water-soluble dispersant further comprises deionized water and a pH adjuster; wherein the raw materials for the production of the water-soluble dispersant preferably comprise the following components by weight: polyether-modified polymer A 70 to 220 pieces, Amide polymer B 40 to 70 pieces, deionized water 80 to 200 pieces, and pH adjuster which adjusts the pH value of the system to between 7 and 10. [10] Manufacturing process for the water-soluble dispersant according to any one of claims 1 to 9, comprising the following steps: (1) adding an active polyether macromonomer in a formulation quantity to a reactor, heating, then adding a vinylbenzene monomer, an allyl succinic anhydride and an optional initiator and carrying out a reaction under heat preservation, then adding a monohydric alkyl alcohol and an optional catalyst successively, carrying out another reaction under heat preservation, taking and testing samples every 30 minutes until the difference between the acid values ​​of the system in two adjacent tests is ≤ 2 mgKOH / g, and stopping the reaction to obtain the polyether-modified polymer A, and (2) Cooling the polyether-modified polymer A obtained in step (1), then adding optionally deionized water and the amide polymer B, and then optionally adding a pH adjuster and stirring to obtain the water-soluble dispersant. [11] Manufacturing process according to claim 10, wherein the heating in step (1) is heating to 100 to 150 °C. [12] Manufacturing process according to claim 10 or 11, wherein the heat-preserving reaction in step (1) is carried out at a temperature of 100 to 150 °C and the heat-preserving reaction is carried out for a period of 1 to 3 h, wherein preferably the other heat-preserving reaction in step (1) is carried out at a temperature of 100 to 150 °C and the other heat-preserving reaction is carried out for a period of 2 to 10 h. [13] Manufacturing process according to one of claims 10 to 12, wherein step (1) and step (2) are both carried out under protective gas, preferably cooling to 50 to 60 °C in step (2). [14] Use of the water-soluble dispersing agent according to any one of claims 1 to 9 in a dye dispersion.