Amide polymer and preparation method thereof, polyamide liquid rheological additive and preparation method and application thereof

Abstract

The invention relates to an amide polymer and a preparation method thereof, a polyamide liquid rheological additive and a preparation method and application thereof, and belongs to the technical field of additives. The preparation method of the amide polymer comprises the following steps: (1) sequentially adding a polyamine compound, dibasic acid and diamine into a reaction container, and carrying out amidation reaction to obtain a first polymer; and (2) adding a linking compound and an end-capped polymer or adding the end-capped polymer, so that the end-capped polymer is linked to the first polymer through the linking compound or the end-capped polymer is directly linked to the first polymer. According to the preparation method, end-capped polymers such as polyether or polyester are introduced to be connected into a polyamide structure of the first polymer, and activation is carried out while connection is carried out. The amide polymer is free-flowing liquid, can be added in each link of paint and ink production, and is particularly suitable as a rheological additive of a paint or ink system.

Description

Technical Field

[0001] The invention relates to the technical field of additives, and in particular to an amide polymer and a preparation method thereof, a polyamide liquid rheological additive and applications thereof. Background Art

[0002] In the field of coatings and inks, the viscosity of coatings and inks is crucial to their commercial success. Although the active ingredients (resins and pigments) of coatings and inks determine the final performance of their utility, the overall formulation is also critical to the commercial success of coatings and inks, especially the rheological properties of coatings and inks, which largely determine the way coatings and inks are stored and used.

[0003] There are many types of rheological additives on the market, the more mainstream ones are fumed silica, organic modified bentonite, hydrogenated castor oil and polyethylene wax. Although these rheological additives are widely used, they generally have some disadvantages. For example, fumed silica is not effective enough in thickening thick coatings; organic modified bentonite has a more obvious thickening effect, but poor transparency and poor coating leveling; hydrogenated castor oil must be fully activated before use, and cooling needs to be slow and temperature control needs to be precise, otherwise hydrogenated castor oil is easy to precipitate and cause failure; polyethylene wax has a general anti-sagging effect when used alone.

[0004] The other two major categories of rheological additives are polyamide compounds and polyurea compounds. Polyurea rheological additives are mainly used in certain niche areas due to their complex preparation process and high cost. Among solvent-based rheological additives, polyamide wax powder products dominate the market because of their low price and good application effect. At present, there are many patents and literature on polyamide rheological additives at home and abroad, involving a variety of raw material combinations, preparation processes and their uses. The structure of polyamide rheological additives is mainly a chain structure condensed from dicarboxylic acids and diamines.

[0005] The Japanese company Kusumoto first described the use of monoacid plus diamine to form a polyamide structure and use it as a rheological additive in its 1974 patent US3937678A. Subsequently, the structure formed by monoacid plus diacid plus diamine was used as a rheological additive in patents EP0210157A1, US5214224, and US2012289437A1, and this practice has been used for many years. Kusumoto also modified this structure in its 2011 patent US2012125235A1 to develop a water-based rheological additive.

[0006] The Chinese company PetroChina began to introduce polyamines in patents CN103666414A and CN105368416A to form non-linear structures to increase molecular weight and increase the number of amide functional groups to improve product performance.

[0007] Although these polyamide rheological additives are widely used, their shortcomings are also obvious. First, they are inconvenient to use. When using, they need to be added to the whole bucket of paint and heated at 60° for 1-1.5 hours for activation. Users need to accumulate years of experience to master the use of the product. Secondly, they cannot be added at different stages of coating preparation, which makes them inflexible to use. To solve this problem, various companies have adopted different pre-dispersion methods for early activation, such as activation in resin. The products are generally paste-like and have low effective content. Summary of the invention

[0008] Based on this, the object of the present invention is to provide an amide polymer and a preparation method thereof, a polyamide liquid rheological additive and a preparation method and application thereof. The amide polymer can be used as an effective ingredient of the polyamide liquid rheological additive to prepare coatings or inks to control the rheological properties of the coating or ink system.

[0009] To achieve the above object, the present invention adopts the following technical solutions:

[0010] The first object of the present invention is to provide a method for preparing an amide polymer, comprising the following steps:

[0011] (1) adding a polyamine compound, a dibasic acid, and a diamine into a reaction container in sequence to carry out an amidation reaction to obtain a first polymer;

[0012] (2) adding a connecting compound and a capping polymer or adding a capping polymer, so that the capping polymer is connected to the first polymer through the connecting compound or the capping polymer is directly connected to the first polymer; the connecting compound is at least one of anhydride, dibasic acid, acetoacetate, unsaturated double bond, alkylating agent, isocyanate; the capping polymer is at least one of polyester, polyether, polyacrylate, polymethyl methacrylate;

[0013] Assuming that the polyamine compound has a amine groups, a≥3, when a connecting compound and a blocked polymer are added, the molar ratio of the polyamine compound, the dibasic acid, the diamine, the connecting compound and the blocked polymer is 1:(a-10a):(a-10a):(1-a):(1-a); when a blocked polymer is added, the molar ratio of the polyamine compound, the dibasic acid, the diamine and the blocked polymer is 1:(a-10a):(a-10a):(1-a).

[0014] In the method for preparing the amide polymer of the present invention, in step (1), a carboxyl group in the dibasic acid and an amine group (e.g., -NH 2, -NH-) reacts with an active hydrogen on the polyamine compound, thereby connecting multiple dibasic acids to the polyamine compound, creating conditions for forming multiple branches; by adding the diamine to connect with another unreacted carboxyl group in the dibasic acid (or further connecting to form a repeating unit of dibasic acid-diamine), a first polymer with multiple amide bonds and high branches (multiple branches) is obtained. The amide bonds in the structure of the first polymer are distributed in a three-dimensional spatial structure, which is conducive to the formation of a three-dimensional hydrogen bond structure in space, and the branches connected to the polyamine compound are easily entangled with each other, obtaining a network structure with denser physical cross-linking points and more stable, and such a structure is conducive to improving the suspension characteristics of the coating system. However, although the first polymer has more amide groups, it has a high melting point and poor compatibility. In the chemical field, it is generally used only as a base resin for coatings and inks or as an adhesive; at the same time, the first polymer has a strong intermolecular force, is easy to crystallize, and is difficult to dissolve in common aromatic solvents, so it is not easy to operate in the subsequent swelling activation step.

[0015] In the preparation method of the amide polymer of the present invention, in step (2), by adding a connecting compound and an end-capping polymer or adding an end-capping polymer, the end-capping polymer is connected to the first polymer through the connecting compound or the end-capping polymer is directly connected to the first polymer, thereby introducing the end-capping polymer into the structure of the first polymer. The end-capping polymer is at least one of polyester, polyether, polyacrylate, and polymethyl methacrylate, that is, in the present invention, at least one of polyester, polyether, polyacrylate, and polymethyl methacrylate is connected to the first polymer through step (2), and during and after the connection reaction, at least one of polyester, polyether, polyacrylate, and polymethyl methacrylate simultaneously activates the polyamide part in the first polymer, so that the obtained amide polymer is a free-flowing liquid, which is significantly different from the traditional paste-like amide polymer, and is suitable for being made into a liquid rheological additive for use in a coating or ink system, and can be added in various links of the coating or ink production.

[0016] In step (2), the end-capping polymer can be introduced into the first polymer by direct reaction (e.g., through imine formation, Michael addition), or by indirect reaction of a linking compound (e.g., through alkylation, through anhydride to form amide, or through isocyanate to form urea, etc.).

[0017] In the preparation method of the amide polymer of the present invention, based on the number of amine groups on the polyamine compound, a≥3, when adding the linking compound and the end-capping polymer, the molar ratio of the polyamine compound, the dibasic acid, the diamine, the linking compound, and the end-capping polymer is 1:(a-10a):(a-10a):(1-a):(1-a); when adding the end-capping polymer, the molar ratio of the polyamine compound, the dibasic acid, the diamine, and the end-capping polymer is 1:(a-10a):(a-10a):(1-a). The molar ratio of the above substances is limited, which is conducive to forming multiple branches with the polyamine compound as the core, the dibasic acid and the diamine (or its repeating units) in step (1); in step (2), by introducing the end-capping polymer, the ends of some or all of the multiple branches are capped (preferably the ends of some branches are capped), and the amide structure is activated at the same time.

[0018] Furthermore, in step (1), the polyamine compound has the following general structural formula: NH 2 -(R 1 -NH)qR 1 -NH 2 , the dibasic acid has the following general structural formula: COOH-R 2 -COOH, where R 1 is at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 aromatic group or an aralkyl group; q is 1-100. 1 The groups may be branched or unbranched.

[0019] As a preferred embodiment, in step (1), the polyamine compound is an aliphatic polyamine compound, and the aliphatic polyamine compound is at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyetheramine.

[0020] Furthermore, in step (1), the dibasic acid has the following general structural formula: COOH-R 2 -COOH, where R 2 It is at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 aromatic group or an aralkyl group. The above groups may be branched or unbranched.

[0021] As a preferred embodiment, in step (1), the dibasic acid is an aliphatic dibasic acid, and the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, docosanedioc acid, a dimer of an unsaturated C18 acid, dodecenyl thiocarboxylic acid, and a dimer fatty acid (e.g., C36-dimer acid).

[0022] Furthermore, in step (1), the diamine has the following general structural formula: NH 2 -R 3 -NH 3 , where R 3 It is at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 aromatic group or aralkyl group, and a polyether. The above groups may be branched or unbranched.

[0023] As a preferred solution, in step (1), the diamine is an aliphatic diamine, and the aliphatic diamine is at least one of ethylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, decanediamine, dodecanediamine, octadecanediamine, and a dibasic polyetheramine.

[0024] As a preferred solution, in step (1), the above three raw materials (polyamine compound, dibasic acid, diamine) are added successively and reacted at a temperature of 150-200° C. for 1-10 hours. Preferably, the reaction is carried out at 150-170° C. for 1-8 hours. Of course, the specific reaction temperature and time of each substance reaction can be adjusted by those skilled in the art according to the knowledge in the art (for example, specific temperature and time are designed respectively according to the order of reaction), which will not be described in detail here.

[0025] Furthermore, in step (1), the reaction can be carried out in a solvent-free or organic solvent medium, and the organic solvent is at least one of xylene, mineral white oil, aromatic solvent S-100, and hydrogenated aromatic D40. Since the reaction byproduct of step (1) is water, and the above-mentioned solvent can form an azeotrope with water, a water separator and other devices can be used during the reaction process to remove the byproduct of the reaction to accelerate the reaction speed and make the condensation reaction more complete. If a reaction method with a solvent is adopted, the amount of the organic solvent is 100-200% of the total weight of the polyamine compound, dibasic acid, and diamine in step (1). If a solvent-free reaction method is adopted, the byproducts produced during the reaction can also be blown out via nitrogen to allow the reaction to proceed.

[0026] As a preferred solution, in step (2), a connecting compound and an end-capping polymer are added, so that the end-capping polymer is connected to the first polymer through the connecting compound. Preferably, the connecting compound is at least one of an anhydride and a dibasic acid, and the end-capping polymer is a polyether.

[0027] Furthermore, in step (2), the acid anhydride is a C2-C18 aliphatic or aromatic acid anhydride, and the acid anhydride is at least one of succinic anhydride, maleic anhydride, and phthalic anhydride.

[0028] Furthermore, the dibasic acid in step (2) has the same selectable range as the dibasic acid in step (1), that is, the dibasic acid in step (2) has the following general structural formula: COOH-R 2 -COOH, where R 2 is at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 type aromatic group or an aralkyl group. The above groups may be branched or unbranched. As a preferred embodiment, the dibasic acid in step (2) is a fatty acid, and the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, docosanediol, a dimer of an unsaturated C18 acid, dodecenyl thiocarboxylic acid and a dimerized fatty acid.

[0029] Furthermore, in step (2), the polyether has the following general structural formula: A-(EO) v -(PO) w -R 4 ; Where A is -OH, -SH, -NH 2 At least one of; v, w are 0-500 respectively; R 4 is at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 aromatic group or an aralkyl group, wherein R 4 It can be branched or unbranched. As a preferred solution, the polyether is at least one of a monofunctional hydroxyl-terminated polyether or a polyetheramine. Preferably, the polyetheramine is at least one of the polyetheramines Shandong Zhengda ZM-1207, Huntsman M-1207, Wuxi Akeli MEP-1100, and MEP-1207.

[0030] As another preferred solution, in step (2), a capping polymer is added so that the capping polymer is directly connected to the first polymer. Preferably, the capping polymer is polyethylene glycol methacrylate; the polyethylene glycol methacrylate is connected to the first polymer through a Michael addition reaction.

[0031] As a preferred embodiment, when the connecting compound is not added, the molar ratio of the polyamine compound, the dibasic acid, the diamine, and the end-capped polymer is 1: (3-30): (3-30): (1-10); when the connecting compound is added, the molar ratio of the polyamine compound, the dibasic acid, the diamine, the connecting compound, and the end-capped polymer is 1: (3-30): (3-30): (1-10): (1-10).

[0032] As a preferred solution, in step (2), the reaction is carried out at a temperature of 50-130° C. for 1-10 h. Of course, the specific reaction temperature and time of the reaction of each substance can be adjusted by those skilled in the art according to the knowledge in the field, and will not be described in detail here.

[0033] As a preferred solution, in the molecular structure of the amide polymer, the end-capped polymer chain segment accounts for 15-60 wt % of the amide polymer.

[0034] The second object of the present invention is to provide an amide polymer obtained by any of the above-mentioned methods for preparing the amide polymer.

[0035] The third object of the present invention is to provide a polyamide liquid rheology additive, comprising the polyamide polymer and a solvent.

[0036] Furthermore, the solvent is a mixed solvent of hydrogenated aromatic hydrocarbons and alcohol.

[0037] Furthermore, the hydrogenated aromatic hydrocarbon is at least one of D40 solvent oil, D60 solvent oil, and D80 solvent oil; the alcohol is at least one of methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, benzyl alcohol, and alcohol ether. The alcohol ether is at least one of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

[0038] Furthermore, in the mixed solvent, the mass ratio of the hydrogenated aromatic hydrocarbon to the alcohol is 1:0.1-5.

[0039] The fourth object of the present invention is to provide a method for preparing any of the polyamide liquid rheological additives described above, wherein the amide polymer is added to the solvent and stirred evenly to obtain the liquid rheological additive.

[0040] As a preferred solution, the amide polymer is added to the solvent at a temperature of 50-110° C. and a stirring speed of 100±5 rpm, and stirred until a uniform liquid is formed, thereby obtaining the polyamide liquid rheological additive.

[0041] The fifth object of the present invention is to provide an application of any of the above-mentioned polyamide liquid rheological additives in coatings or inks.

[0042] Specifically, the present invention provides a coating or ink, comprising any of the above-mentioned polyamide liquid rheological additives. Preferably, the mass content of the polyamide liquid rheological additive in the coating or ink is 0.01-3%.

[0043] The polyamide liquid rheological additive is used to prepare coatings or inks. The polyamide liquid rheological additive can be conveniently added to the coating or ink system to prevent the pigment or filler from settling and agglomerating during storage, avoid the coating from falling and sagging during coating, improve the leveling performance of the coating film, and have broad application prospects in industrial coatings. The coating or ink includes solvent-based, UV-curable (solvent-free) or water-based coatings or inks.

[0044] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0045] (1) The preparation steps of the amide polymer and polyamide liquid rheological additive of the present invention are simple and the raw materials are easily available;

[0046] (2) The present invention introduces certain other polymer compounds (capped polymers) such as polyether or polyester into the polyamide structure of the first polymer, and activates the polyamide part during the reaction or during the cooling process after the reaction. Therefore, such amide polymer is a free-flowing liquid and can be added in various links of the production of coatings and inks, and is particularly suitable as a rheological additive for coatings or ink systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 The following is a synthetic route diagram of a preferred embodiment of the amide polymer of the present invention. DETAILED DESCRIPTION

[0048] The present invention is further described below in conjunction with examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.

[0049] The present invention provides a method for preparing an amide polymer. As a preferred solution, the process synthesis route thereof can be found in Figure 1 , triethylenetetramine is used as a polyamine compound, and reacts with a dibasic acid and a diamine to obtain a first polymer (see the structural formula Figure 1 ), the present invention further adds a connecting compound (succinic anhydride) and a capped polymer (polyether amine) to react to obtain an amide polymer. Figure 1 In the process, each branch chain on the amide polymer is capped. In actual application, some branches can be capped and some branches can be uncapped. In addition, the selection of connecting compounds and capping polymers can also be adjusted according to actual conditions.

[0050] Example 1

[0051] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0052] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 119.4 g of C36-dimer acid were added and N 2 , heated to 150°C, reacted for 3 hours; added 24.7 g of 1,6-hexanediamine, heated to 170°C, reacted for 3 hours; cooled to 110°C, added 2.66 g of succinic anhydride, reacted for 1 hour; added 53.2 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0053] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0054] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 90 g of D40 solvent oil; cooling to 50° C., adding 160 g of tert-butanol, to obtain a dark yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0055] Example 2

[0056] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0057] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 119.4 g of C36-dimer acid were added and N 2 , heated to 150°C, reacted for 3 hours; added 24.7 g of 1,6-hexanediamine, heated to 170°C, reacted for 3 hours; cooled to 110°C, added 5.32 g of succinic anhydride, reacted for 1 hour; added 106.4 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0058] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0059] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 90 g of D40 solvent oil; cooling to 50° C., adding 160 g of tert-butanol, to obtain a dark yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0060] Example 3

[0061] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0062] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 119.4 g of C36-dimer acid were added and N 2 , heated to 150°C, reacted for 3 hours; added 24.7 g of 1,6-hexanediamine, heated to 170°C, reacted for 3 hours; cooled to 110°C, added 10.6 g of succinic anhydride, reacted for 1 hour; added 212.8 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0063] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0064] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 75 g of D40 solvent oil; cooling to 50° C., adding 150 g of tert-butyl alcohol, to obtain a yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0065] Example 4

[0066] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0067] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 59.7 g of C36-dimer acid were added and stirred at room temperature. 2 , heat to 150°C, react for 3 hours; add 12.35 g of ethylenediamine, heat to 170°C, react for 3 hours; cool to 110°C, add 2.66 g of succinic anhydride, react for 1 hour; add 53.2 g of polyetheramine ZM-1207 (Shandong Zhengda), heat to 130°C, react for 3 hours to obtain an amide polymer.

[0068] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0069] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 60 g of D40 solvent oil; cooling to 50° C., adding 120 g of tert-butyl alcohol, and obtaining a dark yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0070] Example 5

[0071] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0072] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 119.4 g of C36-dimer acid were added and N 2 , heated to 150°C, reacted for 3 hours; added 21.7 g of 1,5-pentanediamine, heated to 170°C, reacted for 3 hours; cooled to 110°C, added 2.66 g of succinic anhydride, reacted for 1 hour; added 53.2 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0073] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0074] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 90 g of D40 solvent oil; cooling to 50° C., adding 170 g of isobutyl alcohol, and obtaining a yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0075] Example 6

[0076] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0077] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of triethylenetetramine (TETA) and 100 g of C36-dimer acid were added and heated to 40 ℃ for 1 h. 2 , heated to 150°C, reacted for 3 hours; added 18.8 g of 1,4-butanediamine, heated to 170°C, reacted for 3 hours; cooled to 110°C, added 2.66 g of succinic anhydride, reacted for 1 hour; added 53.2 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0078] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0079] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 75 g of D40 solvent oil; cooling to 50° C., adding 160 g of isobutyl alcohol, and obtaining a yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0080] Example 7

[0081] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0082] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of tetraethylenepentamine (TEPA) and 115.5 g of C36-dimer acid were added.2 , heated to 150°C, reacted for 3 hours; added 23.9 g of 1,6-hexanediamine, heated to 180°C, reacted for 3 hours; cooled to 110°C, added 2.06 g of succinic anhydride, reacted for 1 hour; added 41.2 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0083] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0084] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 80 g of D40 solvent oil; cooling to 50° C., adding 165 g of tert-butanol, to obtain a light yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0085] Example 8

[0086] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0087] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of tetraethylenepentamine (TEPA) and 115.5 g of C36-dimer acid were added. 2 , heated to 150°C, reacted for 3 hours; added 23.9 g of 1,6-hexanediamine, heated to 180°C, reacted for 3 hours; cooled to 110°C, added 6.18 g of succinic anhydride, reacted for 1 hour; added 123.6 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0088] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0089] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 80 g of D40 solvent oil; cooling to 50° C., adding 165 g of tert-butanol, to obtain a light yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0090] Example 9

[0091] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0092] In a reaction flask equipped with a thermometer, condenser, water separator, and stirring device, 3.9 g of diethylenetriamine and 127.2 g of C36-dimer acid were added. 2, heated to 150°C, reacted for 3 hours; added 26.4 g of 1,6-hexanediamine, heated to 180°C, reacted for 3 hours; cooled to 110°C, added 3.78 g of succinic anhydride, reacted for 1 hour; added 75.6 g of polyetheramine ZM-1207 (Shandong Zhengda), heated to 130°C, reacted for 3 hours, and obtained an amide polymer.

[0093] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0094] The following experiments were continued in the reaction bottle of the amide polymer prepared above: cooling to 100° C., adding 90 g of D40 solvent oil; cooling to 50° C., adding 190 g of tert-butanol to obtain a yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0095] Example 10

[0096] This embodiment provides a method for preparing an amide polymer, comprising the following steps:

[0097] In a reaction flask equipped with a thermometer, condenser, water separator and stirring device, 3.9 g of tetraethylenepentamine (TEPA) and 115.5 g of C36-dimer acid were added. 2 , heat to 150°C, react for 3 hours; add 23.9g of 1,6-hexanediamine, heat to 170°C, react for 3 hours; cool to 110°C, add 60g of D40 solvent oil; cool to 50°C, add 60g of isobutanol, add 27.2g of A060M (Korea Green), react for 1 hour to obtain an amide polymer;.

[0098] This embodiment also provides a method for preparing a polyamide liquid rheological additive, comprising the following steps:

[0099] The following experiment was continued in the reaction bottle of the amide polymer prepared above: at 50°C, 100 g of isobutanol was added (in the process of preparing the amide polymer, D40 solvent oil and part of isobutanol were added in advance to facilitate the smooth reaction, so part of isobutanol can be added in this process) to obtain a light yellow transparent liquid, i.e., a polyamide liquid rheological additive.

[0100] Performance Testing

[0101] In order to test the thickening effect of the polyamide liquid rheological additives of Examples 1-10, the polyamide liquid rheological additives of Examples 1-12 were slowly stirred into the mixture of the resin and the solvent according to the coating formula in Table 1, and quickly stirred for 30-60 minutes to mix well. The thickening effect, transparency and compatibility were evaluated respectively.

[0102] Table 1 Coating formula

[0103] Components weight AP-5753(additional chemical) 73.5g Propylene glycol monomethyl ether acetate / butyl acetate (1:1) 24.5g Liquid rheology additives for polyamide 2g total 100g

[0104] Table 2 Test results

[0105] sample Thickening effect transparency Compatibility Example 1 5 4.5 Almost no particles Example 2 4 5 No particles Example 3 3 5 No particles Example 4 3 4 Slight particles Example 5 4 3 Slight particles Example 6 3 3 Slight particles Example 7 5 4.5 Almost no particles Example 8 3 5 No particles Example 9 3 4 Slight particles Example 10 4 4 Slight particles

[0106] Note: 5: best, 1: worst.

[0107] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, and the present invention is also intended to include these modifications and modifications.

Claims

1. A method for preparing an amide polymer, characterized in that: The following steps are involved: (1) adding a polyamine compound, a dibasic acid, and a diamine into a reaction container in sequence to carry out an amidation reaction to obtain a first polymer; (2) adding a connecting compound and a capping polymer or adding a capping polymer, so that the capping polymer is connected to the first polymer through the connecting compound or the capping polymer is directly connected to the first polymer; the connecting compound is at least one of anhydride, dibasic acid, acetoacetate, unsaturated double bond, alkylating agent, isocyanate; the capping polymer is at least one of polyester, polyether, polyacrylate, polymethyl methacrylate; Assuming that the polyamine compound has a amine groups, a≥3, when a connecting compound and a blocked polymer are added, the molar ratio of the polyamine compound, the dibasic acid, the diamine, the connecting compound and the blocked polymer is 1:(a-10a):(a-10a):(1-a):(1-a); when a blocked polymer is added, the molar ratio of the polyamine compound, the dibasic acid, the diamine and the blocked polymer is 1:(a-10a):(a-10a):(1-a).

2. The method for preparing an amide polymer according to claim 1, characterized in that: In step (1), the polyamine compound has the following general structural formula: NH2-(R1-NH)q-R1-NH2, the dibasic acid has the following general structural formula: COOH-R2-COOH, and the diamine has the following general structural formula: NH2-R3-NH2; Wherein, R1, R2, and R3 are independently at least one of a C1-C24 alkyl group, a C4-C10 cycloalkyl group, a C6-C18 aromatic group, or an aralkyl group; and q is 1-100.

3. The method for preparing an amide polymer according to claim 1, characterized in that: In step (1), the polyamine compound is an aliphatic polyamine compound, and the aliphatic polyamine compound is at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and a polyetheramine; the dibasic acid is an aliphatic dibasic acid, and the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, docosanediic acid, a dimer of unsaturated C18 acid, dodecenyl thiocyanate, and a dimerized fatty acid; the diamine is an aliphatic diamine, and the aliphatic diamine is at least one of ethylenediamine, butanediamine, hexamethylenediamine, decanediamine, dodecanediamine, octadecanediamine, and a divalent polyetheramine.

4. The method for preparing an amide polymer according to claim 1, characterized in that: In step (2), a connecting compound and an end-capping polymer are added; the connecting compound is at least one of an anhydride and a dibasic acid, the anhydride in step (2) is a C2-C18 aliphatic or aromatic anhydride, and the dibasic acid in step (2) has the following general structural formula: COOH-R2-COOH; the end-capping polymer is a polyether, and the polyether has the following general structural formula: A-(EO) v -(PO) w -R4; Among them, R2 and R4 are independently at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aromatic or aralkyl; A is at least one of -OH, -SH, -NH2; v and w are independently 0-500.

5. The method for preparing an amide polymer according to claim 4, characterized in that: The acid anhydride in step (2) is at least one of succinic anhydride, maleic anhydride, and phthalic anhydride; the dibasic acid in step (2) is an aliphatic dibasic acid, and the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, docosanedioc acid, a dimer of unsaturated C18 acid, dodecenyl thiocarboxylic acid, and a dimerized fatty acid; the polyether in step (2) is a polyetheramine.

6. The method for preparing an amide polymer according to claim 1, characterized in that: In step (2), a capping polymer is added; the capping polymer is polyethylene glycol methacrylate; the polyethylene glycol methacrylate is connected to the first polymer through a Michael addition reaction.

7. An amide polymer, characterized in that: The amide polymer is obtained by the preparation method of any one of claims 1 to 6.

8. A polyamide liquid rheological additive, characterized in that: Comprising the amide polymer as claimed in claim 7 and a solvent.

9. A method for preparing a polyamide liquid rheological additive, characterized in that: The following steps are involved: The amide polymer according to claim 7 is mixed with the solvent to obtain the polyamide liquid rheology additive.

10. Use of the polyamide liquid rheological additive according to claim 8 in coatings or inks.

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