CN119684597A - Amide polymer and preparation method thereof, polyamide liquid rheological additive and preparation method and application thereof - Google Patents
Amide polymer and preparation method thereof, polyamide liquid rheological additive and preparation method and application thereof Download PDFInfo
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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 of (1) adding polyamine compound, dibasic acid and diamine into a reaction container in sequence to carry out amidation reaction to obtain a first polymer, and (2) adding a connecting compound and a terminal polymer or adding the terminal polymer to enable the terminal polymer to be connected with the first polymer through the connecting compound or enable the terminal polymer to be directly connected with the first polymer. The invention is activated by introducing a polyether or polyester or other polymer to incorporate into the polyamide structure of the first polymer, while incorporating. The amide polymer is a free flowing liquid and can be added in various links of the production of the coating ink, and is particularly suitable as a rheological aid of a coating or ink system.
Description
Technical Field
The invention relates to the technical field of assistants, in particular to an amide polymer, a preparation method thereof, a polyamide liquid rheological assistant and application thereof.
Background
In the field of paints and inks, the viscosity of the paint and ink is critical to its commercial success. While the effective components (resins and pigments) of the coatings and inks determine the ultimate performance of their utility, the overall formulation is also critical to the commercial success of the coatings and inks, particularly the rheological properties of the coatings and inks, largely determining the manner in which the coatings and inks are stored and used.
There are many types of rheological aids on the market, the mainstream of which is fumed silica, organomodified bentonite, hydrogenated castor oil, polyethylene wax and the like. These rheological adjuvants, although widely used, generally have some drawbacks. For example, the thickening effect of the fumed silica on the thick coating is insufficient, the thickening effect of the organic modified bentonite is obvious, but the transparency is poor, the coating is not good in leveling, the hydrogenated castor oil needs to be fully activated before being used, the cooling is required to be slow and the temperature control is required to be accurate, otherwise, the hydrogenated castor oil is easy to separate out to cause failure, and the anti-sagging effect of the polyethylene wax is common when the hydrogenated castor oil is singly used.
Two other major classes of rheology aids are polyamide compounds and polyurea compounds. The polyurea rheological auxiliary agent is mainly applied to certain subdivision fields due to complex preparation process and higher cost. Among the solvent-based rheology aids, polyamide wax powder products dominate the market because of their low cost and good application. At present, a plurality of patents and documents related to polyamide rheological aids at home and abroad relate to various raw material combinations, preparation processes and applications thereof. The structure of the polyamide rheological auxiliary agent is mainly a chain structure formed by condensing dicarboxylic acid and diamine.
The use of monoacids plus diamines to form polyamide structures and as rheology aids was described earliest in patent US3937678a by Kusumoto, japan, 1974. The subsequent use of structures formed from monoacids plus diacids plus diamines as rheology aids in patent EP0210157A1, patent US5214224, patent US2012289437A1 has been done for many years. Kusumoto also modified this structure in 2011, patent US2012125235A1, to develop an aqueous rheology aid.
Petroleum in China corporation began to incorporate polyamines in patent CN103666414A and patent CN105368416A to form non-linear structures to increase molecular weight and increase the number of amide functionalities to improve product performance.
Although these polyamide-based rheology aids are widely used, their short plates are also apparent. Firstly, the use is inconvenient, the paint needs to be added into the whole barrel of paint and heated at 60 ℃ for 1-1.5 hours for activation, and users need to accumulate years of experience to grasp the use of the product. Secondly, the paint cannot be added in different stages of paint preparation, and the use is inflexible. To solve this problem, various companies have adopted different pre-dispersion methods to perform pre-activation, such as activation in resins, and products are generally mainly pasty and have low effective components.
Disclosure of Invention
Based on this, it is an object of the present invention to provide an amide polymer which can be used as an active ingredient of a polyamide liquid rheology aid for preparing a coating or ink to control the rheology of a coating or ink system, a process for preparing the same, a polyamide liquid rheology aid, a process for preparing the same and applications thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a first object of the present invention is to provide a process for producing an amide polymer, comprising the steps of:
(1) Sequentially adding a polyamine compound, a dibasic acid and diamine into a reaction container for amidation reaction to obtain a first polymer;
(2) Adding a connecting compound and a capping polymer or adding a capping polymer, and connecting the capping polymer to a first polymer through the connecting compound or directly connecting the capping polymer to the first polymer, wherein the connecting compound is at least one of acid anhydride, diacid, acetoacetate, unsaturated double bond, alkylating agent and isocyanate;
The polyamine compound has a mole ratio of 1 (a-10 a): (a-10 a): (1-a): (1-a) based on the polyamine compound having a number of a amine groups of a not less than 3, and when the linking compound and the end-capped polymer are added, the polyamine compound, the dibasic acid, the diamine, the linking compound, and the end-capped polymer have a mole ratio of 1 (a-10 a): (a-10 a): (1-a).
In the preparation method of the amide polymer, in the step (1), one carboxyl group in the dibasic acid reacts with one active hydrogen on an amine group (for example, -NH 2, -NH-) on the polyamine compound, so that a plurality of dibasic acids are connected on the polyamine compound, conditions are created for forming a plurality of branched chains, and the first polymer which has a polyamide bond and is highly branched (multi-branched) is obtained by adding the dibasic amine and connecting the other unreacted carboxyl group in the dibasic acid (or further connecting to form a dibasic acid-dibasic amine repeating unit). The amide bonds in the structure of the first polymer are distributed in a three-dimensional space structure, which is favorable for the formation of a space three-dimensional hydrogen bond structure, and the branched chains connected to the polyamine compound are easy to intertwine, so that a network structure with dense physical crosslinking points and stability is obtained, and the structure is favorable for improving the suspension characteristic of a coating system. However, the first polymer has a high melting point and poor compatibility, and is generally used only as a matrix resin for paints and inks or as a binder in the chemical field, and the first polymer has strong intermolecular forces, is easily crystallized and is hardly soluble in a general aromatic hydrocarbon solvent, so that the first polymer is not easy to operate in a subsequent swelling activation step.
In the method for producing an amide polymer of the present invention, in the step (2), the terminal polymer is incorporated into the structure of the first polymer by adding a linking compound and the terminal polymer or adding the terminal polymer, and the terminal polymer is linked to the first polymer through the linking compound or the terminal polymer is directly linked to the first polymer. The end-capped polymer is at least one of polyester, polyether, polyacrylate and polymethyl methacrylate, namely, the invention is characterized in that at least one of polyester, polyether, polyacrylate and polymethyl methacrylate is grafted into the first polymer through the step (2), and at least one of polyester, polyether, polyacrylate and polymethyl methacrylate simultaneously activates a polyamide part in the first polymer during and after the grafting reaction, so that the obtained amide polymer is free flowing liquid, has obvious difference with the traditional pasty amide polymer, is suitable for being used for a coating or ink system after being prepared into a liquid rheological aid, and can be added in various links of coating or ink production.
In step (2), the introduction of the end-capped polymer onto the first polymer may be carried out by direct reaction (e.g., by imine formation, michael addition), or by indirect reaction of the linking compound (e.g., by alkylation, amide formation by anhydride, or urea formation by isocyanate, etc.).
In the preparation method of the amide polymer, a is more than or equal to 3 based on the condition that a amine groups are arranged on the polyamine compound, when a connecting compound and a capping polymer are added, the mole ratio of the polyamine compound, the diacid, the diamine, the connecting compound and the capping polymer is 1 (a-10 a): (a-10 a): (1-a): (1-a), and when the capping polymer is added, the mole ratio of the polyamine compound, the diacid, the diamine and the capping polymer is 1 (a-10 a): (a-10 a). The molar ratio of the above substances is defined to facilitate the formation of a plurality of branches with a polyamine compound as a core, a dibasic acid and a diamine (or a repeating unit thereof) in the step (1), and the end capping of part or all of the branches (preferably, the end capping of part of the branches) and the activation of the amide structure thereof in the step (2) by the introduction of a capping polymer.
Further, in the step (1), the polyamine compound has a structural formula of NH 2-(R1-NH)q-R1-NH2, the dibasic acid has a structural formula of COOH-R 2 -COOH, wherein R 1 is at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aryl or aralkyl, and q is 1-100. The R 1 groups described above may be branched or unbranched.
In a preferred embodiment, in the 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 polyvalent polyether amine.
Further, in the step (1), the dibasic acid has the following structural general formula of COOH-R 2 -COOH, wherein R 2 is at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aryl or aralkyl. The above groups may be branched or unbranched.
Preferably, in the 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, behenic acid, a dimer of an unsaturated C18 acid, dodecenyl succinic acid, and a dimer fatty acid (e.g., C36-dimer acid).
Further, in the step (1), the diamine has the following structural general formula of NH 2-R3-NH3, wherein R 3 is at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aryl or aralkyl, and polyether. The above groups may be branched or unbranched.
In a preferred embodiment, in the step (1), the diamine is aliphatic diamine, and the aliphatic diamine is at least one of ethylenediamine, butanediamine, pentanediamine, hexanediamine, decanediamine, dodecanediamine, octadecanediamine, and diamine polyether amine.
In the step (1), the three raw materials (polyamine compound, diacid and diamine) are added in sequence and reacted for 1-10h at the temperature of 150-200 ℃. Preferably at 150-170 ℃ for 1-8 hours. Of course, the specific reaction temperature and time of each material reaction can be adjusted according to the knowledge in the art (for example, specific temperature and time are respectively designed according to the sequence of the reactions) by those skilled in the art, and will not be described herein.
Further, in the step (1), the reaction may be performed in a solvent-free or in an organic solvent medium, and the organic solvent is at least one of xylene, mineral white oil, aromatic solvent S-100, and hydrogenated aromatic hydrocarbon D40. Because the reaction byproduct in the step (1) is water, the solvent can form an azeotrope with the water, and devices such as a water separator and the like can be used in the reaction process to remove the reaction byproduct so as to accelerate the reaction speed and enable the condensation reaction to be more complete. If a reaction mode with a solvent is adopted, the dosage of the organic solvent is 100-200% of the total weight of the polyamine compound, the dibasic acid and the diamine in the step (1). If a solvent-free reaction mode is adopted, byproducts generated during the reaction can be blown out by nitrogen so as to lead the reaction to proceed forwards.
In a preferred embodiment, in step (2), a linking compound and a capping polymer are added, and the capping polymer is linked to the first polymer via the linking compound. Preferably, the connecting compound is at least one of anhydride and dibasic acid, and the end-capped polymer is polyether.
Further, in the step (2), the acid anhydride is an aliphatic or aromatic acid anhydride of C2-C18, and the acid anhydride is at least one of succinic anhydride, maleic anhydride and phthalic anhydride.
Further, the diacid in step (2) has the same optional range as the diacid in step (1), i.e., the diacid in step (2) has the following general structural formula of COOH-R 2 -COOH, wherein R 2 is at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aryl or aralkyl. The above groups may be branched or unbranched. Preferably, the dibasic acid in the step (2) is a fatty acid, and the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, behenic acid, dimer of unsaturated C18 acid, dodecenyl succinic acid and dimer fatty acid.
Further, in the step (2), the polyether has the following structural general formula of A- (EO) v-(PO)w-R4, wherein A is at least one of-OH, -SH and-NH 2, v and w are respectively 0-500, R 4 is at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aryl or aralkyl, and R 4 can be branched or unbranched. Preferably, the polyether is at least one of a monofunctional hydroxyl-terminated polyether or a polyetheramine. Preferably, the polyetheramine is at least one of polyetheramine Shandong Zhengda ZM-1207, hensmei M-1207, wuxi Aldrich MEP-1100 and MEP-1207.
As another preferred embodiment, in step (2) a capping polymer is added, which is directly attached to the first polymer. Preferably, the end-capped polymer is polyethylene glycol methacrylate, which is attached to the first polymer by a Michael addition reaction.
As a preferable mode, when the connecting compound is not added, the mole ratio of the polyamine compound, the dibasic acid, the diamine and the end-capped polymer is 1 (3-30): 1-10, and when the connecting compound is added, the mole ratio of the polyamine compound, the dibasic acid, the diamine, the connecting compound and the end-capped polymer is 1 (3-30): 1-10.
As a preferred scheme, in the step (2), the reaction is carried out for 1 to 10 hours under the temperature condition of 50 to 130 ℃. Of course, the specific reaction temperature and time of each material reaction can be adjusted by those skilled in the art according to the knowledge in the art, and will not be described herein.
As a preferred embodiment, the molecular structure of the amide polymer comprises 15-60wt% of the amide polymer, the polymer segments being terminated.
It is a second object of the present invention to provide an amide polymer obtained by the process for producing an amide polymer as described in any one of the above.
It is a third object of the present invention to provide a polyamide liquid rheology aid comprising the amide polymer and a solvent.
Further, the solvent is a mixed solvent of hydrogenated aromatic hydrocarbon and alcohol.
Further, the hydrogenated aromatic hydrocarbon is at least one of D40 solvent oil, D60 solvent oil and D80 solvent oil, and the alcohol is at least one of methanol, ethanol, isopropanol, n-butanol, isobutanol, tertiary 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.
Further, in the mixed solvent, the mass ratio of the hydrogenated aromatic hydrocarbon to the alcohol is 1:0.1-5.
The fourth object of the present invention is to provide a method for preparing the polyamide liquid rheological additive, wherein the polyamide polymer is added into the solvent and stirred uniformly to obtain the liquid rheological additive.
As a preferable scheme, the amide polymer is added into the solvent under the conditions that the temperature is 50-110 ℃ and the stirring speed is 100+/-5 revolutions per minute, and the polyamide liquid rheological auxiliary agent is obtained after stirring until uniform liquid is formed.
A fifth object of the present invention is to provide the use of a polyamide liquid rheology additive as described in any of the above in a coating or ink.
In particular, the present invention provides a coating or ink comprising a polyamide liquid rheology additive as described in any of the preceding. Preferably, the polyamide liquid rheology auxiliary agent is present in the coating or ink in an amount of 0.01-3% by mass.
The polyamide liquid rheological additive is used for preparing paint or ink, can be conveniently added into a paint or ink system, prevents pigment or filler from settling and caking in the storage process of the paint or ink, avoids paint from falling and sagging in the coating process, improves the leveling property of a coating film, and has wide application prospect in industrial paint. The coating or ink comprises a solvent-based, UV-curable (solvent-free) or aqueous coating or ink.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation steps of the amide polymer and the polyamide liquid rheological additive are simple, and the raw materials are easy to obtain;
(2) The invention introduces a certain polyether or polyester and other high molecular compounds (end-capped polymers) into the polyamide structure of the first polymer, and activates the polyamide part simultaneously during the process of the connection reaction or the cooling process after the reaction. Such amide polymers are therefore free-flowing liquids, which can be added at various stages of the production of the coating inks, and are particularly suitable as rheology auxiliaries for coating or ink systems.
Drawings
FIG. 1 is a synthetic route diagram of a preferred embodiment of the amide polymer of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental methods in the examples below, in which specific conditions are not specified, are generally conducted under the conditions conventional in the art or according to the conditions recommended by the manufacturer, and the raw materials, reagents, etc. used, unless otherwise specified, are commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The invention provides a preparation method of an amide polymer, which is used as a preferable scheme, wherein the technological synthetic route is shown in figure 1, triethylene tetramine is used as a polyamine compound, a first polymer (structural formula is shown in figure 1) is obtained after the triethylene tetramine reacts with dibasic acid and diamine, and a connecting compound (succinic anhydride) and a terminated polymer (polyether amine) are added for reaction to obtain the amide polymer. In FIG. 1, each branched chain on the amide polymer is blocked, and in the practical application process, a part of branched chain is blocked and a part of branched chain is not blocked, and in addition, the selection of the connecting compound and the blocked polymer can be adjusted according to practical situations.
Example 1
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 119.4g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, the mixture is heated to 150 ℃ through N 2 for 3 hours, 24.7g of 1, 6-hexamethylenediamine is added, the mixture is heated to 170 ℃ for 3 hours, the mixture is cooled to 110 ℃ and 2.66g of succinic anhydride is added for 1 hour, 53.2g of polyetheramine ZM-1207 (big in Shandong) is added, the mixture is heated to 130 ℃ for 3 hours, and the amide polymer is obtained.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 90g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 160g of tertiary butanol is added, and dark yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 2
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 119.4g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, the mixture is heated to 150 ℃ through N 2 to react for 3 hours, 24.7g of 1, 6-hexamethylenediamine is added to react for 3 hours at 170 ℃, the mixture is cooled to 110 ℃, 5.32g of succinic anhydride is added to react for 1 hour, 106.4g of polyetheramine ZM-1207 (big in Shandong) is added to react for 3 hours, and the amide polymer is obtained.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 90g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 160g of tertiary butanol is added, and dark yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 3
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 119.4g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, the mixture is heated to 150 ℃ through N 2 for 3 hours, 24.7g of 1, 6-hexamethylenediamine is added, the mixture is heated to 170 ℃ for 3 hours, the mixture is cooled to 110 ℃, 10.6g of succinic anhydride is added for 1 hour, 212.8g of polyetheramine ZM-1207 (big in Shandong) is added, the mixture is heated to 130 ℃ for 3 hours, and the amide polymer is obtained.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 75g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 150g of tertiary butanol is added, and yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 4
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 59.7g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser pipe, a water separator and a stirring device, the mixture is heated to 150 ℃ through N 2 for 3 hours, 12.35g of ethylenediamine is added, the mixture is heated to 170 ℃ for 3 hours, the mixture is cooled to 110 ℃ and 2.66g of succinic anhydride is added for 1 hour, 53.2g of polyetheramine ZM-1207 (Shandong's major) is added, and the mixture is heated to 130 ℃ for 3 hours to obtain the amide polymer.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 60g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 120g of tertiary butanol is added, and dark yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 5
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 119.4g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, the mixture is heated to 150 ℃ through N 2 for 3 hours, 21.7g of 1, 5-pentanediamine is added, the mixture is heated to 170 ℃ for 3 hours, the mixture is cooled to 110 ℃ and 2.66g of succinic anhydride is added for 1 hour, 53.2g of polyetheramine ZM-1207 (big in Shandong) is added, the mixture is heated to 130 ℃ for 3 hours, and the amide polymer is obtained.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 90g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 170g of isobutanol is added, and yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 6
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
3.9g of triethylene tetramine (TETA) and 100g of C36-dimer acid are added into a reaction bottle provided with a thermometer, a condenser pipe, a water separator and a stirring device, N 2 is introduced, the mixture is heated to 150 ℃ for 3 hours, 18.8g of 1, 4-butanediamine is added, the mixture is heated to 170 ℃ for 3 hours, the mixture is cooled to 110 ℃, 2.66g of succinic anhydride is added for 1 hour, 53.2g of polyetheramine ZM-1207 (big in Shandong) is added, the mixture is heated to 130 ℃ for 3 hours, and the amide polymer is obtained.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 75g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 160g of isobutanol is added, and yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 7
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
Adding 3.9g of Tetraethylenepentamine (TEPA) and 115.5g of C36-dimer acid into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, introducing N 2, heating to 150 ℃ for reaction for 3 hours, adding 23.9g of 1, 6-hexamethylenediamine, heating to 180 ℃ for reaction for 3 hours, cooling to 110 ℃, adding 2.06g of succinic anhydride for reaction for 1 hour, adding 41.2g of polyetheramine ZM-1207 (the big part of Shandong), heating to 130 ℃, and reacting for 3 hours to obtain an amide polymer.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 80g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 165g of tertiary butanol is added, and light yellow transparent liquid, namely the polyamide liquid rheological additive, is obtained.
Example 8
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
Adding 3.9g of Tetraethylenepentamine (TEPA) and 115.5g of C36-dimer acid into a reaction bottle provided with a thermometer, a condenser tube, a water separator and a stirring device, introducing N 2, heating to 150 ℃ for reaction for 3 hours, adding 23.9g of 1, 6-hexamethylenediamine, heating to 180 ℃ for reaction for 3 hours, cooling to 110 ℃, adding 6.18g of succinic anhydride for reaction for 1 hour, adding 123.6g of polyetheramine ZM-1207 (the big part of Shandong), heating to 130 ℃, and reacting for 3 hours to obtain an amide polymer.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 80g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 165g of tertiary butanol is added, and light yellow transparent liquid, namely the polyamide liquid rheological additive, is obtained.
Example 9
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
Adding 3.9g of diethylenetriamine and 127.2g of C36-dimer acid into a reaction bottle provided with a thermometer, a condenser pipe, a water separator and a stirring device, introducing N 2, heating to 150 ℃ for 3 hours, adding 26.4g of 1, 6-hexamethylenediamine, heating to 180 ℃ for 3 hours, cooling to 110 ℃, adding 3.78g of succinic anhydride, reacting for 1 hour, adding 75.6g of polyetheramine ZM-1207 (Shandong's big), heating to 130 ℃ and reacting for 3 hours to obtain an amide polymer.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that the temperature is reduced to 100 ℃, 90g of D40 solvent oil is added, the temperature is reduced to 50 ℃, 190g of tertiary butanol is added, and yellow transparent liquid, namely the polyamide liquid rheological aid is obtained.
Example 10
The present embodiment provides a method for producing an amide polymer, comprising the steps of:
Adding Tetraethylenepentamine (TEPA) 3.9g and C36-dimer acid 115.5g into a reaction bottle equipped with a thermometer, a condenser, a water separator and a stirring device, introducing N 2, heating to 150 ℃ for reaction for 3 hours, adding 1, 6-hexamethylenediamine 23.9g, heating to 170 ℃ for reaction for 3 hours, cooling to 110 ℃, adding D40 solvent oil 60g, cooling to 50 ℃, adding isobutanol 60g, adding A060M (Korean Green) 27.2g, and reacting for 1 hour to obtain an amide polymer.
The embodiment also provides a preparation method of the polyamide liquid rheological additive, which comprises the following steps:
The reaction bottle of the prepared amide polymer is continuously subjected to the following experiment that 100g of isobutanol is added at 50 ℃ (because D40 solvent oil and part of isobutanol are added in advance in order to facilitate the smooth reaction in the process of preparing the amide polymer, and part of isobutanol is added in the process), so as to obtain pale yellow transparent liquid, namely the polyamide liquid rheological aid.
Performance testing
To facilitate testing the thickening effect of the polyamide liquid rheology aids of examples 1-10, the polyamide liquid rheology aids of examples 1-12 were each added to the resin and solvent mixture according to the coating formulation of table 1 with slow stirring and rapid stirring for 30-60 minutes to mix thoroughly. The thickening effect, transparency, and compatibility were evaluated, respectively.
Table 1 paint formulation
| Component (A) | Weight of (E) |
| AP-5753 (dotting chemical industry) | 73.5g |
| Propylene glycol monomethyl ether acetate/butyl acetate (1:1) | 24.5g |
| Polyamide liquid rheology aid | 2g |
| Totals to | 100g |
Table 2 test results
| Sample of | Thickening effect | Transparency of the film | Compatibility of |
| Example 1 | 5 | 4.5 | Substantially free of 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 | Substantially free of particles |
| Example 8 | 3 | 5 | No particles |
| Example 9 | 3 | 4 | Slight particles |
| Example 10 | 4 | 4 | Slight particles |
Note that 5 is best, 1 is worst.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.
Claims (10)
1. A preparation method of an amide polymer is characterized by comprising the following steps:
(1) Sequentially adding a polyamine compound, a dibasic acid and diamine into a reaction container for amidation reaction to obtain a first polymer;
(2) Adding a connecting compound and a capping polymer or adding a capping polymer, and connecting the capping polymer to a first polymer through the connecting compound or directly connecting the capping polymer to the first polymer, wherein the connecting compound is at least one of acid anhydride, diacid, acetoacetate, unsaturated double bond, alkylating agent and isocyanate;
The polyamine compound has a mole ratio of 1 (a-10 a): (a-10 a): (1-a): (1-a) based on the polyamine compound having a number of a amine groups of a not less than 3, and when the linking compound and the end-capped polymer are added, the polyamine compound, the dibasic acid, the diamine, the linking compound, and the end-capped polymer have a mole ratio of 1 (a-10 a): (a-10 a): (1-a).
2. The method for producing an amide polymer according to claim 1, wherein in the step (1), the polyamine compound has the following structural formula NH 2-(R1-NH)q-R1-NH2, the dibasic acid has the structural formula COOH-R 2 -COOH, the diamine has the structural formula NH 2-R3-NH2, wherein R 1、R2、R3 is independently at least one of C1-C24 alkyl, C4-C10 cycloalkyl, C6-C18 aromatic or aralkyl, and q is 1-100.
3. The method for producing an amide polymer according to claim 1, wherein in the step (1), the polyamine compound is an aliphatic polyamine compound, the aliphatic polyamine compound is at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and a polyether amine, the dibasic acid is an aliphatic dibasic acid, the aliphatic dibasic acid is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, behenic acid, a dimer of an unsaturated C18 acid, dodecenyl-fp-one, and a dimer fatty acid, the dibasic amine is an aliphatic diamine, and the aliphatic diamine is at least one of ethylenediamine, butanediamine, hexamethylenediamine, decanediamine, dodecanediamine, octadecanediamine, and polyether amine.
4. The method of producing an amide polymer according to claim 1, wherein in the step (2), a linking compound and a capping polymer are added, wherein the linking compound is at least one of an acid anhydride and a dibasic acid, the acid anhydride in the step (2) is an aliphatic or aromatic acid anhydride of C2-C18, the dibasic acid in the step (2) has a structural formula of COOH-R 2 -COOH, the capping polymer is a polyether having a structural formula of A- (EO) v-(PO)w-R4, wherein R 2、R4 is at least one of an alkyl group of C1-C24, a cycloalkyl group of C4-C10, an aryl group of C6-C18 type or an aralkyl group, A is at least one of-OH, -SH, -NH 2, and v and w are each independently 0 to 500.
5. The method for producing an amide polymer according to claim 4, wherein the acid anhydride in the step (2) is at least one of succinic anhydride, maleic anhydride and phthalic anhydride, the dibasic acid in the step (2) is an aliphatic dibasic acid which is at least one of sebacic acid, dodecanedioic acid, hexadecanedioic acid, behenic acid, dimer of unsaturated C18 acid, dodecenyl-succinic acid and dimer fatty acid, and the polyether in the step (2) is polyetheramine.
6. The method of preparing an amide polymer according to claim 1, wherein in step (2), a capping polymer is added, wherein the capping polymer is polyethylene glycol methacrylate, and wherein the polyethylene glycol methacrylate is attached to the first polymer by Michael addition reaction.
7. An amide polymer obtained by the process for producing an amide polymer according to any one of claims 1 to 6.
8. A polyamide liquid rheology assistant, comprising an amide polymer as claimed in claim 7 and a solvent.
9. A process for preparing a polyamide liquid rheology additive comprising the step of mixing the amide polymer of claim 7 with the solvent to obtain the polyamide liquid rheology additive.
10. Use of the polyamide liquid rheology additive of claim 8 in a coating or ink.
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