Preparation method of straight-chain dimer acid, polyamide resin and preparation method of polyamide resin

Abstract

The invention discloses a preparation method of straight-chain dimer acid, polyamide resin and a preparation method thereof, and the polyamide resin is composed of the following components: 1000 parts by weight of straight-chain dimer acid, 100 parts by weight of glacial acetic acid, 0.4 part by weight of an auxiliary agent and 169.2 parts by weight of ethidene diamine. According to the preparation method, the straight-chain dimer acid, the monocyclic dimer acid and the bicyclic dimer acid in the mixed dimer acid are separated by gel permeation chromatography to obtain the straight-chain dimer acid, and the polyamide resin synthesized by the straight-chain dimer acid is used as an ink binder, so that the glossiness of the ink can be improved while the cost is not greatly increased.

Description

Technical Field

[0001] The present invention relates to the technical field of polymers, and particularly relates to a method for preparing linear dimer acid, a polyamide resin and a method for preparing the same. Background Art

[0002] Dimer acid gets its name because its molecule contains two carboxylic acid groups, and it is a dimer compound mainly composed of C36 formed by the reaction of C18 unsaturated fatty acids under certain conditions. Currently, commercially available dimer acids on the market are mainly mixtures composed of three types of structures: linear, monocyclic and bicyclic. Among them, the molecular structural formula of linear dimer acid is as shown in formula (1), the molecular structural formula of monocyclic dimer acid is as shown in formula (2), and the molecular structural formula of bicyclic dimer acid is as shown in formula (3).

[0003]

[0004] Synthesizing polyamide resin is the largest use of dimer acid, accounting for more than 75% of the consumption of dimer acid. Polyamide resins synthesized from dimer acids with the same content but different structures have significant differences in physical properties such as viscosity, softening point, and freezing point, and the corresponding application ranges and application effects also vary greatly. Ink mainly consists of pigments, binders, auxiliary materials fillers and solvents. Among them, the polyamide resin as the binder accounts for 20 - 35%. The binder is the heart of the ink, which can make the coloring agent pigment be ground and dispersed evenly on the dispersing equipment, make the pigment adhere firmly to the printing substrate, and endow the ink with necessary gloss, drying performance and printing suitability, etc. The main properties of the ink, such as glossiness and printing adaptability, etc. all depend on the binder, so it is the key to the quality of the ink.

[0005] Currently, the dimer acids used to synthesize polyamide resin for ink are all mixtures, and their glossiness is always not ideal. Ink users need to add gloss enhancers additionally during the use process, which not only increases the cost, but also brings other side effects. The market urgently needs polyamide resin for high - brightness ink. Summary of the Invention

[0006] Therefore, the technical problem to be solved by the present invention is to provide a method for preparing linear dimer acid, a polyamide resin and a method for preparing the same, which uses gel permeation chromatography to separate the linear, monocyclic and bicyclic types in the mixed dimer acid to obtain linear dimer acid, and uses the polyamide resin synthesized from the linear dimer acid as the ink binder, which can improve the ink glossiness without significantly increasing the cost.

[0007] To solve the above - mentioned technical problem, the present invention provides the following technical solutions:

[0008] A method for preparing linear dimer acid, comprising the following steps:

[0009] (S1) Prepare dimer acid;

[0010] (S2) Separate the dimer acid obtained in step (S1) to obtain linear dimer acid. The specific operation is as follows:

[0011] Heat the dimer acid to 78 - 82 °C, then pump it into a φ200×950 mm gel chromatography column. Next, pump the eluent heated to 80 °C into the gel chromatography column at a linear velocity of 2 - 4 cm / min. Connect the outlet of the gel chromatography column to a receiving container, and sequentially collect the eluent from the 0th to 6th minute, the eluent from the 7th to 21st minute, and the eluent from the 22nd to 30th minute. Recover the eluent collected from the 22nd to 30th minute, and linear dimer acid can be obtained.

[0012] In the above method for preparing linear dimer acid, the eluent is N,N-dimethylformamide or / and dimethyl sulfoxide.

[0013] In the above method for preparing linear dimer acid, when the eluent is a mixed solution composed of N,N-dimethylformamide and dimethyl sulfoxide, the dosage ratio of N,N-dimethylformamide to dimethyl sulfoxide is (0 - 2):(0 - 2).

[0014] In the above method for preparing linear dimer acid, the dosage ratio of N,N-dimethylformamide to dimethyl sulfoxide is 1:2 - 2:1.

[0015] In the above method for preparing linear dimer acid, the dosage ratio of N,N-dimethylformamide to dimethyl sulfoxide is 1:1 - 2:1.

[0016] A polyamide resin is composed of the following components: 1000 parts by weight of linear dimer acid, 100 parts by weight of organic acid, 0.4 parts by weight of phosphate-based auxiliary, and 169.2 parts by weight of diamine monomer. Among them, the linear dimer acid is the linear dimer acid prepared according to the above method for preparing linear dimer acid.

[0017] In the above polyamide resin, the organic acid is one or more of glacial acetic acid, propionic acid, n-butyric acid, and isobutyric acid.

[0018] In the above polyamide resin, the diamine monomer is one or more of ethylenediamine, hexamethylenediamine, and propanediamine.

[0019] A method for preparing a polyamide resin includes the following steps:

[0020] (I) Prepare linear dimer acid according to the above method for preparing linear dimer acid;

[0021] (II) Prepare materials according to the following formula: 1000 parts by weight of linear dimer acid, 100 parts by weight of organic acid, 0.4 parts by weight of phosphate-based auxiliary agent, and 169.2 parts by weight of diamine monomer. The linear dimer acid is the linear dimer acid obtained in step (I);

[0022] (III) Mix the linear dimer acid, organic acid, and phosphate-based auxiliary agent, heat to 80 °C, then dropwise add the diamine monomer over 30 minutes. Then heat to 120 °C and hold for 1 hour, then raise the temperature to 220 °C and hold for 2 hours. Then continue to raise the temperature to 230 °C, hold and evacuate for 1 hour, and cool to room temperature to obtain the polyamide resin.

[0023] The technical solution of the present invention has achieved the following beneficial technical effects:

[0024] Separate the mixed dimer acid by gel permeation chromatography to obtain linear dimer acid, and use the linear dimer acid to prepare the corresponding polyamide resin. The ink with the polyamide resin synthesized from linear dimer acid as the binder has the best glossiness and can meet the user's glossiness requirements. Specific embodiments

[0025] Examples

[0026] The polyamide resin in the present invention is composed of the following components: 1000 parts by weight of linear dimer acid, 100 parts by weight of glacial acetic acid, 0.4 parts by weight of auxiliary agent, and 169.2 parts by weight of ethylenediamine, and is prepared through the following steps:

[0027] (I) Prepare linear dimer acid, and the specific steps are as follows:

[0028] (S1) Prepare dimer acid;

[0029] (S2) Separate the dimer acid obtained in step (S1) to obtain linear dimer acid. The specific operation is as follows:

[0030] Heat the dimer acid to 80 °C, then pump it into a φ200×950 mm gel chromatography column. Then pump the eluent heated to 80 °C into the gel chromatography column at a linear velocity of 3 cm / min. Connect the outlet of the gel chromatography column to a receiving container, and sequentially collect the eluent from the 0th to 6th minutes, the eluent from the 7th to 21st minutes, and the eluent from the 22nd to 30th minutes. Recover the eluent from the eluent collected from the 22nd to 30th minutes to obtain linear dimer acid;

[0031] (II) Prepare materials according to the following formula: 1000 parts by weight of linear dimer acid, 100 parts by weight of glacial acetic acid, 0.4 parts by weight of auxiliary agent, and 169.2 parts by weight of ethylenediamine. The linear dimer acid is the linear dimer acid obtained in step (I);

[0032] (III) Mix the linear dimer acid, glacial acetic acid and auxiliary agent, heat the mixture to 80 °C, then dropwise add ethylenediamine over 30 min. Next, heat the mixture to 120 °C and keep it warm for 1 hour, then raise the temperature to 220 °C and keep it warm for 2 h. Then, continue to raise the temperature to 230 °C, keep it warm and evacuate the air for 1 hour. After cooling to room temperature, the polyamide resin can be obtained.

[0033] In this example, the eluent used is N,N-dimethylformamide.

[0034] Example 2

[0035] The difference between this example and Example 1 is that the eluent used in the preparation of the linear dimer acid is dimethyl sulfoxide.

[0036] Example 3

[0037] The difference between this example and Example 1 is that the eluent used in the preparation of the linear dimer acid is a mixed solution composed of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 1:1.

[0038] Example 4

[0039] The difference between this example and Example 1 is that the eluent used in the preparation of the linear dimer acid is a mixed solution composed of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 1:2.

[0040] Example 5

[0041] The difference between this example and Example 1 is that the eluent used in the preparation of the linear dimer acid is a mixed solution composed of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 2:1.

[0042] Comparative Example 1

[0043] The difference between this example and Example 1 is that the dimer acid used in the preparation of the polyamide resin is a monocyclic dimer acid.

[0044] Comparative Example 2

[0045] The difference between this example and Example 1 is that the dimer acid used in the preparation of the polyamide resin is a bicyclic dimer acid.

[0046] Comparative Example 3

[0047] The difference between this example and Example 1 is that the dimer acid used in the preparation of the polyamide resin is the dimer acid obtained in step (S1).

[0048] In the present invention, the yields of the linear dimer acid in Examples 1 to 5 are shown in Table 1.

[0049] Table 1 Yields of the linear dimer acid in Examples 1 to 5

[0050] Eluent (DMF: DMSO) 1:0 0:1 1:1 1:2 2:1 Yield of linear dimer acid (%) 80 74 89 85 95

[0051] The polyamide resins prepared in Example 1 and Comparative Examples 1 to 3 were used as the binder of the ink to prepare the ink, and then the adhesion of the ink was tested, and the gloss was tested according to the gloss test method of liquid ink in the GB / T 13217 standard. The test results are shown in Table 2.

[0052] Table 2 Adhesion and gloss of the ink

[0053] Sample name Adhesion Glossiness Sample 1 Excellent 90～96 Sample 2 Excellent 75～85 Sample 3 Good 65～75 Sample 4 Excellent 70～80

[0054] Among them, Sample 1 is the ink using the polyamide resin in Example 1 as the binder, Sample 2 is the ink using the polyamide resin in Comparative Example 1 as the binder, Sample 3 is the ink using the polyamide resin in Comparative Example 2 as the binder, and Sample 4 is the ink using the polyamide resin in Comparative Example 3 as the binder. It can be seen from the data recorded in Table 2 that the gloss of the ink using the polyamide resin prepared in Example 1 as the binder has been significantly improved compared with the ink using the polyamide resin in Comparative Example 3 as the binder.

[0055] Obviously, the above examples are only for clear illustration and not for limitation of the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the claims of this patent application.

Claims

1. A method for preparing a linear dimer acid, characterized in that: The following steps are involved: (S1) preparing dimer acid; (S2) separating the dimer acid obtained in step (S1) to obtain a linear dimer acid, the specific operation is as follows: The dimer acid is heated to 78-82°C and then pumped into a φ200×950mm gel chromatography column. Subsequently, an eluent heated to 80°C is injected into the gel chromatography column at a linear velocity of 2-4 cm / min. The outlet of the gel chromatography column is connected to a receiving container, and the eluent from 0 to 6 minutes, the eluent from 7 to 21 minutes, and the eluent from 22 to 30 minutes are collected in sequence. The eluent collected from 22 to 30 minutes is subjected to eluent recovery to obtain a straight-chain dimer acid.

2. The method for preparing a linear dimer acid according to claim 1, characterized in that: The eluent is N,N-dimethylformamide or / and dimethyl sulfoxide.

3. The method for preparing a linear dimer acid according to claim 2, characterized in that: When the eluent is a mixed solution composed of N,N-dimethylamide and dimethyl sulfoxide, the ratio of N,N-dimethylamide to dimethyl sulfoxide is (0-2):(0-2).

4. The method for preparing a linear dimer acid according to claim 3, characterized in that: The ratio of N,N-dimethylamide to dimethyl sulfoxide is 1:2 to 2:

1.

5. The method for preparing a linear dimer acid according to claim 3, characterized in that: The ratio of N,N-dimethylamide to dimethyl sulfoxide is 1:1 to 2:

1.

6. A polyamide resin, characterized in that The invention is composed of the following components: 1000 parts by weight of a linear dimer acid, 100 parts by weight of an organic acid, 0.4 parts by weight of a phosphate additive and 169.2 parts by weight of a diamine monomer, wherein the linear dimer acid is the linear dimer acid prepared in claim 1.

7. The polyamide resin according to claim 6, characterized in that The organic acid is one or more of glacial acetic acid, propionic acid, n-butyric acid and isobutyric acid.

8. The polyamide resin according to claim 6, characterized in that The diamine monomer is one or more of ethylenediamine, hexamethylenediamine and propylenediamine.

9. The method for preparing the polyamide resin according to claim 6, characterized in that: The steps include: (I) preparing a linear dimer acid according to the method for preparing a linear dimer acid according to claim 1; (II) preparing materials according to the following formula: 1000 parts by weight of a linear dimer acid, 100 parts by weight of an organic acid, 0.4 parts by weight of a phosphate additive, and 169.2 parts by weight of a diamine monomer, wherein the linear dimer acid is the linear dimer acid obtained in step (I); (III) The straight-chain dimer acid, organic acid and phosphate additive are mixed and heated to 80°C, and then the diamine monomer is added dropwise for 30 minutes. The mixture is then heated to 120°C and kept warm for 1 hour. The mixture is then heated to 220°C and kept warm for 2 hours. The mixture is then heated to 230°C and kept warm for 1 hour, and then vacuumed. The polyamide resin is obtained after cooling to room temperature.

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