PREPARATION METHOD OF REPROCESSABLE THERMOSETTING POLYESTERAMIDE (PEA), AND THERMOSETTING PEA PREPARED THEREBY

Abstract

A preparation method of a reprocessable thermosetting polyesteramide (PEA) includes: (1) mixing 30 to 200 parts by weight of a liquid dicarboxylic acid and 15 to 95 parts by weight of a β-hydroxyl-containing diamine compound, and heating for dissolution to obtain a reaction solution; (2) adding 0.05 to 0.5 parts by weight of a catalyst to the reaction solution, and heating under a nitrogen atmosphere to allow a reaction at 65° C. to 100° C. for 1 h to 6 h; (3) heating a reaction system obtained in step (2) to allow a reaction at 100° C. to 180° C. for 3 h to 18 h; (4) heating a reaction system obtained in step (3) to allow a reaction at 180° C. to 240° C. for 0.5 h to 4 h; and (5) cooling a reaction system obtained in step (4) to 100° C. to 180° C. A PEA prepared by the above preparation method is further provided.

Claims

1. A preparation method of a reprocessable thermosetting polyesteramide (PEA), comprising the following steps: (1) mixing 30 to 200 parts by weight of a liquid dicarboxylic acid and 15 to 95 parts by weight of a β-hydroxyl-containing diamine compound to obtain a first mixture, heating the first mixture for dissolution to obtain a dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 0.05 to 0.5 parts by weight of a catalyst to the reaction solution to obtain a second mixture, and heating the second mixture under a nitrogen atmosphere to allow a first reaction at 65° C. to 100° C. for 1 h to 6 h to obtain a first reaction system; (3) heating the first reaction system obtained in step (2) to allow a second reaction at 100° C. to 180° C. for 3 h to 18 h to obtain a second reaction system; (4) heating the second reaction system obtained in step (3) to allow a third reaction at 180° C. to 240° C. for 0.5 h to 4 h to obtain a third reaction system; (5) cooling the third reaction system obtained in step (4) to 100° C. to 180° C. to obtain the reprocessable thermosetting PEA.

2. The preparation method of the reprocessable thermosetting PEA according to claim 1, wherein the liquid dicarboxylic acid has a structural formula of ##STR00004## and the β-hydroxyl-containing diamine compound has a structural formula of ##STR00005##

3. The preparation method of the reprocessable thermosetting PEA according to claim 1, wherein the catalyst comprises any one selected from the group consisting of sodium phosphite, sodium hypophosphite (SHP), and zinc acetate.

4. The preparation method of the reprocessable thermosetting PEA according to claim 1, wherein the liquid dicarboxylic acid comprises one or more selected from the group consisting of the following structural formulas: ##STR00006##

5. The preparation method of the reprocessable thermosetting PEA according to claim 1, wherein the β-hydroxyl-containing diamine compound is 1,3-diamino-2-propanol.

6. The preparation method of the reprocessable thermosetting PEA according to claim 1, wherein the liquid dicarboxylic acid comprises a tall oil-derived diacid.

7. The preparation method of the reprocessable thermosetting PEA according to claim 5, comprising the following steps: (1) mixing 41.6 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain the dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain the second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain the first reaction system; (3) heating the first reaction system obtained in step 2 to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step 3 to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step 4 to 140° C. to obtain the reprocessable thermosetting PEA.

8. The preparation method of the reprocessable thermosetting PEA according to claim 5, comprising the following steps: (1) mixing 38.4 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain the dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain the second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain the first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

9. The preparation method of the reprocessable thermosetting PEA according to claim 5, comprising the following steps: (1) mixing 35.2 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain a dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain a second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain a first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

10. The preparation method of the reprocessable thermosetting PEA according to claim 5, comprising the following steps: (1) mixing 44.8 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain a first mixture, heating the first mixture for dissolution to obtain a dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain a second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain a first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

11. A reprocessable thermosetting PEA prepared by the preparation method according to claim 1.

12. The reprocessable thermosetting PEA according to claim 11, wherein in the preparation method, the liquid dicarboxylic acid has a structural formula of ##STR00007## and the β-hydroxyl-containing diamine compound has a structural formula of ##STR00008##

13. The reprocessable thermosetting PEA according to claim 11, wherein in the preparation method, the catalyst comprises any one selected from the group consisting of sodium phosphite, sodium hypophosphite (SHP), and zinc acetate.

14. The reprocessable thermosetting PEA according to claim 11, wherein in the preparation method, the liquid dicarboxylic acid comprises one or more selected from the group consisting of the following structural formulas: ##STR00009##

15. The reprocessable thermosetting PEA according to claim 11, wherein in the preparation method, the β-hydroxyl-containing diamine compound is 1,3-diamino-2-propanol.

16. The reprocessable thermosetting PEA according to claim 11, wherein in the preparation method, the liquid dicarboxylic acid comprises a tall oil-derived diacid.

17. The reprocessable thermosetting PEA according to claim 15, wherein the preparation method comprises the following steps: (1) mixing 41.6 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain the dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain the second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain the first reaction system; (3) heating the first reaction system obtained in step 2 to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step 3 to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step 4 to 140° C. to obtain the reprocessable thermosetting PEA.

18. The reprocessable thermosetting PEA according to claim 15, wherein the preparation method comprises the following steps: (1) mixing 38.4 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain the dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain the second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain the first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

19. The reprocessable thermosetting PEA according to claim 15, wherein the preparation method comprises the following steps: (1) mixing 35.2 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain the first mixture, heating the first mixture for dissolution to obtain a dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain a second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain a first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

20. The reprocessable thermosetting PEA according to claim 15, wherein the preparation method comprises the following steps: (1) mixing 44.8 g of a tall oil-derived diacid and 6.8 g of the 1,3-diamino-2-propanol to obtain a first mixture, heating the first mixture for dissolution to obtain a dissolved mixture, and stirring the dissolved mixture evenly to obtain a reaction solution; (2) adding 80 mg of sodium phosphite to the reaction solution to obtain a second mixture, and heating the second mixture under the nitrogen atmosphere to allow the first reaction at 80° C. for 1 h to obtain a first reaction system; (3) heating the first reaction system obtained in step (2) to allow the second reaction at 140° C. for 12 h and then allow a fourth reaction at 180° C. for 6 h to obtain the second reaction system; (4) heating the second reaction system obtained in step (3) to allow the third reaction at 230° C. for 2 h to obtain the third reaction system; and (5) cooling the third reaction system obtained in step (4) to 140° C. to obtain the reprocessable thermosetting PEA.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0068] FIG. 1 is a schematic diagram illustrating a reaction structure of the tall oil-derived diacid in an example of the present disclosure.

[0069] FIG. 2 shows an infrared (IR) spectrum of the PEA in Example 1 of the present disclosure.

[0070] FIG. 3 shows stress-strain curves of PEAs in Examples 1-5 of the present disclosure.

[0071] FIG. 4 shows glass transition temperature changes of PEAs in Examples 1 to 5 of the present disclosure.

[0072] FIG. 5 shows the comparison of IR spectra of the PEA in Example 1 of the present disclosure that is repeatedly formed.

[0073] FIG. 6 shows comparison photos of the PEA in Example 1 of the present disclosure before and after repeated forming.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0074] In order to make the objectives, technical solutions, and advantages of the examples of the present disclosure clearer, the technical solutions in the examples of the present disclosure will be clearly and completely described below with reference to the examples of the present disclosure. Apparently, the described examples are some rather than all of the examples. All other examples obtained by a person of ordinary skill in the art based on the examples of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.

[0075] The experimental materials, reagents, and the like used in the following examples are all commercially available, unless otherwise specified.

[0076] If specific techniques or conditions are not indicated in an example, a process shall be conducted in accordance with the techniques or conditions described in literatures in the art or in accordance with a product specification.

[0077] The tall oil-derived diacid in the following examples is provided by the MeadWestvaco (China) Holding Co., Ltd.

Example 1

[0078] A PEA was prepared, specifically including the following steps:

[0079] 32 g of a tall oil-derived diacid, 6.8 g of 1,3-diamino-2-propanol, and 80 mg of sodium phosphite were added to a three-necked flask. A resulting mixture was thoroughly stirred by a mechanical stirrer and under a nitrogen atmosphere. A resulting reaction system was heated to allow a reaction at 80° C. for 1 h, allow a reaction at 140° C. for 12 h, allow a reaction at 180° C. for 6 h, and allow a reaction at 230° C. for 2 h. The reaction system was finally cooled to 140° C.; and after the reaction was completed, a product was taken out and stored in a sealed container, which was named PEA 1.

[0080] As shown in FIG. 1, after the raw material tall oil-derived diacid of the present disclosure reacts according to Example 1, the peak of carboxyl groups basically disappears, and the peaks of amido and ester groups are newly generated, indicating that the reaction is successful and the amino group is basically converted into an amido group. In addition, due to the presence of hydroxyl groups, the hydroxyl groups react with carboxyl groups to produce ester groups, that is, the PEA is successfully prepared in the present disclosure.

[0081] The tall oil-derived diacid is a bifunctional mixture, and the tall oil-derived diacid is subjected to polycondensation with a trifunctional β-hydroxyl-containing monomer. The activity of the amino group is allowed to be higher than the activity of the hydroxyl group. The low-temperature reaction time is fully extended, such that the amino group reacts as much as possible and then the unreacted carboxyl groups and hydroxyl groups are cross-linked at a high temperature. Because the raw materials are fed according to a specified molar ratio, a quantity of carboxyl groups is always smaller than a total quantity of hydroxyl and amino groups, and there are still hydroxyl groups at a reaction end point as indicated by the hydroxyl peak at 3,300 cm.sup.−1 in FTIR spectrum. In addition, according to the transesterification reaction mechanism, the cross-linked polymer has reprocessability.

Example 2

[0082] A PEA was prepared, specifically including the following steps:

[0083] 35.2 g of a tall oil-derived diacid, 6.8 g of 1,3-diamino-2-propanol, and 80 mg of sodium phosphite were added to a three-necked flask. A resulting mixture was thoroughly stirred by a mechanical stirrer. Under a nitrogen atmosphere, a resulting reaction system was heated to allow a reaction at 80° C. for 1 h, allow a reaction at 140° C. for 12 h, allow a reaction at 180° C. for 6 h, and allow a reaction at 230° C. for 2 h. The reaction system was finally cooled to 140° C. After the reaction was completed, a product was taken out and stored in a sealed container, which was named PEA 2.

Example 3

[0084] A PEA was prepared, specifically including the following steps:

[0085] 38.4 g of a tall oil-derived diacid, 6.8 g of 1,3-diamino-2-propanol, and 80 mg of sodium phosphite were added to a three-necked flask. A resulting mixture was thoroughly stirred by a mechanical stirrer. Under a nitrogen atmosphere, a resulting reaction system was heated to allow a reaction at 80° C. for 1 h, allow a reaction at 140° C. for 12 h, allow a reaction at 180° C. for 6 h, and allow a reaction at 230° C. for 2 h. The reaction system was finally cooled to 140° C.; and after the reaction was completed, a product was taken out and stored in a sealed container, which was named PEA 3.

Example 4

[0086] A PEA was prepared, specifically including the following steps:

[0087] 41.6 g of a tall oil-derived diacid, 6.8 g of 1,3-diamino-2-propanol, and 80 mg of sodium phosphite were added to a three-necked flask, a resulting mixture was thoroughly stirred by a mechanical stirrer, and under a nitrogen atmosphere, a resulting reaction system was heated to allow a reaction at 80° C. for 1 h, allow a reaction at 140° C. for 12 h, allow a reaction at 180° C. for 6 h, and allow a reaction at 230° C. for 2 h; the reaction system was finally cooled to 140° C.; and after the reaction was completed, a product was taken out and stored in a sealed container, which was named PEA 4.

Example 5

[0088] A PEA was prepared, specifically including the following steps:

[0089] 44.8 g of a tall oil-derived diacid, 6.8 g of 1,3-diamino-2-propanol, and 80 mg of sodium phosphite were added to a three-necked flask, a resulting mixture was thoroughly stirred by a mechanical stirrer, and under a nitrogen atmosphere, a resulting reaction system was heated to allow a reaction at 80° C. for 1 h, allow a reaction at 140° C. for 12 h, allow a reaction at 180° C. for 6 h, and allow a reaction at 230° C. for 2 h; the reaction system was finally cooled to 140° C.; and after the reaction was completed, a product was taken out and stored in a sealed container, which was named PEA 5.

[0090] The tall oil-derived diacid is a multi-component mixture, and FIG. 2 is a conceptual diagram of the reaction of the tall oil-derived diacid.

[0091] As shown in FIG. 3, it can be seen from the preparation of PEAs 1, 2, 3, 4, and 5 that, with the content of 1,3-diamino-2-propanol unchanged, as the tall oil-derived diacid content increases, the material gradually transitions from a plastic to an elastomer in terms of mechanical properties. The tensile properties of a sample stripe were tested according to GB/T 1040.3-2006 at a tensile rate of 10 mm/min, a constant temperature, and a constant humidity.

[0092] As shown in FIG. 4, it can be seen from the preparation of PEAs 1, 2, 3, 4, and 5 that, with the content of 1,3-diamino-2-propanol unchanged, as the tall oil-derived diacid content increases, the glass transition temperature of the material gradually decreases.

[0093] As shown in FIG. 5, after the PEA 1 is repeatedly formed, groups indicated by IR spectroscopy do not change, indicating that the material can be reprocessed.

[0094] As shown in FIG. 6, after being preformed, the PEA 1 can still be cut into pieces and formed.

[0095] The above examples are used only to describe the technical solutions of the present disclosure, and are not intended to limit the present disclosure. Although the present disclosure is described in detail with reference to the above examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the above examples, or make equivalent substitutions to some technical features therein. These modifications or substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the examples of the present disclosure.