Method for synthesizing long carbon chain semi-aromatic nylon

Patent metadata

Field	Value
Publication number	US-11905370-B2
Application number	US-202117477927-A
Country	US
Kind code	B2
Filing date	Sep 17, 2021
Priority date	Nov 10, 2020
Publication date	Feb 20, 2024
Grant date	Feb 20, 2024

Abstract

The disclosure relates to a synthesis method of long carbon chain semi-aromatic nylon. The synthesis method comprises the following steps: mixing a wet powdery nylon salt, an antioxidant, a catalyst, a surfactant and pellets, and carrying out a one-step solid state polymerization under dynamic mixing to obtain a powdery nylon; under dynamic mixing, enabling the pellets to promote the stirring and mixing of the material and reducing material adhesion to the wall; the one-step solid state polymerization comprises a pre-solid state polymerization and a post-solid state polymerization; in the pre-solid state polymerization, ensuring the nylon salt and the prepolymer not to be molten; in the post-solid state polymerization, gradually reducing the system pressure to vacuum, and keeping the system pressure in vacuum state for at least 1 hour; the temperature of the post-solid state polymerization is not lower than the termination temperature of the pre-solid state polymerization.

First claim

What is claimed is:

1. A method for synthesizing a long carbon chain semi-aromatic nylon, wherein the method comprises:
mixing a wet powdery nylon salt, an antioxidant, a catalyst, a surfactant, and pellets and carrying out a one-step solid state polymerization under dynamic mixing to obtain a powdery nylon,
wherein the wet powdery nylon salt has a solvent content of 5-40% wt, and is prepared by salt-forming reaction of terephthalic acid and a long carbon chain diamine with 10-14 carbon atoms in the solvent,
wherein the pellets promote stirring and mixing of materials and reduce sticking of materials to a wall under dynamic mixing,
wherein the one-step solid state polymerization includes pre-solid state polymerization and post-solid state polymerization; in the pre-solid state polymerization, gradually increasing temperature of the system from 150-190° C. to 180-220° C., ensuring the nylon salt and the prepolymer not to be molten, and increasing the solvent vapor pressure to 1.00-2.20 MPa during the period; in the post-solid state polymerization, gradually reducing the system pressure to vacuum and holding for at least 1 h; the temperature of the post-solid state polymerization should not be lower than the termination temperature of the pre-solid state polymerization; and
wherein, in the pre-solid state polymerization, gradually increasing the temperature from 150-190° C. to 180-220° C. includes: holding the temperature at 150-190° C. for 0.5-2 h, then increasing the temperature to 180-220° C. at a rate of 5-10° C. for 0.5-1 h, and holding for 0.5-2 h.

2. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the time of the pre-solid state polymerization is 2-6 h.

3. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein gradually reducing the system pressure to vacuum comprises steam releasing and vacuuming after steam releasing, and the stream releasing time is 1-3 h.

4. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 3 , wherein the temperature is increased to 200-240° C. at a rate of 3-10° C. for 0.5-1 h after steam releasing for 0.5 h.

5. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the vacuum holding time is 1-6 h.

6. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 2 , wherein the vacuum holding time is 1-6 h.

7. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 3 , wherein the vacuum holding time is 1-6 h.

8. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 4 , wherein the vacuum holding time is 1-6 h.

9. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the catalyst is one or more selected from a group consisting of phosphorous acid, sodium hypophosphite, triphenyl phosphate, and H10, and an amount of the catalyst is 0.1-0.5% of the dry mass of the wet powdery nylon salt.

10. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the antioxidant is one or more selected from a group consisting of sodium hypophosphite, 1010, s9228, SH120, and B215, and an amount of the antioxidant is 0.1-0.5% of the dry mass of the wet powdery nylon salt.

11. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the solvent in the wet powdery nylon salt is one or more selected from a group consisting of water, ethanol, and methanol.

12. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 1 , wherein the long carbon chain diamine is one or more selected from a group consisting of decanediamine, undecanediamine, dodecanediamine, tridecanediamine, and tetradecanediamine.

13. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 9 , wherein the long carbon chain diamine is one or more selected from a group consisting of decanediamine, undecanediamine, dodecanediamine, tridecanediamine, and tetradecanediamine.

14. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 10 , wherein the long carbon chain diamine is one or more selected from a group consisting of decanediamine, undecanediamine, dodecanediamine, tridecanediamine, and tetradecanediamine.

15. The method for synthesizing the long carbon chain semi-aromatic nylon according to claim 11 , wherein the long carbon chain diamine is one or more selected from a group consisting of decanediamine, undecanediamine, dodecanediamine, tridecanediamine, and tetradecanediamine.

16. A method for synthesizing a long carbon chain semi-aromatic nylon, wherein the method comprises:
mixing a wet powdery nylon salt, an antioxidant, a catalyst, a surfactant, and pellets and carrying out a one-step solid state polymerization under dynamic mixing to obtain a powdery nylon,
wherein the wet powdery nylon salt has a solvent content of 5-40% wt, and is prepared by salt-forming reaction of terephthalic acid and a long carbon chain diamine with 10-14 carbon atoms in the solvent,
wherein the pellets promote stirring and mixing of materials and reduce sticking of materials to a wall under dynamic mixing,
wherein the one-step solid state polymerization includes pre-solid state polymerization and post-solid state polymerization; in the pre-solid state polymerization, gradually increasing temperature of the system from 150-190° C. to 180-220° C., ensuring the nylon salt and the prepolymer not to be molten, and increasing the solvent vapor pressure to 1.00-2.20 MPa during the period; in the post-solid state polymerization, gradually reducing the system pressure to vacuum and holding for at least 1 h; the temperature of the post-solid state polymerization should not be lower than the termination temperature of the pre-solid state polymerization;
wherein gradually reducing the system pressure to vacuum comprises steam releasing and vacuuming after stream releasing, and the steam releasing time is 1-3 h; and
wherein the temperature of the post-solid state polymerization is increased to 200-240° C. at a rate of 3-10° C. for 0.5-1 h after steam releasing for 0.5 h.

Assignees

• Univ Zhengzhou

Inventors

• Liu Minying
• Xue Bingfeng
• Fu Peng
• Cui Zhe
• Zhang Xiaomeng
• Zhao Wei
• Pang Xinchang
• Zhao Qingxiang

Classifications

• C08G69/30 Primary

  Solid state polycondensation · CPC title

• C08G69/06

  Solid state polycondensation · CPC title

• C08G69/26 Primary

  derived from polyamines and polycarboxylic acids · CPC title

• C08L77/00

  Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers · CPC title