Production method of semi-aromatic polyamide, and semi-aromatic polyamide

Patent metadata

Field	Value
Publication number	US-10844171-B2
Application number	US-201715779414-A
Country	US
Kind code	B2
Filing date	Jun 29, 2017
Priority date	Dec 28, 2016
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

The present disclosure provides a production method of a semi-aromatic polyamide, and a semi-aromatic polyamide. Said production method of a semi-aromatic polyamide includes: step 1 of subjecting an initial charge of a diamine and a binary acid in an amine/acid molar ratio of less than 1.0 to form a slurry together with water and a catalyst, and subjecting the slurry to heating and dissolution to form a saline solution; step 2 of dehydrating said saline solution after detecting the composition thereof, detecting the content of diamine in a steam condensate from a dehydration unit, adjusting the amine/acid molar ratio to be larger than 1.0 by a molten diamine and a monoacid as a molecular weight regulator, and performing pre-polymerization; and step 3 of subjecting a pre-polymerization solution to post-polycondensation after vacuum flashing. The semi-aromatic polyamide of the present disclosure has a low gel content, excellent performance and extensive scope of application.

First claim

The invention claimed is:

1. A production method of a semi-aromatic polyamide, comprising:
step 1 forming a slurry by combining an initial charge of a diamine and a binary acid in an amine/acid molar ratio of less than 1.0 together with water and a catalyst, and subjecting the slurry to heating and dissolution to form a saline solution,
step 2 dehydrating said saline solution after detecting the composition thereof, detecting the content of diamine in a steam condensate from a dehydration unit, adjusting the amine/acid molar ratio to be larger than 1.0 by diamine and a monoacid as a molecular weight regulator, and performing pre-polymerization, and
subjecting a pre-polymerization solution to post-polycondensation after vacuum flashing,
wherein the temperature of the dehydration is 170-260° C., the pressure of the dehydration is 0.7-2.0 MPa, and the dehydration time is 10-40 min; the temperature of said pre-polymerization is 250-350 C., the pressure of said pre-polymerization is 10-30 MPa, and the reaction time is 1-15 min; the reaction temperature of said post-polycondensation is 300-350° C., and the reaction time is 0.5-5 min.

2. The method according to claim 1 , wherein the amine/acid molar ratio of the initial charge in said step 1 is from 0.90 to 0.99.

3. The method according to claim 1 , wherein said binary acid comprises aromatic dibasic acid and aliphatic dibasic acid, the molar ratio of said aromatic dibasic acid to said aliphatic dibasic acid is 100:0 to 40:60.

4. The method according to claim 3 , wherein said aliphatic dibasic acid is one or more selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; and said aromatic dibasic acid is one or more selected from isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid.

5. The method according to claim 1 , wherein said diamine is one or more selected from hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine and xylylenediamine, preferably, said diamine is one or more selected from hexamethylenediamine, octamethylenediamine and decamethylenediamine.

6. The method according to claim 1 , wherein said monoacid as the molecular weight regulator is one or more selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, lauric acid, palm acid, palmitic acid, stearic acid, benzoic acid and phenylacetic acid.

7. The method according to claim 1 , wherein the mole number of said monoacid as the molecular weight regulator is from 0.1 to 5% relative to the total mole number of the binary acid in the initial charge.

8. The method according to claim 1 , wherein the mass of said catalyst is from 0.01 to 2.5% relative to the total mass of the binary acid in the initial charge.

9. The method according to claim 1 , wherein said step 1 further comprises a step of detecting the composition of the binary acid in said saline solution and keeping the composition of the binary acid stable by adding an aromatic dibasic acid and/or an aliphatic dibasic acid.

10. The method according to claim 9 , wherein the detection in said step 1 uses online Raman spectroscopy.

11. The method according to claim 1 , wherein the detection in said step 2 uses online Raman spectroscopy.

12. The method according to claim 1 , wherein the amine/acid molar ratio in said step 2 is from 1.005 to 1.05.

13. The method according to claim 1 , wherein steam generated from a dehydration procedure in said step 2 can be used as a heat source for the heating and dissolution of a slurry, and excessive steam can be combined after condensation with a condensate generated from a heating process as supplementary water for use in a procedure of forming a slurry.

14. The method according to claim 9 , wherein the detection in said step 2 uses online Raman spectroscopy.

15. The method according to claim 2 , wherein the amine/acid molar ratio of the initial charge in said step 1 is from 0.92 to 0.98.

16. The method according to claim 3 , wherein the molar ratio of said aromatic dibasic acid to said aliphatic dibasic acid is 100:0 to 50:50.

Assignees

• Zhejiang Nhu Special Mat Co Ltd
• Univ Zhejiang
• Zhejiang Nhu Co Ltd

Inventors

• Chen Zhirong
• Yin Hong
• Zhang Qin
• Wu Xiaoxiao
• Hong Wengang
• Deng Hangjun
• Zhou Guiyang
• Wang Changze

Classifications

• C08G69/265 Primary

  from at least two different diamines or at least two different dicarboxylic acids · CPC title

• C08G69/28 Primary

  Preparatory processes · 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

• C08L77/08

  from polyamines and polymerised unsaturated fatty acids · CPC title