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

{
  "publication_number": "US10844171B2",
  "country": "US",
  "kind": "B2",
  "title": "Production method of semi-aromatic polyamide, and semi-aromatic polyamide",
  "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.",
  "claims": [
    "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."
  ],
  "description_excerpt": "The present disclosure relates to a production method of a semi-aromatic polyamide, and a semi-aromatic polyamide, particularly a continuous production method of a low-gel semi-aromatic polyamide.\n\nA semi-aromatic polyamide is usually a polyamide with a benzene ring, obtained by subjecting an aromatic dibasic acid, an aliphatic dibasic acid and an aliphatic diamine to polycondensation. Due to the introduction of an aromatic ring structure in the main chain, the semi-aromatic polyamide has good heat resistance and mechanical properties, low water absorption, and has proper cost performance, thus filling the gap between the general engineering plastics and high temperature-resistant engineering plastics PEEK, and is applicable to the field such as electronics, electrical appliances, automobiles, clothing fibers, and the like.\n\nThe preparation of semi-aromatic polyamide usually uses a pre-polymerization-post-polycondensation process, wherein the pre-polymerization usually uses water as a reaction solvent, and a binary acid and a diamine are firstly neutralized in a salt-forming kettle to form a saline solution, and then heated to a certain temperature for dehydration and pre-polymerization to obtain a prepolymer aqueous solution, which is subjected to vacuum flashing to obtain a prepolymer solid or melt; the prepolymer is further subjected to solid phase or melt post-polycondensation to obtain a semi-aromatic polyamide product having a certain molecular weight. In order to stabilize the product quality, it is generally desired to use a continuous production process.",
  "cpc": [
    "C08G 69/28",
    "C08G 69/265",
    "C08L 77/00",
    "C08L 77/08"
  ],
  "ipc": [
    "C08G 69/26",
    "C08G 69/28",
    "C08L 77/08"
  ],
  "assignees": [
    "Zhejiang University ZJU",
    "Zhejiang NHU Co Ltd",
    "Zhejiang NHU Special Materials Co Ltd"
  ],
  "inventors": [
    "Zhirong Chen",
    "Hong Yin",
    "Qin Zhang",
    "Xiaoxiao Wu",
    "Wengang Hong",
    "Hangjun Deng",
    "Guiyang Zhou",
    "Changze Wang"
  ],
  "filing_date": "2017-06-29",
  "publication_date": "2020-11-24",
  "grant_date": "2020-11-24",
  "priority_date": "2016-12-28",
  "application_number": "US-201715779414-A",
  "family_id": "58903678",
  "cited_by_count": 1,
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}