Process for producing aromatic polyimides

Patent metadata

Field	Value
Publication number	US-10745520-B2
Application number	US-201515535884-A
Country	US
Kind code	B2
Filing date	Dec 17, 2015
Priority date	Dec 18, 2014
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

The invention relates to a process for producing aromatic polyimides, comprising the following steps: (a) preparation of one or more solid salt(s) by reacting one or more aromatic tetracarboxylic acid(s) and one or more diamine(s) according to a mole ratio ranging from 0.95 to 1.05; (b) drying of the solid salt(s), (c) addition, to the dry salt resulting from step (b), of one or more compound(s) (C) comprising one or more group(s) chosen from a carboxylic acid group, an anhydride group, an ester group and an acyl chloride group; (d) solid-state polymerization of said solid salt(s) in the presence of the compound(s) (C).

First claim

The invention claimed is:

1. A process for manufacturing aromatic polyimides, characterized in that it comprises the following steps:
(a) preparing one or more solid salts by reacting, one or more aromatic tetracarboxylic acids and one or more diamines in a mole ratio ranging from 0.95 to 1.05;
(b) drying the solid salt(s);
(c) preparing a polymerization reaction by dry mixing the dry salt derived from step (b) with one or more compounds (C) in a dry state, selected from pyromellitic acid (PMA) and phthalic acid (PHTA), and mixtures thereof; and
(d) solid-state polymerization of said solid salt(s) in the presence of the one or more compound(s) (C).

2. The process as claimed in claim 1 , characterized in that the solid salt(s) are prepared by reacting one or more aromatic tetracarboxylic acids and one or more diamines in a mole ratio ranging from 0.99 to 1.01.

3. The process as claimed in claim 1 , characterized in that the solid salt(s) are prepared by reacting in stoichiometric amount one or more aromatic tetracarboxylic acids and one or more diamines.

4. The process as claimed in claim 1 , characterized in that said aromatic tetracarboxylic acids or dianhydrides used in step (a) are chosen from pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3,3′-benzophenonetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3,3′,4,4′-tetraphenylsilanetetracarboxylic acid, and 2,2′-bis(3,4-bicarboxyphenyl) hexafluoropropanetetracarboxylic acid.

5. The process as claimed in claim 1 , characterized in that the diamines are molecules of formula H 2 N—R—NH 2 with a linear or branched, saturated or unsaturated aliphatic, cycloaliphatic or aromatic divalent hydrocarbon-based radical R, optionally comprising one or more heteroatoms.

6. The process as claimed in claim 5 , characterized in that the radical R comprises from 2 to 50 carbon atoms, and optionally one or more heteroatoms.

7. The process as claimed in claim 1 , characterized in that the diamines are aliphatic diamines selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, hexamethylenediamine, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, and 1,14-diaminotetradecane.

8. The process as claimed in claim 1 , characterized in that the diamine(s) are chosen from cycloaliphatic diamines, and preferably from isophorone diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 4,4′-methylenebis(cyclohexylamine) and 4,4′-methylenebis(2-methylcyclohexylamine).

9. The process as claimed in claim 1 , characterized in that the diamine(s) are aromatic diamines selected from m-phenylenediamine, p-phenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, m-xylylenediamine and p-xylylenediamine.

10. The process as claimed in claim 1 , characterized in that the amount of compound (C) introduced into step (c) is greater than 0.5% as number of moles relative to the total number of moles of aromatic tetracarboxylic acid and of diamine used in step (a).

11. The process as claimed in claim 1 , characterized in that, during step (d), the polymerization is performed at a temperature T which obeys the following relationship: Tf of the salt from step (a)>T>Tg of the polyimide to be obtained.

12. The process as claimed in claim 1 , characterized in that, during step (d), the polymerization is performed at an absolute pressure ranging from 0.005 to 1 MPa.

13. The process as claimed in claim 1 , characterized in that, during step (d), the polymerization is performed at a temperature ranging from 50° C. to 250° C.

14. The process as claimed in claim 1 , characterized in that the number-average molar mass M n of the polyimide(s) obtained in step (d) ranges from 500 to 50 000 g/mol.

15. The process as claimed in claim 11 , wherein the manufactured aromatic polyimide has a Tg of less than 150° C.

Assignees

• Rhodia Operations
• Institut Nat Des Sciences Appliques De Lyon
• Centre Nat Rech Scient
• Univ Claude Bernard Lyon
• Univ Jean Monnet Saint-Etienne
• Univ Claude Bernard Lyon1
• Inst Nat Sciences Appliquees Lyon

Inventors

• Jeol Stéphane
• Rossin René
• Mollet Vincent
• Paci Benjamin
• Fenouillot-Rimlinger Françoise
• Rousseau Alain

Classifications

• C08G73/1067

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C08G73/105

  with oxygen only in the diamino moiety · CPC title

• C08G73/1082 Primary

  wholly aromatic in the tetracarboxylic moiety · CPC title

• C08G73/1028

  characterised by the process itself, e.g. steps, continuous · CPC title