Method for producing highly viscous polyamides

Patent metadata

Field	Value
Publication number	US-9738756-B2
Application number	US-201414888243-A
Country	US
Kind code	B2
Filing date	Apr 30, 2014
Priority date	May 2, 2013
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

The invention relates to a method for synthesizing a polyamide, in which method an aqueous solution is sprayed onto the polyamide before and/or during a solid-state post-condensation process. The aqueous solution comprises at least a first compound, selected from the group comprising phosphoric acid, fully neutralized salts of phosphoric acid, partially neutralized salts of phosphoric acid, and mixtures thereof, and a second compound, selected from the group comprising an acid, an anhydride, a lactone, ammonia, an amine, and mixtures thereof, with the stipulation that the second compound is not phosphoric acid and is not phosphoric acid anhydride. The spraying occurs at a temperature that lies below the boiling point of water. A polyamide that can be produced by means of the method according to the invention can be used in particular to produce films, monofilaments, fibers, threads, or textile sheet materials.

First claim

The invention claimed is:

1. A process for preparing polyamides, comprising:
1) preparing a polyamide prepolymer by
a) providing an aqueous composition comprising at least one component which is suitable for polyamide formation and is selected from the group consisting of lactams, ω-amino acids, aminocarbonitriles, and salts of at least one dicarboxylic acid and at least one diamine,
b) polymerizing the composition provided in step a) at elevated temperature in the presence of water to obtain a polyamide prepolymer,
c) subjecting the polyamide prepolymer obtained in step b) to a shaping operation to obtain polyamide particles,
d) optionally subjecting the polyamide particles obtained in step c) to an extraction and/or a drying step,

2) solid phase postpolymerizing the polyamide particles, wherein the polyamide particles are contacted immediately prior to and/or during the solid phase postpolymerization, but after step 1), with an aqueous composition comprising:
A) at least one first compound selected from the group consisting of phosphoric acid, fully neutralized salts of phosphoric acid, and partly neutralized salts of phosphoric acid, and
B) at least one second compound other than A), selected from the group consisting of an acid, an anhydride, a lactone, and an amine, with the proviso that the second compound is not a phosphoric anhydride,

and wherein the polyamide particles are contacted with the aqueous composition at a temperature and a pressure at which the aqueous composition is liquid.

2. The process according to claim 1 , wherein the polyamide is selected from the group consisting of PA 6, PA 11, PA 12, PA 46, PA 66, PA 666, PA 69, PA 610, PA 612, PA 96, PA 99, PA 910, PA 912, PA 1212, PA 6T, PA 9T, PA 10T, PA 12T, PA 6I, PA 9I, PA 10I, PA 12I, PA 6T 6I, PA MXD6, PA MACM I, PA MACM T, PA PACM I, PA PACM T and copolymers and mixtures thereof.

3. The process according to claim 1 , wherein component B) comprises at least one acid selected from the group consisting of monocarboxylic acids R 1 —COOH and dicarboxylic acids R 2 —(COOH) 2 , in which R 1 is hydrogen, C 1 C 10 -alkyl or phenyl and R 2 is a chemical bond, C 1 -C 10 -alkylene or phenylene.

4. The process according to claim 1 , wherein component B) comprises succinic acid.

5. The process according to claim 1 , wherein component B) comprises at least one acid selected from the group consisting of phosphonic acid, phosphinic acid and phosphonates.

6. The process according to claim 1 , wherein component B) comprises at least one anhydride selected from the group consisting of:
aliphatic anhydrides R 3 C(═O)—O—C(═O)—R 4 , in which R 3 and R 4 are each independently C 1 -C 10 -alkyl and
alicyclic or aromatic anhydrides of the formula in which R 5 is C 2 -C 6 -alkylene, C 2 -C 6 -alkenylene, C 2 -C 6 -alkynylene or a divalent saturated or mono- or polyunsaturated or aromatic cyclic radical.

7. The process according to claim 1 , wherein component B) comprises at least one lactone selected from the group consisting of γ-lactones, δ-lactones, and εlactones.

8. The process according to claim 1 , wherein component B) comprises at least one amine selected from the group consisting of ammonia, primary amines R 6 NH 2 , secondary amines R 6 R 7 -NH 2 , tertiary amines R 6 R 7 R 8 -N, quaternary amines R 6 R 7 R 8 R 9 -N + (X − ), and diamines (H 2 N)-R 10 -(NH 2 ), in which R 6 , R 7 , R 8 , R 9 are each independently C 1 -C 20 -alkyl, C 3 -C 8 -cycloalkyl, aryl, C 7 -C 20 -arylalkyl or C 8 -C 20 -alkylarylalkyl, R 10 is C 2 -C 10 -alkylene and X − is one anion equivalent.

9. The process according to claim 1 , wherein the aqueous composition is sprayed onto the polyamide particles.

10. The process according to claim 9 , wherein the spray application of the aqueous composition is effected continuously.

11. The process according to claim 1 , wherein the aqueous composition is contacted with the polyamide particles within a period of not more than 30 seconds.

12. The process according to claim 1 , wherein the aqueous solution is distributed mechanically on the surface of the polyamide particles.

13. The process according to claim 12 , wherein the mechanical distribution is effected by means of mixing and dispersing elements.

14. The process according to claim 1 , wherein the aqueous composition comprises 0.25% by weight to 1% by weight of at least one phosphorus-containing component A).

15. The process according to claim 1 , wherein the aqueous solution comprises 0.25% by weight to 1% by weight of component B).

16. The process according to claim 1 , wherein the prepolymer contains reactive groups, and wherein the molar ratio of component B to the reactive groups in the prepolymer is 1:50 to 1:5.

17. The process according to claim 1 , wherein the prepolymer contains amino end groups, wherein component B is selected from the group consisting of acids, anhydrides, and lactones, and wherein the molar ratio of component B to the amino end groups of the prepolymer is 1:50 to 1:5.

18. The process according to claim 1 , wherein the prepolymer contains carboxyl end groups, wherein component B is selected from the group consisting of amines and ammonia, and wherein the molar ratio of component B to the carboxyl end groups of the prepolymer is 1:50 to 1:5.

19. The process according to claim 1 , wherein component B) consists of succinic acid.

20. The process according to claim 1 , wherein the aqueous composition is contacted with the polyamide particles within a period of not more than 10 seconds.

Assignees

• Basf Se

Inventors

• Häffner Rüdiger
• Grützner Rolf-Egbert
• Stammer Achim
• Ulzhöfer Angela

Classifications

• C08G69/06 Primary

  Solid state polycondensation · CPC title

• C08J2377/02

  Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08J2377/10 takes precedence) · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08G69/46 Primary

  Post-polymerisation treatment · CPC title

• C08G69/30

  Solid state polycondensation · CPC title