Method for producing polyamide composite materials containing silicon

Patent metadata

Field	Value
Publication number	US-9580550-B2
Application number	US-201414891852-A
Country	US
Kind code	B2
Filing date	May 16, 2014
Priority date	May 17, 2013
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

The invention relates to a method for producing polyamide composite materials containing silicon, comprising the copolymerisation of: a) at least one silicon compound (SV) having at least one silicon atom, said silicon atom having at least one lactamyl group of formula (A) bonded by means of the nitrogen atom thereof; b) the method also comprises copolymerisation with at least one comonomer (CM) that is selected from among ammonium salts of dicarboxylic acids, amino acids, amino acid amides and lactams. In formula (A), m represents a whole number between 1 and 11, in particular in between 2 and 9, and specifically 3, and # represents the connection to the silicon atom of the compound (SV).

First claim

We claim:

1. A process for producing a silicon-containing polyamide composite material, comprising copolymerizing:
a. at least one silicon compound SV comprising a silicon atom comprising a lactamoyl radical attached via its nitrogen atom and having a formula (A),

where m is an integer from 1 to 11 and # is the point of attachment to the silicon atom; with

b. at least one comonomer CM selected from the group consisting of an ammonium salt of a dicarboxylic acid, an aminocarboxylic acid, an aminocarboxamide, and a lactam,

wherein the at least one comonomer CM is such that water is formed during the copolymerizing, or water is added to the copolymerization reaction,
wherein the silicon compound SV and the comonomer CM are present in such an amount of substance ratio that during the reaction at least 0.7 mol of water is formed per mole of lactam radicals of formula A attached to silicon atoms in the silicon compound SV, or a corresponding amount of water is added.

2. The process according to claim 1 wherein the silicon compound SV is selected from the group consisting of i), ii) and iii):
i) a compound of formula (I)

where m is an integer from 1 to 11,
x is 1, 2, 3 or 4, and
R is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl,
optionally substituted C 1 -C 6 -alkoxy, optionally substituted C 3 -C 6 -cycloalkyl,
optionally substituted phenyl or optionally substituted phenyl-C 1 -C 6 -alkyl;

ii) an oligomer comprising a repeat unit of formula (II);

where in is an integer from 1 to 11 and R′ is a lactamyl radical of formula (A) or has one of the meanings indicated for R in formula (I); and

iii) a mixture of compounds of formula (I) and the oligomers comprising repeat units of formula (II).

3. The process according to claim 2 , wherein the silicon compound SV is a compound of formula (I) where x is 3 or 4.

4. The process according to claim 1 , wherein the copolymerizing is conducted at a temperature in a range from 150 to 280° C.

5. The process according to claim 1 , wherein the comonomer is selected from the group consisting of:
b1) an aminocarboxylic acid;
b2) an ammonium salt of a dicarboxylic acid;
b3) a mixture of at least one lactam with at least one ammonium salt of a dicarboxylic acid; and
b4) a mixture of at least one lactam with at least one aminocarboxylic acid.

6. The process according to claim 1 , wherein the comonomer is
a mixture of at least one lactam and at least one aminocarboxylic acid or
a mixture of at least one lactam and at least one ammonium salt of a dicarboxylic acid.

7. The process according to claim 6 wherein a molar ratio of the lactam to the aminocarboxylic acid or to the ammonium salt of a dicarboxylic acid is at least 1.1:1.

8. The process according to claim 5 , wherein the aminocarboxylic acid or the ammonium salt of the dicarboxylic acid and the silicon compound SV are present in such an amount of substance ratio that a molar ratio of carboxyl groups in the comonomer to the lactam radicals of formula (A) attached to silicon atoms in the silicon compound SV is at least 0.9:1.

9. The process according to claim 1 , wherein the comonomer comprises a lactam having a formula (III)

where in is an integer from 1 to 11.

10. The process according to claim 1 , wherein the comonomer comprises an aminocarboxylic acid selected from the group consisting of compounds of formulae (IV) and (V)
H 2 N—(CH 2 ) y —COOH  (IV)

H 2 N—CHR x —COOH  (V)

wherein:
y in formula (IV) is from 1 to 20 and
R x in formula (V) is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 1 -C 6 -alkoxy, optionally substituted C 3 -C 6 -cycloalkyl, optionally substituted phenyl or optionally substituted phenyl-C 1 -C 6 -alkyl.

11. The process according to claim 1 , wherein the comonomer comprises an ammonium salt of a dicarboxylic acid that is a salt of dicarboxylic of formula (IV) with a diamine of formula (VII)
HOOC—(CH 2 ) z —COOH  (VI)

H 2 N—(CH 2 ) v —NH 2   (VII)

where z in formula (VI) is an integer from 1 to 12 and v in formula (VII) is an integer from 2 to 12.

12. A silicon-containing polyamide composite material obtained by the process according to claim 1 .

13. The polyamide composite material according to claim 12 comprising from 0.1% to 10.0% by weight of silicon, based on a total weight of the composite material.

14. A film, fiber, monofilament, pipe, profile, semi-fabricated product, or plastic article, comprising the polyamide composite material according to claim 12 .

15. The process according to claim 1 , wherein the comonomer comprises an ammonium salt of a dicarboxylic acid.

16. The process according to claim 1 , wherein the comonomer comprises an aminocaboxylic acid.

17. The process according to claim 1 , wherein the comonomer comprises an aminocarboxamide.

18. The process according to claim 1 , wherein the comonomer comprises a lactam.

Assignees

• Basf Se

Inventors

• Gruetzner Rolf-Egbert
• Lange Arno
• Kassner Lysann
• Seifert Andreas
• Spange Stefan

Classifications

• 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

• C08G77/455

  containing polyamide, polyesteramide or polyimide sequences · CPC title

• C08G69/16

  Preparatory processes · CPC title

• C08G83/001

  Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica · CPC title

• C08L77/02

  Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08L77/10 takes precedence) · CPC title