Process for producing a thermoplastic polymer containing segments of a diamide

Patent metadata

Field	Value
Publication number	US-10040904-B2
Application number	US-201414911336-A
Country	US
Kind code	B2
Filing date	Jul 10, 2014
Priority date	Aug 16, 2013
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Process for the production of a thermoplastic polymer comprising segments of a diamide, the process comprising: 1) a first step of preparing a reaction mixture comprising a diamine H 2 N—Y—NH 2 Form. (I), and a diester of a dicarboxylic acid Form. (II) 2) a second step of heating the reaction mixture to a temperature at least 5° C. above the crystallization temperature of the diester and a least 5° C. below the melting temperature of the formed amide (formula III) in the presence of an alkaline or earth alkaline alkoxy catalyst Form. (III) wherein X and Y are the same or different and are an aliphatic group comprising 2-12 carbon atoms or an aromatic group comprising 6-20 carbon atoms, R1 and R2 are the same or different and are an aliphatic group comprising 2-15 carbon atoms and wherein R equals R1 or R2 and are the same or different. 3) optionally a third step of quenching the catalyst of the reaction mixture obtained in the second step by adding an acid to the reaction mixture and 4) a fourth step of adding further components to the reaction mixture obtained in the second step, or if the third step has been applied to the reaction mixture obtained in the third step, and so producing the thermoplastic polymer comprising the segments of the diamide.

First claim

The invention claimed is:

1. A process for producing a thermoplastic polymer comprising amide segments of a diamide, the process comprising:
1) a first step of preparing a reaction mixture comprising a diamine of formula I:
H 2 N—Y—NH 2   (formula I),

 and
 a diester of a dicarboxylic acid of formula II:

2) a second step of heating the reaction mixture to a temperature at least 5° C. above the crystallization temperature of the diester, as measured by DSC, according to ISO 11357-1:1997 under nitrogen atmosphere with a purge of 50ml/min using a heating and cooling rate of 20 K/min and a least 5° C. below the melting temperature of the formed amid according to formula III as measured by DSC, according to ISO 11357-1:1997 under nitrogen atmosphere with a purge of 50 ml/min using a heating and cooling rate of 20 K/min in the presence of an alkaline or earth alkaline alkoxy catalyst:

 wherein each of X and Y, which may be the same or different, is an aliphatic group comprising 2-12 carbon atoms or an aromatic group comprising 6-20 carbon atoms, each of R 1 and R 2 , which may be the same or different, is an aliphatic group comprising 2-15 carbon atoms, and wherein each R, which may be the same or different, equals R 1 or R 2 ;
3) optionally a third step of quenching the catalyst of the reaction mixture obtained in the second step by adding an acid to the reaction mixture; and
4) a fourth step of adding further components to the reaction mixture obtained in the second step, or if practiced to the reaction mixture obtained in the third step, to thereby produce the thermoplastic polymer comprising the amide segments of the diamide, wherein the fourth step comprises a reaction time sufficient to achieve a conversion in the absence of purification of more than 85% of the amine groups to the amide groups as determined by ([amide]/([amine]+[amide]))*100% with concentrations of the amine groups and the amide groups in the reaction mixture being obtained by 1 H NMR.

2. The process according to claim 1 , wherein the temperature in the second step is at least 25° C. below the melting temperature of the formed amide.

3. The process according to claim 1 , wherein the temperature in the second step is at least 25° C. above the crystallization temperature of the diester.

4. The process according to claim 1 , wherein each of R 1 and R 2 , which may be the same or different, is an aliphatic group comprising 4-12 carbon atoms.

5. The process according to claim 1 , wherein the diester of the dicarboxylic acid and the diamine are present in the reaction mixture of the first step to provide a molar ratio of the diester of the dicarboxylic acid: the diamine in the reaction mixture of the first step which is between 3:1 to 8:1.

6. The process according to claim 5 , wherein the molar ratio of the diester of the dicarboxylic acid: the diamine in the reaction mixture of the first step is between 4:1-6:1.

7. The process according to claim 1 , wherein the reaction time of the fourth step is such that conversion in the absence of purification of the amine groups to the amide groups is at least 90%.

8. The process according to claim 1 , wherein the reaction time of the fourth step is such that the conversion in the absence of purification of the amine groups to the amide groups is at least 95%.

9. The process according to claim 1 , wherein the acid for quenching is selected from the group consisting of organic acids, inorganic acids, and trialkyl ammonium salts or mixtures thereof.

10. The process according to claim 1 , wherein the acid for quenching is an organic acid or a trialkylammonium salt thereof.

11. The process according to claim 1 , wherein the acid for quenching is a cyanuric acid.

12. The process according to claim 1 , wherein the fourth step comprises adding a polymeric diol as a further component to the reaction mixture.

13. The process according to claim 1 , wherein the thermoplastic polymer is a thermoplastic copolyamide elastomer that contains the diamide as hard segments and soft segments derived from a polyether, a polyester, a polycarbonate, a polyalkane, a dimer fatty acid and/or a derivative thereof.

14. The process according to claim 1 , wherein the reaction mixture contains less than 10 wt. % of solvent in each reaction step.

15. The process according to claim 1 , wherein the reaction mixture contains less than 5 wt. % of solvent in each reaction step.

16. The process according to claim 1 , wherein the reaction mixture contains less than 2 wt. % of solvent in each reaction step.

Assignees

• Dsm Ip Assets Bv

Inventors

• Appel Wilhelmus Petrus Johannes
• Fitié Carel Frederik Constantijn
• Nijenhuis Atze Jan
• Keestra Beert Jacobus
• Krijgsman Josien
• Van Houtem Michel Henri Chrétien Joseph
• Janssen Henricus Marie

Classifications

• C07C231/02

  from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines · CPC title

• C08G69/40

  Polyamides containing oxygen in the form of ether groups (C08G69/12, C08G69/32 take precedence) · CPC title

• C08G69/28 Primary

  Preparatory processes · CPC title

• C08G69/44

  Polyester-amides · CPC title

• C07C233/78

  with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom · CPC title