Polymer, process and composition

• US 9,296,860 B2
• Filed: 12/21/2010
• Issued: 03/29/2016
• Est. Priority Date: 12/21/2009
• Status: Expired due to Fees

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Friederichs, Joseph Petronella, Vermeulen, Jacobus Adriaan Antonius, Driessen, Marco Marcus Matheus
• Primary Examiner(s): Stanley, Jane L
• Application Number:
  US13/517,333
• Publication Number:
  US 20130211003A1
• Time in Patent Office: 1,925 Days
• Field of Search: 524/606
• US Class Current: 1/1
• CPC Class Codes: C08G 69/26 derived from polyamines and polycarboxylic acids
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08G 83/005 Hyperbranched macromolecules

Abstract

There is described a process for producing a gel free hyperbranched polyamide polymer having primary amino groups (useful as a crosslinker). The process comprises the step of reacting at least one diamine and at least one unsaturated diester in a molar ratio of diamine to diester greater than 1 but less than 3 (preferably 2.1 to 2.9); to form the polyamide in a two stage reaction Michael addition and then amidation. The diamine in kept in excess with at least 5% of water by total weight of the diamine and diester, a reaction temperature less than the boiling point of the diamine; and is held under reduced pressure (30 mbar to 1 atms). Gelation does not occur even after substantially all ethylenic (—C═C—) double bonds; and >95% ester [—C(O)═O] groups have reacted. This violates the Flory rules which predict a gel would form based on the number of functional groups present and their degree of conversion.

Claims

1. A process for preparing a substantially gel free non-dendrimer polyamide comprising primary amino groups, the process comprising the step of reacting Reagent A and Reagent B in a reaction mixture in the presence of at least 5.1% and less than 23.3% water by weight of a total amount of Reagents A and B sufficient to prevent gelation, wherein

Reagent A comprises at least one diaminoC_1-12hydrocarbon;

and

Reagent B comprises at least one di(C_1-12hydrocarbo-oxy) C_3-10hydrocarbo-enedioate and/or anhydride thereof, wherein

Reagent A and Reagent B are present in an amount to provide a molar ratio Rt of Reagent A to Reagent B which is in a range of 1.1 to 2.9.

2. The process as claimed in claim 1, wherein

Reagent A comprises a diaminoC_1-10alkane;

and

Reagent B comprises a di(C_1-6alkoxy)C_4-6alkenedioate ester; and

wherein

Rt is in the range from 2.0. to 2.8; and

wherein

the reaction is carried out in the presence of from 6% to 20% water by weight of the total amount of Reagents A and B.

3. The process as claimed in claim 1, wherein Rt is in the range from 2.1. to 2.7.

4. The process as claimed in claim 1, wherein the process is carried out in the presence of an amount of water which is from 7% to 15% by weight of the total amount of Reagents A and B.

5. The process as claimed in claim 1, wherein the process is performed at a pressure lower than atmospheric pressure and greater than 30 mbar.

6. The process as claimed in claim 1, wherein the process is performed a temperature between 0°

C. and a boiling point of the Reagent A.

7. The process as claimed min claim 1, wherein the Reagent A is selected from the group consisting of 1,4-diaminobutane (DAB), 1,5-diamino-2-methylpentane (M PM D), 1,5-pentanediamine hexamethylene-diamine (HMDA), 1,5-diamino-2-carboxypentane, lysine esters and lysine salts.

8. The process as claimed min claim 1, wherein the Reagent B is selected from the group consisting of dialkyl maleate, dialkyl fumarate, dialkyl itaconate, dialkyl citraconate, dialkyl mesaconate and mixtures thereof.

9. The process as claimed in claim 1, wherein the process his performed until the reaction mixture satisfies at least one condition of:

(i) being substantially free of ethylenic double bonds as measured by proton NMR; and

(ii) comprising no more than 5% equivalents of an initial amount of Reagent B of ester double bonds as measured by proton NMR.

10. A non-dendrimer polymer comprising amino groups, obtained by the process as claimed in claim 1.

11. The non-dendrimer polymer as claimed in claim 10, wherein the polymer comprises or more amino functional polyamide molecules represented by Formula 1:

12. The non-dendrimer polymer as claimed in claim 11, wherein R¹ independently in each case is C_2-6alkylyne, and wherein R², R³ and R⁴ independently in each case and of each other represent C_2-6alkylene.

13. The non-dendrimer polymer as claimed in claim 12, wherein R¹ independently in each case is ethylyne, and wherein R², R³ and R⁴ independently in each case and of each other represent ethylene.

14. The non-dendrimer polymer as claimed in claim 10, wherein the polymer has a polydispersity of at least 1.5.

15. The non-dendrimer polymer as claimed in claim 10, wherein the polymer has a number average molecular weight (Mn) of at least 500 daltons.

16. The non-dendrimer polymer in claim 10, wherein the polymer has on average at least four amine groups per polymer macromolecule.

17. A method comprising a step of reacting the non-dendrimer polymer as claimed in claim 10 with a second polymer comprising groups thereon which react with amino groups to form a polymeric reaction product.

18. A coating comprising the non-dendrimer polymer as claimed in claim 10.

19. An article coated with the coating as claimed in claim 18.