Thermal grafts of polyamides with pendant carboxylic acid groups, methods for producing the same, compositions containing the same, and methods of using the same

• US 6,429,266 B2
• Filed: 06/30/1998
• Issued: 08/06/2002
• Est. Priority Date: 06/30/1998
• Status: Expired due to Fees

• Current Assignee: Construction Research & Technology GmbH (BASF SE), MBT Holding AG, University of South Alabama
• Original Assignee: MBT Holding AG, University of South Alabama
• Inventors: Sikes, C. Steven, Vickers, Thomas M. Jr.
• Primary Examiner(s): WOODWARD, ANA LUCRECIA
• Application Number:
  US09/106,452
• Publication Number:
  US 20020013422A1
• Time in Patent Office: 1,498 Days
• Field of Search: 525/420, 525/926
• US Class Current: 525/420
• 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: Y10S 525/926 Polyamide containing a plurality of oxyalkylene groups

Abstract

Heating an intimate mixture of: (a) a polyamide which contains pendant carboxylic acid groups; and (b) a compound which contains an amino group efficiently affords graft polymers with a high graft density. Such graft polymers are particularly useful as additives for cementitious compositions.

Claims

1. A method for preparing a graft polymer, said method comprising:

(i) heating an intimate mixture, substantially free of water and substantially free of organic solvent, of;

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group of formula (III)

2. The method of claim 1, wherein said polyamide which contains pendant carboxylic acid groups is selected from the group consisting of polyaspartic acid, polyglutamic acid, and copolymers of aspartic acid and glutamic acid.

3. The method of claim 1, wherein said polyamide which contains pendant carboxylic acid groups is polyaspartic acid.

4. The method of claim 3, wherein the polyaspartic acid has at least 75% of its pendant carboxy groups as acid groups, not salified.

5. The method of claim 3, wherein the polyaspartic acid has essentially 100% of its pendant carboxy groups as acid groups, not salified.

6. The method of claim 1, wherein said heating said intimate mixture of:

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group is carried out without condensing and returning solvent to said intimate mixture.

7. The method of claim 1, wherein the graft efficiency of the compound (b) onto the polyamide (a) is from 50 to 100%.

8. The method of claim 1, wherein the graft efficiency of the compound (b) onto the polyamide (a) is from 80 to 100%.

9. A method for preparing a graft polymer, said method comprising:

(i) heating an intimate mixture, substantially free of water and substantially free of organic solvent, of;

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group of the formula (II);

10. The method of claim 9, wherein said polyamide which contains pendant carboxylic acid groups is selected from the group consisting of polyaspartic acid, polyglutamic acid, and copolymers of aspartic and glutamic acid.

11. The method of claim 9, wherein said polyamide which contains pendant carboxylic acid groups is polyaspartic acid.

12. The method of claim 11, wherein the polyaspartic acid has at least 75% of its pendant carboxy groups as acid groups, not salified.

13. The method of claim 11, wherein the polyaspartic acid has essentially 100% of its pendant carboxy groups as acid groups, not salified.

14. A graft polymer, produced by a process comprising:

(i) heating an intimate mixture, substantially free of water and substantially free of organic solvent, of;

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group, to obtain said graft polymer,

wherein said compound which contains an amino group has the formula (II);

15. The graft polymer of claim 14, wherein said polyamide which contains pendant carboxylic acid groups is selected from the group consisting of polyaspartic acid, polyglutamic acid, and copolymers of aspartic acid and glutamic acid.

16. The graft polymer of claim 14, wherein said polyamide which contains pendant carboxylic acid groups is polyaspartic acid.

17. The graft polymer of claim 14, wherein said heating said intimate mixture of:

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group is carried out without condensing and returning solvent to said intimate mixture.

18. The graft polymer of claim 14, wherein said graft polymer has a graft density of at least 30%.

19. A graft polymer, produced by a process comprising:

(i) heating an intimate mixture, substantially free of water and substantially free of organic solvent, of;

(a) a polyamide which contains pendant carboxylic acid groups; and

(b) a compound which contains an amino group, to obtain said graft polymer,

wherein said compound which contains an amino group has the formula (III);

20. The graft polymer of claim 19, wherein said polyamide which contains pendant carboxylic acid groups is selected from the group consisting of polyaspartic acid, polyglutamic acid, and copolymers of aspartic acid and glutamic acid.

21. The graft polymer of claim 19, wherein said polyamide which contains pendant carboxylic acid groups is polyaspartic acid.

22. The graft polymer of claim 19, wherein said heating is carried out in the solid state.

23. The graft polymer of claim 19, wherein said graft polymer has a graft density of at least 30%.

24. A polymer of formula (IV):

wherein;

each X independent of the other is hydrogen, an alkali metal ion, an alkaline earth metal ion, ammonium ion, or substituted ammonium;

each —

NH—

Z—

is a monomer unit derived from a compound which contains (i) a —

NH₂ group and (ii) a —

CO₂H or a —

SO₃H group;

m, m′

, n, and n′

are each independently 0 or an integer between 1 and about 20,

a, b, c, d and reflect the mole fraction of each unit wherein the sum of a+b+c+d equals one, wherein a is a decimal value of 0 to 0.75;

b is a decimal value of 0 to 0.75;

c is a decimal value of 0.25 to 1; and

d is a decimal value of 0 to 0.5; and

Q has the formulae (V);

25. The polymer of claim 24, wherein m, m′

, n, and n′

are each independently 0 to 2.

26. A polymer of formula (IV′

);

wherein;

each X independent of the other is hydrogen, an alkali metal ion, an alkaline earth metal ion, ammonium ion, or substituted ammonium;

each —

NH—

Z—

is a monomer unit derived from a compound which contains (i) a —

NH₂ group and (ii) a —

CO₂H or a —

SO₃H group;

m, m′

, n, and n′

are each independently 0 or an integer between 1 and about 20,

a, b, c, and d represent the mole fraction of each unit wherein the sum of a+b+c+d equals one, wherein a is a decimal value of 0 to 0.75;

b is a decimal value of 0 to 0.75;

c is a decimal value of 0.25 to 1; and

d is a decimal value of 0 to 0.5; and

Q has the formulae (VI);

27. The polymer of claim 26, wherein m, m′

, n, and n′

are each independently 0 to 2.

28. The polymer of claim 26, wherein the polymer has a density of grafted units of at least 25%.

29. The polymer of claim 26, wherein m, m′

, n and n′

are each independently 0 or an integer of 1 to 2.