Thermoplastic hydrogels

• US 4,064,086 A
• Filed: 07/13/1976
• Issued: 12/20/1977
• Est. Priority Date: 07/13/1976
• Status: Expired due to Term

• Current Assignee: GP Strategies Corporation (Learning Technologies Group Plc)
• Original Assignee: GP Strategies Corporation (Learning Technologies Group Plc)
• Inventors: Cowsar, Donald Roy, Tanquary, Albert Charles
• Primary Examiner(s): Anderson, Harold D.
• Assistant Examiner(s): Nielsen, E. A.
• Application Number:
  US05/704,888
• Time in Patent Office: 525 Days
• Field of Search: 260/78.3 R, 260/29.2 R, 260/29.2 N, 260/29.2 E, 260/78 TF, 260/77.5 AQ, 260/47 CZ, 260/47 C, 260/343.6, 260/484 A, 260/561 B
• US Class Current: 524/601
• CPC Class Codes: C08G 69/02 Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids

Abstract

Thermoplastic hydrogels are prepared by making condensation polymers of spirolactones of the formula: ##STR1## with a difunctional compound capable of opening the lactone rings. The thermoplastic hydrogels can be cross-linked. In the formula the total of n and m and also of n'"'"' and m'"'"' is 2 to 5 and the R groups are H or hydrocarbyl with not over 3 R groups being hydrocarbyl. Most preferably all R groups are H and n, m, n'"'"' and m'"'"' are all 1.

Claims

1. A thermoplastic hydrophilic polymer having hydroxyl groups and capable of forming a hydrogel, said polymer being a condensation product of (1) a spirolactone of the formula:

##STR13## where the total of n and m is 2 to 5 and the total of n'"'"' and m'"'"' is 2 to 5 and the R groups are H or hydrocarbyl with the proviso that not over 3 R groups are hydrocarbyl with (2) a difunctional compound having two groups capable of opening the lactone ring which groups are selected from the group consisting of primary amino, secondary amino, alcoholic hydroxy and phenolic hydroxyl, (1) and (2) being employed in the range of 0.1 to 1 mole of (1) with 1 to 0.1 mole of (2).

2. A thermoplastic polymer according to claim 1, wherein the groups capable of opening the lactone ring are primary amino groups or secondary amino groups.

3. A thermoplastic polymer according to claim 2 wherein both amino groups are primary amino groups.

4. A thermoplastic polymer according to claim 1 wherein the spirolactone is 4,4-spirobibutyrolactone.

5. A thermoplastic polymer according to claim 4 wherein the groups capable of opening the lactone ring are primary amino groups or secondary amino groups.

6. A thermoplastic polymer according to claim 5 wherein both amino groups are primary amino groups.

23. A hydrogel of the polymer of claim 6.

24. A hydrogel of the polymer of claim 4.

25. A hydrogel of the polymer of claim 1.

39. A polymer according to claim 1 wherein (1) and (2) are employed in the mole ratio of 1:

1.

40. A polymer according to claim 39 wherein the spirolactone is 4,4-spirobibutyrolactone.

7. A crosslinked thermoplastic polymer prepared by crosslinking a thermoplastic hydrophilic polymer having hydroxyl groups and capable of forming a hydrogel, said polymer being a condensation product of (1) a spirolactone of the formula:

##STR14## where the total of n and m is to 2 to 5 and the total of n'"'"' and m'"'"' is 2 to 5 and the R groups are H or hydrocarbyl with the proviso that not over 3 R groups are hydrocarbyl with (2) a difunctional compound capable of opening the lactone ring having two groups capable of opening the lactone ring which groups are selected from the group consisting of primary amino, secondary amino, alcoholic hydroxy and phenolic hydroxyl with a compound containing at least two functional groups capable of reacting with alcoholic hydroxyl groups, the amount of crosslinking agent being insufficient to destroy the hydrogel forming properties of the polymer.

8. A polymer according to claim 7 wherein the crosslinking compound has isocyanato groups, carboxylic acid groups, methylol groups or at least three amino groups selected from the group consisting of primary and secondary amino groups.

9. A crosslinked thermoplastic polymer according to claim 7 wherein the spirolactone is 4,4-spirobibutyrolactone.

10. A crosslinked polymer according to claim 9 wherein the groups capable of opening the lactone ring are primary amino groups or secondary amino groups.

11. A crosslinked polymer according to claim 10 wherein the crosslinking agent has isocyanato groups.

12. A crosslinked polymer according to claim 11 wherein the compound capable of opening the lactone ring is an alkylene diamine having 2 to 18 carbon atoms, xylylene diamine or piperazine.

13. A crosslinked polymer according to claim 12 wherein the diamine is an alkylene diamine having 6 to 12 dicarbon atoms.

14. A crosslinked polymer according to claim 13 wherein the isocyanate is an alkylene diisocyanate or 4,4'"'"' -methylenebis (phenylisocyanate).

15. A crosslinked polymer according to claim 14 wherein the diamine is dodecamethylenediamine and the isocyanate is hexamethylenediisocyanate.

16. A crosslinked polymer according to claim 15 reacted with 5 to 10 mol percent of the diisocyanate per molecular unit of the polymer containing two hydroxyl groups.

17. A crosslinked polymer according to claim 16 reacted with 10 mol percent of diisocyanate.

18. A crosslinked polymer according to claim 11 wherein the diisocyanate is used in an amount of 5 to 10 mol percent per molecular unit of the polymer containing two hydroxyl units.

19. A hydrogel including the polymer according to claim 17.

20. A hydrogel including the polymer of claim 11.

21. A hydrogel including the polymer of claim 9.

22. A hydrogel including the polymer of claim 7.

33. A polymer according to claim 7 wherein (1) and (2) are employed in the range of 0.1 to 1 mole of (1) with 1 to 0.1 mole of (2).

34. A polymer according to claim 33 wherein (1) and (2) are employed in the mole ratio of 1:

1.

26. A polymer capable of forming a hydrogel, said polymer containing the repeating unit:

##STR15## where the R groups are H or hydrocarbyl with the proviso that not over 3 R groups are hydrocarbyl, the total of n + m is 2 to 5, the total of n'"'"' + m'"'"' is 2 to 5, R'"'"' is alkylene, alkylidene, cycloalkylene or arylene, A is --O--, --NH-- or ##STR16## where R'"'"' is alkyl, aryl or cycloalkyl and x is the number of units in the polymer.

27. A polymer according to claim 26 wherein all the R groups are hydrogen.

28. A polymer according to claim 27 wherein A is NH of ##STR17##

29. A crosslinked polymer capable of forming a hydrogel, said crosslinked polymer having been prepared by reacting the polymer of claim 27 with a compound containing at least two functional groups capable of reacting with alcoholic hydroxyl groups, the amount of crosslinking agent being insufficient to destroy the hydrogel forming properties of the polymer.

30. A crosslinked polymer according to claim 29 capable of adsorbing at least 20 weight percent of water.

31. A hydrogel of the polymer of claim 30.

32. A polymer containing a:

##STR18## group prepared by heating a polymer according to claim 27 having repeating units of the formula;

##STR19## where x is the number of units in the polymer.

35. A hydrogel of a thermoplastic hydrophilic polymer having hydroxyl groups and capable of forming a hydrogel, said polymer being a condensation product of (1) a spirolactone of the formula:

##STR20## where the total of n and m is 2 to 5 and the total of n'"'"' and m'"'"' is 2 to 5 and the R groups are H or hydrocarbyl with the proviso that not over 3 R groups are hydrocarbyl with (2) a difunctional compound capable of opening the lactone ring having two groups capable of opening the lactone ring which groups are selected from the group consisting of primary amino, secondary amino, alcoholic hydroxy and phenolic hydroxyl.

36. A hydrogel according to claim 35 wherein the spirolactone is 4,4-spirobibutyrolactone.

37. A hydrogel according to claim 36 wherein the spirolactone and (2) are employed in the mole ratio of 1:

1.

38. A hydrogel according to claim 35 wherein (1) and (2) are employed in the mole ratio of 1:

1.