(Meth)acrylic esters of polyalkoxylated glycerine

• US 20050165208A1
• Filed: 06/10/2003
• Published: 07/28/2005
• Est. Priority Date: 06/11/2002
• Status: Abandoned Application

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Popp, Andreas A, Kaworek, Thomas, Riegel, Ulrich, Schwalm, Reinhold, Daniel, Thomas, Weismantel, Matthias, Funk, Rudiger, Schroder, Jurgen
• Application Number:
  US10/516,702
• Publication Number:
  US 20050165208A1
• Time in Patent Office: Days
• US Class Current: 528/300
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C08G 2650/58 Ethylene oxide or propylene oxide copolymers, e.g. pluronics
• CPC Class Codes: C08G 65/2609 containing aliphatic hydroxyl groups
• CPC Class Codes: C08G 65/3322 acyclic

Abstract

The present invention relates to novel (meth)acrylic esters of polyalkoxylated glycerol, a simplified process for preparing these esters and the use of reaction mixtures thus obtainable.

Claims

1. An ester F of formula Ia

4. The ester F of claim 1 wherein m1+m2+m3+n1+n2+n3 or p1+p2+p3 is equal to 3 or 5.

5. The ester F of claim 1 wherein 3 POs are present in total.

6. The ester F of claim 1 wherein at least one PO is present in each of the 3 alkoxy chains of glycerol.

7. A process for preparing an ester F of claim 1 from an alkoxylated glycerol of the formula IIa, IIb, or IIc

8. The process of claim 7 wherein

a molar excess of (meth)acrylic acid to alkoxylated glycerol is at least 3.15:

1 and

the optionally neutralized (meth)acrylic acid present in the reaction mixture after the last process step substantially remains in the reaction mixture.

10. The process of claim 7 wherein the (meth)acrylic acid is not more than 75% by weight re-moved from the reaction mixture obtained after the last process step, which reaction mixture contains the ester F.

11. The process of claim 7 wherein the reaction mixture obtained after the last process step, which comprises the ester F, has a DIN EN 3682 acid number of at least 25 mg of KOH/g.

12. The process of claim 7 wherein the reaction mixture obtained after the last process step, which comprises the ester F, has a (meth)acrylic acid content of at least 0.5% by weight.

13. The process of claim 7 wherein the molar ratio of (meth)acrylic acid to alkoxylated glycerol in step a) is at least 15:

1.

14. The process for preparing a crosslinked hydrogel, comprising the steps of

k) polymerizing an ester F of claim 1 or an ester F of the formula Ia

wherein AO is for each AO independently EO or PO,

EO is O—

CH2—

CH2—

,

PO is at each instance independently O—

CH2—

CH(CH3)—

or O—

CH(CH3)—

CH2—

p1+p2+p3 is 3, 4, or 5,

R1, R2, and R3 are independently H or CH3,

with (meth)acrylic acid, optionally an additional monoethylenically unsaturated compound N, and optionally one further copolymerizable hydrophilic monomer M, in the presence of at least one free-radical initiator K and optionally of at least one grafting base L,

l) optionally postcrosslinking the reaction mixture obtained from k),

m) drying the reaction mixture obtained from k) or l), and

n) optionally grinding and/or sieving the reaction mixture obtained from k), l), or m).

15. The process of claim 14 wherein AO is EO.

16. The process for preparing a crosslinked hydrogel, comprising steps a) to i) of claim 7 and additionally

k) polymerizing the reaction mixture from one of stages a) to i) if performed, with an optionally additional monoethylenically unsaturated compound N, and optionally at least one further co-polymerizable hydrophilic monomer M, in the presence of at least one free-radical initiator K and optionally at least one grafting base L,

l) optionally postcrosslinking the reaction mixture obtained from k),

m) drying the reaction mixture obtained from k) or l), and

n) optionally grinding and/or sieving the reaction mixture obtained from k), l), or m).

17. A polymer prepared by the process of claim 14.

18. A crosslinked hydrogel comprising at least one hydrophilic monomer M in polymerized form crosslinked with an ester F of claim 1 or an ester F of formula Ia

21. A composition comprising

from 0.1% to 40% by weight of at least one ester F of claim 1 or an ester F of formula Ia

wherein AO is for each AO independently EO or PO,

EO is O—

CH2—

CH2—

p1+p2+p3 is 3, 4, or 5,

R1, R2, and R3 are independently H or CH3,

and (meth)acrylic acid,

0.5-99.9% by weight of at least one hydrophilic monomer M,

0-10% by weight of at least one esterification catalyst C,

0-5% by weight of at least one polymerization inhibitor D, and

0-10% by weight of a solvent E,

with the proviso that the sum total is always 100% by weight.

22. The composition of claim 21 further comprising a diluent G.

23. A crosslinked hydrogel prepared from a composition of claim 21 and optionally postcrosslinked.

26. A crosslinked hydrogel of claim 17 having a saponification index of less than 11.

27. A crosslinked hydrogel of claim 17 having a residual crosslinker content of less than 10 ppm.

29. An article comprising a polymer pared according to the method of claim 14.

30. The article of claim 29 selected from the group consisting of a hygiene article, a packaging material, and a nonwoven.

32. The crosslinked hydrogel of claim 26 having a saponification index of less than 8.

33. The crosslinked hydrogel of claim 26 having a saponification index of less than 5.

34. The crosslinked hydrogel of claim 27 having a residual crosslinker content of less than 5 ppm.

2. (canceled)

3. (canceled)

9. (canceled)

19. (canceled)

20. (canceled)

24. (canceled)

25. A crosslinked hydrogel having a saponification index of less than 10.

31. The crosslinked hydrogel of claim 25 having a saponification index of less than 8.

28. (canceled)