(Meth)acrylic esters of polyalkoxylated trimethylolpropane

• US 20050215752A1
• Filed: 06/06/2003
• Published: 09/29/2005
• Est. Priority Date: 06/11/2002
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Riegel, Ulrich, Schwalm, Reinhold, Daniel, Thomas, Jaworek, Thomas, Weismantel, Matthias, Funk, Rudiger, Popp, Andreas, Schroder, Jurgen
• Granted Patent: US 7,199,211 B2
• Time in Patent Office: Days
• US Class Current: 528/272
• 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 65/2609 containing aliphatic hydroxyl groups
• CPC Class Codes: C08G 65/3322 acyclic
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component

Abstract

The present invention relates to novel (meth)acrylic esters of polyalkoxylated trimethylolpropane of the formula where AO is for each AO independently at each instance EO, PO or BO where EO is O—CH2-CH2- PO is independently at each instance O—CH2-CH(CH3)- or O—CH(CH3)-CH2- BO is independently at each instance O—CH2-CH(CH2-CH3)- or O—CH(CH2-CH3)-CH2- p1+p2+p3 is 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74 or 75, R1, R2 and R3 are independently H or CH3, a simplified process for preparing these esters and the use of reaction mixtures thus obtainable.

Claims

1. An ester F of formula Ib

3. The ester F of claim 1 wherein n1, n2, and n3 are independently 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

4. The ester F of claim 1 wherein m1, m2, and m3 are independently 1, 2, 3, 4, or 5.

5. The ester F of claim 1 wherein m1+m2+m3 is 5 or 10.

6. The ester F of claim 1 wherein n1+n2+n3 is 30 or 50.

7. The ester F of claim 1 wherein R1, R2, and R3 are identical.

8. A process for preparing an ester F of claim 1 from an alkoxylated trimethylolpropane of the formula IIb or IIc

9. The process of claim 8 wherein

a molar excess of (meth)acrylic acid to alkoxylated trimethylolpropane 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.

11. The process of claim 8 wherein the (meth)acrylic acid is not more than 75% by weight removed from the reaction mixture obtained after the process last step, which reaction mixture contains the ester F.

12. The process of claim 8 wherein the reaction mixture obtained after the process last step, which contains the ester F, has a DIN EN 3682 acid number of at least 25 mg of KOH/g.

13. The process of claim 8 wherein the reaction mixture obtained after the process last step, which contains the ester F, has a (meth)acrylic acid content of at least 0.5% by weight.

14. The process of claim 8 wherein the molar ratio of (meth)acrylic acid to alkoxylated trimethylolpropane in step a) is at least 15:

1.

15. A process for preparing a crosslinked hydrogel, comprising the steps of

k) polymerizing an ester F of claim 1 with (meth)acrylic acid, and an optional additional monoethylenically unsaturated compound N and optionally at least one further copolymerizable hydrophilic monomer M, in the presence of at least one free-radical initiator K and optionally of at least one grating 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).

16. The process for preparing a crosslinked hydrogel comprising steps a) to i) of claim 8 and additionally

k) polymerizing the reaction mixture from one of steps a) to i) if performed, with an optional additional monoethylenically unsaturated compound N and optionally at least 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).

17. A crosslinked hydrogel prepared according to the process of claim 15.

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

19. A crosslinked hydrogel containing at least one hydrophilic monomer M in polymerized form crosslinked with a reaction mixture which contains an ester F and is prepared according to the process of claim 8.

21. A composition comprising

from 0.1% to 40% by weight of at least one ester F of claim 1 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 additionally

optionally postcrosslinked.

25. A crosslinked hydrogel of claim 18 having a residual crosslinker content of less than 10 ppm.

27. The ester F of claim 1 wherein R1, R2, and R3 are H.

32. An article comprising a crosslinked hydrogel of claim 18.

33. The article of claim 32 selected from the group consisting of a hygiene article, a packaging material, and a nonwoven.

34. The crosslinked hydrogel of claim 25 having a residual crosslinked content of less than 5 ppm.

2. (cancelled)

10. A process for preparing an ester F of alkoxylated trimethylolpropane of the formula IIa

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

29. The process of claim 10 wherein the reaction mixture obtained after the last process step, which contains the ester F, has a DIN EN 3682 acid number of at least 25 mg of KOH/g.

30. The process of claim 10 wherein the reaction mixture obtained after the last process step, which contains the ester F, has a (meth)acrylic acid content of at least 0.5% by weight.

31. The process of claim 10 wherein the molar ratio of (meth)acrylic acid to alkoxylated trimethylolpropane in step a) is at least 15:

1.

35. A process for preparing a crosslinked hydrogel, comprising the steps of

k) polymerizing an ester F of claim 10 with (meth)acrylic acid and an optional additional monoethylenically unsaturated compound N and optionally at least one further copolymerizable hydrophilic monomer M, in the presence of at least one free-radical initiator K and optionally of at least one grating 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).

20. (cancelled)

24. (cancelled)

26. (cancelled)