Method for the production of esters of polyalcohols

• US 7,250,481 B2
• Filed: 06/06/2003
• Issued: 07/31/2007
• Est. Priority Date: 06/11/2002
• Status: Expired due to Fees

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Koeniger, Rainer, Schwalm, Reinhold, Daniel, Thomas, Jaworek, Thomas, Wolf, Lothar, Wickel, Stefan, Hartmann, Gabriele
• Primary Examiner(s): Wu; David W.
• Assistant Examiner(s): Bernshteyn; M.
• Application Number:
  US10/514,569
• Publication Number:
  US 20050176910A1
• Time in Patent Office: 1,516 Days
• Field of Search: 526/317.1, 526/318.4, 526/318.43, 526/323.1, 526/323.2, 526/321, 560/205
• US Class Current: 526/321
• 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 65/3322 acyclic

Abstract

Unsaturated acids are esterified with polyalcohols. The resulting reaction mixtures have utility.

Claims

1. A process for preparing a crosslinked hydrogel, which comprises

a) reacting at least one polyalcohol A with at least one ethylenically unsaturated carboxylic acid B in the presence of at least one esterification catalyst C and of at least one polymerization inhibitor D and also optionally of a water-azeotroping solvent E to form an ester F,

b) optionally removing some or all of the water formed in a) from the reaction mixture during and/or after a),

f) optionally neutralizing the reaction mixture,

h) optionally removing any solvent E by distillation and/or

i) stripping with a reaction-inert gas,

k) polymerizing the reaction mixture from one of a) to i), in the presence of at least one radical initiator K and of optionally at least one grafting base L, with optionally at least one additional monoethylenically unsaturated compound bearing no acid groups N and also optionally at least one further copolymerizable hydrophilic monomer M, wherein ester F acts as a crosslinker, whereby a crosslinked hydrogel is formed,

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), wherein said ethylenically unsaturated carboxylic acid B is present in a molar excess to said polyalcohol A per hydroxyl group to be esterified in A of at least 2.5:

1, and the optionally neutralized carboxylic acid B in the reaction mixture obtained after step i) substantially remains in said reaction mixture.

2. The process as claimed in claim 1, wherein not more than 75% by weight of said carboxylic acid B is removed from said reaction mixture obtained after the last of steps a) to i), said reaction mixture containing said ester F.

3. The process as claimed in claim 1, wherein said reaction mixture obtained after the last of steps a) to i), which comprises said ester F, has a DIN EN 3682 acid number of at least 25 mg of KOH/g.

4. The process as claimed in claim 1, wherein said reaction mixture obtained after the last of steps a) to i), which comprises said ester F, contains at least 0.5% by weight of said carboxylic acid B.

5. The process as claimed in claim 1, wherein said polyalcohol A is a polyol which comprises an additional functionality, said additional functionality being at least one ether, carboxyl or C₁–

C₄-alkyloxycarbonyl function.

6. The process as claimed in claim 1, wherein said polyalcohol A is a polyol selected from the group consisting of ditrimethylolpropane, dipentaerythritol, dimethylolpropionic acid, dimethylolbutyric acid, and mixtures thereof.

7. The process as claimed in claim 1, wherein at least one polyalcohol A is selected from the group consisting of polyols, functionalized polyols, alkoxylated polyols, sugar alcohols, partially alkoxylated sugar alcohols, polyetherols, polyesterols, partially or fully alkoxylated polyesterols, partially or fully hydrolyzed alkoxylated polyesterols, and mixtures thereof.

8. The process as claimed in claim 1, wherein said polyalcohol A is a polyol which has been quadruply ethoxylated per hydroxyl group.

9. The process as claimed in claim 8, wherein said polyol is trimethylolpropane or pentaerythritol.

10. The process as claimed in claim 1, wherein said polyalcohol A is a from 3- to 4-tuply ethoxylated glycerol.

11. The process as claimed in claim 1, wherein said ester F in reaction step k) has a degree of esterification (based on the n-hydric polyalcohol A used) of at least 2 and less than n.

12. The process as claimed in claim 1, wherein said polyalcohol has the formula VIIa

R⁸—

(O(CH(R¹⁰)CH(R¹⁰)O)_y—

H)_x 

 

(VIIa),

where

R⁸ is a polyvalent straight-chain or branched C₂–

C₁₀-alkyl radical,

R¹⁰ is independently in each occurrence hydrogen or methyl,

x is independently in each occurrence a positive integer of 2 or greater, and

y is independently in each occurrence a number from 3 to 8 for x=2 and a number from 2 to 7 for x=3 or greater.

13. The process as claimed in claim 12, wherein

R₁₀ is hydrogen and

y is independently in each occurrence a positive integer from 1 to 6 for each x.

14. The process as claimed in claim 12, wherein

R₁₀ is hydrogen and

y is independently in each occurrence a positive integer from 1 to 4 for each x.

15. The process as claimed in claim 12, wherein

R₁₀ is hydrogen and

y is independently in each occurrence a positive integer of more than 8 for x=2 and

y is independently in each occurrence a positive integer of more than 7 for x=3 or greater.

16. The process as claimed in claim 12, wherein

R₁₀ is hydrogen and

y is independently in each occurrence a positive integer of 15 or more for each x.

17. The process as claimed in claim 1, wherein the molar ratio of said at least one ethylenically unsaturated carboxylic acid B to said polyalcohol A in said reaction a) is at least 5:

1, based on the hydroxyl groups of said polyalcohol A.

22. The process as claimed in claim 1, wherein said ethylenically unsaturated carboxylic acid B is present in a molar excess to said polyalcohol A per hydroxyl group to be esterified in A of at least 5:

1.

23. The process as claimed in claim 1, wherein said ethylenically unsaturated carboxylic acid B is present in a molar excess to said polyalcohol A per hydroxyl group to be esterified in A of at least 100:

1.

24. The process as claimed in claim 1, wherein excess ethylenically unsaturated carboxylic acid B is not substantially removed after the last steps a) to i).

25. The process as claimed in claim 1, wherein excess esterification catalyst C is not substantially removed after the last steps a) to i).

26. The process as claimed in claim 1, wherein the polymerization inhibitor is an aerobic polymerization inhibitor.

27. The process as claimed in claim 1, wherein step k) is carried out in a protective, nitrogen gas containing atmosphere.

28. The process as claimed in claim 1, wherein radical initiator K is a peroxide or an azo compound.

29. The process as claimed in claim 1, wherein step k) is carried out with an ester F concentration of 0.01–

5% by weight, based on the amount of polymerizable monomers present.

30. The process as claimed in claim 29, wherein the concentration is 0.1–

0.75% by weight.

18. A crosslinked hydrogel comprising a copolymer obtained by crosslinking at least one hydrophilic monomer M or a copolymer thereof with a compound of the formula

R⁸—

(O(CH(R¹⁰)CH(R¹⁰)O)_y—

C(═

O)—

R⁹)_x 

 

(VII),

where

R⁸ is a polyvalent straight-chain or branched C₂–

C₁₀-alkyl radical,

R⁹ is independently in each occurrence a straight-chain or branched C₂–

C₁₀-alkenyl radical,

R₁₀ is independently in each occurrence hydrogen or methyl,

x is independently in each occurrence a positive integer of 2 or greater, and

y is independently in each occurrence a number greater than 8 for x=2 and a number greater than 7 for x=3 or greater.

19. A crosslinked hydrogel comprising a copolymer obtained by crosslinking at least one hydrophilic monomer M or a copolymer thereof with an ester F of a polyalcohol A with at least one ethylenically unsaturated carboxylic acid B, said polyalcohol A being selected from the group consisting of a polyol which comprises an additional functionality, said additional functionality being at least one carboxyl or C₁–

C₄-alkyloxycarbonyl function, sugar alcohols, partially alkoxylated sugar alcohols, polyesterols, partially or fully alkoxylated polyesterols and partially or fully hydrolyzed alkoxylated polyesterols.

20. A crosslinked hydrogel comprising a copolymer obtained by crosslinking at least one hydrophilic monomer M or a copolymer thereof with an ester F of a polyalcohol A with at least one ethylenically unsaturated carboxylic acid B, said polyalcohol A being selected from the group consisting of ditrimethylolpropane, dipentaerythritol, dimethylolpropionic acid and dimethylolbutyric acid.

21. A crosslinked hydrogel comprising at least one hydrophilic monomer M in interpolymerized form, crosslinked with a reaction mixture comprising an ester F of a polyalcohol A with at least one ethylenically unsaturated carboxylic acid B, said reaction mixture being obtained by reaction of a polyalcohol A with at least one

a) ethylenically unsaturated carboxylic acid B in the presence of at least one esterification catalyst C and of at least one polymerization inhibitor D and also optionally of a water-azeotroping solvent E to form an ester F,

b) optionally removing some or all of the water formed in a) from the reaction mixture during and/or after a),

f) optionally neutralizing the reaction mixture,

h) optionally removing any solvent E by distillation and/or

i) stripping with a reaction-inert gas,

wherein

said ethylenically unsaturated carboxylic acid B is present in a molar excess to said polyalcohol A per hydroxyl group to be esterified in A of at least 2.5:

1, and

the optionally neutralized carboxylic acid B in the reaction mixture obtained after the last step substantially remains in said reaction mixture.