GLYCEROL (METH)ACRYLATE CARBOXYLIC ESTER HAVING A LONG SHELF LIFE

Abstract

The present invention describes storage-stable glycerol (meth)acrylate carboxylic esters and a method for preparing these esters.

Claims

1-14. (canceled)

15. Storage stable glycerol (meth)acrylate carboxylic esters of formula (I): ##STR00007## wherein: R.sub.1=H or CH.sub.3; R.sub.2=hydrogen, or aliphatic carbons with C1 to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with C1 to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, O or P, or unsaturated aliphatic carbon compounds with C2 to C30; and wherein carboxylic acids of formula (II): ##STR00008## wherein: R.sub.2=hydrogen, or aliphatic carbons with C1 to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with C1 to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, O or P, or unsaturated aliphatic carbon compounds with C2 to C30; and carboxylic acids of the formula (III): ##STR00009## wherein: R.sub.3=hydrogen, or aliphatic carbons with Cl to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with Cl to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, 0 or P, or unsaturated aliphatic carbon compounds with C2 to C30, individually or in mixtures; and optionally any further Broensted acids foreign to the system; are present in sum total in a molar excess to the glycidyl (meth)acrylate present.

16. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein the excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.001:1 to 5:1 at the end of the addition of the reactants.

17. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein an excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.01:1 to 2:1 at the end of the addition of the reactants.

18. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein an excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.02:1 to 1.5:1 at the end of the addition of the reactants.

19. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein any desired acid and glycidyl (meth)acrylate are present in a molar ratio of from 1.001:1 to 5:1 in the product at the beginning of the storage.

20. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein the carboxylic acids of formula II are (meth)acrylic acid.

21. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 15, wherein the carboxylic acids of both formula II and formula III are (meth)acrylic acid.

22. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 21, wherein the excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.001:1 to 5:1 at the end of the addition of the reactants.

23. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 21, wherein an excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.01:1 to 2:1 at the end of the addition of the reactants.

24. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 21, wherein an excess of any mixtures of the carboxylic acids according to formula (II) and (III) are present in a molar ratio of from 1.02:1 to 1.5:1 at the end of the addition of the reactants.

25. Storage stable glycerol (meth)acrylate carboxylic esters of formula (I): ##STR00010## wherein: R.sub.1=H or CH.sub.3; R.sub.2=hydrogen, or aliphatic carbons with C1 to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with C1 to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, O or P, or unsaturated aliphatic carbon compounds with C2 to C30; and wherein carboxylic acids of the formula (II): ##STR00011## wherein: R.sub.2=hydrogen, or aliphatic carbons with C1 to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with Cl to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, O or P, or unsaturated aliphatic carbon compounds with C2 to C30; and optionally carboxylic acids of the formula (III): ##STR00012## wherein: R.sub.3=hydrogen, or aliphatic carbons with C1 to C30, or aliphatic cyclic carbon compounds having a ring size of C4 to C8, unsubstituted or substituted by N, S, O or P, or halogenated aliphatic carbon compounds with C1 to C8, or aromatic carbon compounds, or heteroaromatic carbon compounds substituted by N, S, O or P or unsaturated aliphatic carbon compounds with C2 to C30, individually or in mixtures; and optionally any further Broensted acids foreign to the system; are present in sum total in a molar excess to the glycidyl (meth)acrylate present at the beginning of storage.

26. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.001:1 to 5:1 at the beginning of the storage.

27. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.01:1 to 2:1, at the beginning of the storage.

28. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.02:1 to 1.5:1, at the beginning of the storage.

29. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein any desired acid and glycidyl (meth)acrylate are present in a molar ratio of from 1.001:1 to 5:1 in the product at the beginning of the storage.

30. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein the carboxylic acids of formula II are (meth)acrylic acid.

31. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 25, wherein the carboxylic acids of both formula II and formula III are (meth)acrylic acid.

32. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 31, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.001:1 to 5:1 at the beginning of the storage.

33. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 31, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.01:1 to 2:1, at the beginning of the storage.

34. The storage-stable glycerol (meth)acrylate carboxylic esters of claim 31, wherein an excess of any mixtures of the carboxylic acids according to formula (III) is present in a molar ratio to the remaining glycidyl (meth)acrylate of from 1.02:1 to 1.5:1, at the beginning of the storage.

Description

EXAMPLES

[0068] The carboxylic acid, 0.05 g of hydroquinone monomethyl ether and 9.60 g of benzyltriethylammonium chloride as catalyst were initially charged and heated to 90° C. in a 11 Witt's flask with oil circulation, bottom outlet valve, porcelain blade stirrer with stirrer motor, 500 ml addition funnel as well as a thermometer and air inlet. At 90-91 ° C., 300 g of glycidyl (meth)acrylate are added over a period of 60 minutes. At the end of the addition, the mixture is heated to 97° C., the temperature briefly increasing here to a maximum of 100° C. The mixture is maintained at 97° C. for 10 h, then cooled and discharged. From the product thus obtained, storage stability tests were carried out at 30 and 50° C. in order to establish the tendency of the product toward disproportionation.

Preparation Example 1

[0069] Method is distinguished in that 179 g of methacrylic acid is used as carboxylic acid.

[0070] Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

TABLE-US-00001 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.1% 81.7% 53.0% 48.7% 48.4% Triester content [%] max. 3.00  1.6%  5.4% 28.1% 33.3% 33.7% Methacrylic acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.78% n.d. n.d. n.d. n.d.

TABLE-US-00002 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.1% 49.0% 46.8% 47.2% 47.0% Triester content [%] max. 3.00  1.6% 31.9% 33.6% 33.8% 33.6% Methacrylic acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.78% n.d. n.d. n.d. n.d.

[0071] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 2

[0072] Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

[0073] Method is distinguished in that the procedure is carried out analogously to Example 1 but 181.7 g of methacrylic acid is used as carboxylic acid.

TABLE-US-00003 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 81.8% 53.1% 48.8% 48.5% Triester content [%] max. 3.00  1.8%  6.1% 31.5% 37.4% 37.8% Methacrylic acid [%] 0.42% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.72% n.d. n.d. n.d. n.d.

TABLE-US-00004 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 49.1% 46.9% 47.2% 47.1% Triester content [%] max. 3.00  1.8% 35.8% 37.7% 37.9% 37.6% Methacrylic acid [%] 0.42% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.72% n.d. n.d. n.d. n.d.

[0074] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 3

[0075] Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

[0076] Method is distinguished in that the procedure is carried out analogously to Example 1 but 185.3 g of methacrylic acid is used as carboxylic acid.

TABLE-US-00005 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.3% 90.0% 89.8% 89.9% 89.3% Triester content [%] max. 3.00  1.5%  1.5%  1.5%  1.6%  1.9% Methacrylic acid [%] 0.45% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.65% n.d. n.d. n.d. n.d.

TABLE-US-00006 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.3% 89.4% 89.3% 88.7% 87.2% Triester content [%] max. 3.00  1.5%  1.7%  2.0%  2.6%  3.0% Methacrylic acid [%] 0.45% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.65% n.d. n.d. n.d. n.d.

[0077] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 8 months.

Preparation Example 4

[0078] Method is distinguished in that the procedure is carried out analogously to Example 1 but 124.8 g of acetic acid is used as carboxylic acid.

[0079] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00007 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.8% 82.4% 53.5% 49.1% 48.8% Triester content [%] max. 3.00  1.7%  5.8% 29.7% 35.3% 35.7% Acetic acid [%] 0.31% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.88% n.d. n.d. n.d. n.d.

TABLE-US-00008 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.8% 49.5% 47.3% 47.6% 47.4% Triester content [%] max. 3.00  1.7% 33.8% 35.6% 35.8% 35.5% Acetic acid [%] 0.31% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.88% n.d. n.d. n.d. n.d.

[0080] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 5

[0081] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0082] Method is distinguished in that the procedure is carried out analogously to Example 1 but 126.7 g of acetic acid is used as carboxylic acid.

TABLE-US-00009 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 82.5% 53.6% 49.2% 48.9% Triester content [%] max. 3.00  1.8%  6.1% 31.3% 37.2% 37.6% Acetic acid [%] 0.33% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.81% n.d. n.d. n.d. n.d.

TABLE-US-00010 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 49.6% 47.3% 47.7% 47.5% Triester content [%] max. 3.00  1.8% 35.7% 37.5% 37.7% 37.5% Acetic acid [%] 0.33% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.81% n.d. n.d. n.d. n.d.

[0083] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 6

[0084] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0085] Method is distinguished in that the procedure is carried out analogously to Example 1 but 129.3 g of acetic acid is used as carboxylic acid.

TABLE-US-00011 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.4% 90.1% 89.9% 90.0% 89.3% Triester content [%] max. 3.00  1.7%  1.8%  1.7%  1.9%  2.2% Acetic acid [%] 0.35% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.73% n.d. n.d. n.d. n.d.

TABLE-US-00012 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.4% 89.5% 89.4% 88.8% 87.3% Triester content [%] max. 3.00  1.7%  2.1%  2.4%  3.0%  3.5% Acetic acid [%] 0.35% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.73% n.d. n.d. n.d. n.d.

[0086] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 7

[0087] Method is distinguished in that the procedure is carried out analogously to Example 1 but 183.2 g of butyric acid is used as carboxylic acid.

[0088] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00013 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.0% 81.6% 53.0% 48.7% 48.4% Triester content [%] max. 3.00  1.8%  6.2% 31.9% 37.9% 38.3% Butyric acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.78% n.d. n.d. n.d. n.d.

TABLE-US-00014 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.0% 49.0% 46.8% 47.1% 47.0% Triester content [%] max. 3.00  1.8% 36.3% 38.2% 38.4% 38.1% Butyric acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.78% n.d. n.d. n.d. n.d.

[0089] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 8

[0090] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0091] Method is distinguished in that the procedure is carried out analogously to Example 1 but 186 g of butyric acid is used as carboxylic acid.

TABLE-US-00015 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 82.6% 53.6% 49.3% 49.0% Triester content [%] max. 3.00  1.9%  6.4% 33.2% 39.4% 39.8% Butyric acid [%] 0.42% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.71% n.d. n.d. n.d. n.d.

TABLE-US-00016 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 49.6% 47.4% 47.7% 47.5% Triester content [%] max. 3.00  1.9% 37.8% 39.7% 39.9% 39.7% Butyric acid [%] 0.42% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.71% n.d. n.d. n.d. n.d. [%]

[0092] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 9

[0093] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0094] Method is distinguished in that the procedure is carried out analogously to Example 1 but 189.7 g of butyric acid is used as carboxylic acid.

TABLE-US-00017 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.9% 89.6% 89.4% 89.5% 88.9% Triester content [%] max. 3.00  1.7%  1.8%  1.7%  1.9%  2.2% Butyric acid [%] 0.46% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.64% n.d. n.d. n.d. n.d. [%]

TABLE-US-00018 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.9% 89.1% 88.9% 88.4% 86.9% Triester content [%] max. 3.00  1.7%  2.0%  2.4%  3.0%  3.5% Butyric acid [%] 0.46% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.64% n.d. n.d. n.d. n.d. [%]

[0095] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 10

[0096] Method is distinguished in that the procedure is carried out analogously to Example 1 but 591.4 g of stearic acid is used as carboxylic acid.

[0097] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00019 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 82.5% 53.5% 49.2% 48.9% Triester content [%] max. 3.00  1.3%  4.2% 21.7% 25.8% 26.1% Stearic acid [%] 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.42% n.d. n.d. n.d. n.d. [%]

TABLE-US-00020 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 49.6% 47.3% 47.7% 47.5% Triester content [%] max. 3.00  1.3% 24.7% 26.0% 26.2% 26.0% Stearic acid [%] 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.42% n.d. n.d. n.d. n.d. [%]

[0098] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 11

[0099] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0100] Method is distinguished in that the procedure is carried out analogously to Example 1 but 600.4 g of stearic acid is used as carboxylic acid.

TABLE-US-00021 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 81.7% 53.0% 48.8% 48.5% Triester content [%] max. 3.00  1.7%  5.7% 29.4% 34.9% 35.2% Stearic acid [%] 0.74% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.39% n.d. n.d. n.d. n.d. [%]

TABLE-US-00022 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 49.1% 46.9% 47.2% 47.1% Triester content [%] max. 3.00  1.7% 33.4% 35.1% 35.3% 35.1% Stearic acid [%] 0.74% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.39% n.d. n.d. n.d. n.d. [%]

[0101] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 12

[0102] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0103] Method is distinguished in that the procedure is carried out analogously to Example 1 but 612.4 g of stearic acid is used as carboxylic acid.

TABLE-US-00023 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.9% 87.6% 87.4% 87.5% 86.9% Triester content [%] max. 3.00  1.6%  1.7%  1.6%  1.8%  2.0% Stearic acid [%] 0.79% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.35% n.d. n.d. n.d. n.d. [%]

TABLE-US-00024 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.9% 87.1% 86.9% 86.4% 84.9% Triester content [%] max. 3.00  1.6%  1.9%  2.2%  2.8%  3.3% Stearic acid [%] 0.79% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.35% n.d. n.d. n.d. n.d. [%]

[0104] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 13

[0105] Method is distinguished in that the procedure is carried out analogously to Example 1 but 253.9 g of benzoic acid is used as carboxylic acid.

[0106] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00025 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 81.8% 53.1% 48.8% 48.5% Triester content [%] max. 3.00  1.7%  5.8% 30.1% 35.7% 36.1% Benzoic acid [%] 0.49% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.68% n.d. n.d. n.d. n.d. [%]

TABLE-US-00026 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 86.2% 49.1% 46.9% 47.2% 47.1% Triester content [%] max. 3.00  1.7% 34.2% 36.0% 36.2% 36.0% Benzoic acid [%] 0.49% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.68% n.d. n.d. n.d. n.d. [%]

[0107] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 14

[0108] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0109] Method is distinguished in that the procedure is carried out analogously to Example 1 but 257.7 g of benzoic acid is used as carboxylic acid.

TABLE-US-00027 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.1% 83.6% 54.3% 49.9% 49.6% Triester content [%] max. 3.00  1.6%  5.4% 27.8% 33.1% 33.4% Benzoic acid [%] 0.51% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.62% n.d. n.d. n.d. n.d. [%]

TABLE-US-00028 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.1% 50.2% 48.0% 48.3% 48.1% Triester content [%] max. 3.00  1.6% 31.7% 33.3% 33.5% 33.3% Benzoic acid [%] 0.51% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.62% n.d. n.d. n.d. n.d. [%]

[0110] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 15

[0111] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0112] Method is distinguished in that the procedure is carried out analogously to Example 1 but 262.9 g of benzoic acid is used as carboxylic acid.

TABLE-US-00029 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.3% 89.0% 88.8% 88.9% 88.3% Triester content [%] max. 3.00  1.2%  1.3%  1.2%  1.4%  1.6% Benzoic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.56% n.d. n.d. n.d. n.d. [%]

TABLE-US-00030 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.3% 88.5% 88.3% 87.8% 86.3% Triester content [%] max. 3.00  1.2%  1.5%  1.7%  2.2%  2.5% Benzoic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.56% n.d. n.d. n.d. n.d. [%]

[0113] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 8 months.

Preparation Example 16

[0114] Method is distinguished in that the procedure is carried out analogously to Example 1 but 287.1 g of salicylic acid as carboxylic acid and a solvent are used. Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00031 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.7% 84.2% 54.6% 50.2% 49.9% Triester content [%] max. 3.00  1.4%  4.7% 24.1% 28.6% 28.9% Salicylic acid [%] 0.52% n.d. n.d. n.d. n.d. Glycidyl 0.64% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00032 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.7% 50.6% 48.3% 48.6% 48.5% Triester content [%] max. 3.00  1.4% 27.4% 28.8% 29.0% 28.8% Salicylic acid [%] 0.52% n.d. n.d. n.d. n.d. Glycidyl 0.64% n.d. n.d. n.d. n.d. methacrylate [%]

[0115] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 17

[0116] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0117] Method is distinguished in that the procedure is carried out analogously to Example 1 but 291.5 g of salicylic acid as carboxylic acid and a solvent are used.

TABLE-US-00033 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.6% 85.0% 55.2% 50.7% 50.4% Triester content [%] max. 3.00  1.8%  6.2% 32.0% 37.9% 38.4% Salicylic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl 0.59% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00034 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.6% 51.1% 48.8% 49.1% 48.9% Triester content [%] max. 3.00  1.8% 36.4% 38.2% 38.5% 38.2% Salicylic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl 0.59% n.d. n.d. n.d. n.d. methacrylate [%]

[0118] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 18

[0119] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0120] Method is distinguished in that the procedure is carried out analogously to Example 1 but 297.3 g of salicylic acid as carboxylic acid and a solvent are used.

TABLE-US-00035 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.7% 90.4.% 90.2% 90.4% 89.7% Triester content [%] max. 3.00  1.4%  1.5%  1.4%  1.6%  1.8% Salicylic acid [%] 0.59% n.d. n.d. n.d. n.d. Glycidyl 0.53% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00036 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.7% 89.9% 89.7% 89.2% 87.7% Triester content [%] max. 3.00  1.4%  1.7%  2.0%  2.5%  2.9% Salicylic acid [%] 0.59% n.d. n.d. n.d. n.d. Glycidyl 0.53% n.d. n.d. n.d. n.d. methacrylate [%]

[0121] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 8 months.

Preparation Example 19

[0122] Method is distinguished in that the procedure is carried out analogously to Example 1 but 255.9 g of nicotinic acid as carboxylic acid and a solvent are used.

[0123] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00037 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.6% 83.1% 53.9% 49.6% 49.3% Triester content [%] max. 3.00  1.6%  5.4% 27.9% 33.1% 33.5% Nicotinic acid [%] 0.49% n.d. n.d. n.d. n.d. Glycidyl 0.67% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00038 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.6% 49.9% 47.7% 48.0% 47.8% Triester content [%] max. 3.00  1.6% 31.7% 33.4% 33.5% 33.3% Nicotinic acid [%] 0.49% n.d. n.d. n.d. n.d. Glycidyl 0.67% n.d. n.d. n.d. n.d. methacrylate [%]

[0124] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 20

[0125] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0126] Method is distinguished in that the procedure is carried out analogously to Example 1 but 259.8 g of nicotinic acid as carboxylic acid and a solvent are used.

TABLE-US-00039 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 82.5% 53.6% 49.2% 48.9% Triester content [%] max. 3.00  1.8%  5.9% 30.7% 36.5% 36.9% Nicotinic acid [%] 0.51% n.d. n.d. n.d. n.d. Glycidyl 0.62% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00040 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 49.6% 47.3% 47.7% 47.5% Triester content [%] max. 3.00  1.8% 35.0% 36.8% 37.0% 36.7% Nicotinic acid [%] 0.51% n.d. n.d. n.d. n.d. Glycidyl 0.62% n.d. n.d. n.d. n.d. methacrylate [%]

[0127] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 21

[0128] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0129] Method is distinguished in that the procedure is carried out analogously to Example 1 but 265 g of nicotinic acid as carboxylic acid and a solvent are used.

TABLE-US-00041 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.2% 89.9% 89.7% 89.8% 89.2% Triester content [%] max. 3.00  2.0%  2.0%  2.0%  2.2%  2.5% Nicotinic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl 0.56% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00042 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.2% 89.3% 89.2% 88.6% 87.1% Triester content [%] max. 3.00  2.0%  2.3%  2.7%  3.0%  3.7% Nicotinic acid [%] 0.55% n.d. n.d. n.d. n.d. Glycidyl 0.56% n.d. n.d. n.d. n.d. methacrylate [%]

[0130] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 22

[0131] Method is distinguished in that the procedure is carried out analogously to Example 1 but 239.3 g of proline as carboxylic acid and a solvent are used.

[0132] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00043 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.6% 84.1% 54.6% 50.2% 49.9% Triester content [%] max. 3.00  1.9%  6.3% 32.6% 38.7% 39.1% Proline [%] 0.47% n.d. n.d. n.d. n.d. Glycidyl 0.70% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00044 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.6% 50.5% 48.2% 48.6% 48.4% Triester content [%] max. 3.00  1.9% 37.1% 39.0% 39.2% 39.0% Proline [%] 0.47% n.d. n.d. n.d. n.d. Glycidyl 0.70% n.d. n.d. n.d. n.d. methacrylate [%]

[0133] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 23

[0134] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0135] Method is distinguished in that the procedure is carried out analogously to Example 1 but 243 g of proline as carboxylic acid and a solvent are used.

TABLE-US-00045 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 84.4% 54.8% 50.4% 50.1% Triester content [%] max. 3.00  1.8%  5.9% 30.3% 36.0% 36.3% Proline [%] 0.50% n.d. n.d. n.d. n.d. Glycidyl 0.64% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00046 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 50.7% 48.4% 48.8% 48.6% Triester content [%]  max. 3.00  1.8% 34.5% 36.2% 36.4% 36.2% Proline [%] 0.50% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.64% n.d. n.d. n.d. n.d.

[0136] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 24

[0137] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0138] Method is distinguished in that the procedure is carried out analogously to Example 1 but 247.8 g of proline as carboxylic acid and a solvent are used.

TABLE-US-00047 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 86.3% 86.1% 86.2% 85.6% Triester content [%]  max. 3.00  1.1%  1.1%  1.1%  1.2%  1.4% Proline [%] 0.53% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.58% n.d. n.d. n.d. n.d.

TABLE-US-00048 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 85.7% 85.6% 85.1% 83.6% Triester content [%]  max. 3.00  1.1%  1.3%  1.5%  1.9%  2.2% Proline [%] 0.53% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.58% n.d. n.d. n.d. n.d.

[0139] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 25

[0140] Method is distinguished in that the procedure is carried out analogously to Example 1 but 149.8 g of acrylic acid is used as carboxylic acid.

[0141] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00049 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 84.4% 54.8% 50.4% 50.1% Triester content [%]  max. 3.00  1.4%  4.6% 23.8% 28.3% 28.6% Acrylic acid [%] 0.36% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.83% n.d. n.d. n.d. n.d.

TABLE-US-00050 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 50.7% 48.4% 48.8% 48.6% Triester content [%]  max. 3.00  1.4% 27.1% 28.5% 28.7% 28.5% Acrylic acid [%] 0.36% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.83% n.d. n.d. n.d. n.d.

[0142] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 26

[0143] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0144] Method is distinguished in that the procedure is carried out analogously to Example 1 but 152.1 g of acrylic acid is used as carboxylic acid.

TABLE-US-00051 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.2% 83.7% 54.3% 49.9% 49.6% Triester content [%]  max. 3.00  1.8%  6.0% 30.9% 36.7% 37.1% Acrylic acid [%] 0.37% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.77% n.d. n.d. n.d. n.d.

TABLE-US-00052 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.2% 50.3% 48.0% 48.3% 48.2% Triester content [%]  max. 3.00  1.8% 35.2% 37.0% 37.2% 36.9% Acrylic acid [%] 0.37% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.77% n.d. n.d. n.d. n.d.

[0145] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 27

[0146] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0147] Method is distinguished in that the procedure is carried out analogously to Example 1 but 155.1 g of acrylic acid is used as carboxylic acid.

TABLE-US-00053 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.3% 89.0% 88.8% 88.9% 88.3% Triester content [%]  max. 3.00  1.8%  1.9%  1.8%  2.0%  2.3% Acrylic acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.69% n.d. n.d. n.d. n.d.

TABLE-US-00054 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.3% 88.4% 88.3% 87.7% 86.2% Triester content [%]  max. 3.00  1.8%  2.2%  2.4%  2.7%  3.0% Acrylic acid [%] 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.69% n.d. n.d. n.d. n.d.

[0148] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 8 months.

Preparation Example 28

[0149] Method is distinguished in that the procedure is carried out analogously to Example 1 but 587.2 g of oleic acid is used as carboxylic acid.

[0150] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00055 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.6% 83.1% 53.9% 49.6% 49.3% Triester content [%]  max. 3.00  1.2%  4.1% 21.4% 25.4% 25.6% Oleic acid [%] 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.42% n.d. n.d. n.d. n.d.

TABLE-US-00056 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.6% 49.9% 47.7% 48.0% 47.8% Triester content [%]  max. 3.00  1.2% 24.3% 25.6% 25.7% 25.5% Oleic acid [%] 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.42% n.d. n.d. n.d. n.d.

[0151] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 29

[0152] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1 Method is distinguished in that the procedure is carried out analogously to Example 1 but 596.1 g of oleic acid is used as carboxylic acid.

TABLE-US-00057 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.1% 84.6% 54.9% 50.4% 50.2% Triester content [%]  max. 3.00  1.1%  3.8% 19.7% 23.4% 23.7% Oleic acid [%] 0.74% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.39% n.d. n.d. n.d. n.d.

TABLE-US-00058 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.1% 50.8% 48.5% 48.8% 48.7% Triester content [%]  max. 3.00  1.1% 22.5% 23.6% 23.8% 23.6% Oleic acid [%] 0.74% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.39% n.d. n.d. n.d. n.d.

[0153] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 30

[0154] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0155] Method is distinguished in that the procedure is carried out analogously to Example 1 but 608 g of oleic acid is used as carboxylic acid.

TABLE-US-00059 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.7% 88.4% 88.2% 88.3% 87.8% Triester content [%]  max. 3.00  1.4%  1.4%  1.4%  1.5%  1.8% Oleic acid [%] 0.79% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.35% n.d. n.d. n.d. n.d.

TABLE-US-00060 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.7% 87.8% 87.7% 87.1% 85.7% Triester content [%]  max. 3.00  1.4%  1.7%  1.9%  2.4%  2.8% Oleic acid [%] 0.79% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.35% n.d. n.d. n.d. n.d.

[0156] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 8 months.

Preparation Example 31

[0157] Method is distinguished in that the procedure is carried out analogously to Example 1 but 187.3 g of lactic acid is used as carboxylic acid.

[0158] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00061 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 84.4% 54.8% 50.4% 50.1% Triester content [%] max. 3.00  1.0%  3.5% 18.0% 21.4% 21.7% Lactic acid [%] 0.41% n.d. n.d. n.d. n.d. Glycidyl 0.77% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00062 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.0% 50.7% 48.4% 48.8% 48.6% Triester content [%] max. 3.00  1.0% 20.5% 21.6% 21.7% 21.6% Lactic acid [%] 0.41% n.d. n.d. n.d. n.d. Glycidyl 0.77% n.d. n.d. n.d. n.d. methacrylate [%]

[0159] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 32

[0160] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0161] Method is distinguished in that the procedure is carried out analogously to Example 1 but 190.1 g of lactic acid is used as carboxylic acid.

TABLE-US-00063 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.3% 84.8% 55.0% 50.6% 50.3% Triester content [%] max. 3.00  1.6%  5.2% 27.0% 32.1% 32.4% Lactic acid [%] 0.43% n.d. n.d. n.d. n.d. Glycidyl 0.71% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00064 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 89.3% 50.9% 48.6% 49.0% 48.8% Triester content [%] max. 3.00  1.6% 30.8% 32.3% 32.5% 32.3% Lactic acid [%] 0.43% n.d. n.d. n.d. n.d. Glycidyl 0.71% n.d. n.d. n.d. n.d. methacrylate [%]

[0162] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 33

[0163] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02 Method is distinguished in that the procedure is carried out analogously to Example 1 but 193.9 g of lactic acid is used as carboxylic acid.

TABLE-US-00065 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 86.3% 86.1% 86.2% 85.6% Triester content [%] max. 3.00  1.4%  1.4%  1.4%  1.5%  1.7% Lactic acid [%] 0.46% n.d. n.d. n.d. n.d. Glycidyl 0.64% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00066 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 85.7% 85.6% 85.1% 83.6% Triester content [%] max. 3.00  1.4%  1.6%  1.9%  2.4%  2.8% Lactic acid [%] 0.46% n.d. n.d. n.d. n.d. Glycidyl 0.64% n.d. n.d. n.d. n.d. methacrylate [%]

[0164] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 34

[0165] Method is distinguished in that the procedure is carried out analogously to Example 1 but 216.4 g of hydroxyisobutyric acid is used as carboxylic acid.

[0166] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00067 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 82.5% 53.6% 49.2% 48.9% Triester content [%] max. 3.00  1.7%  5.8% 30.2% 35.9% 36.2% Hydroxyisobutyric 0.45% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.73% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00068 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.0% 49.6% 47.4% 47.7% 47.5% Triester content [%] max. 3.00  1.7% 34.4% 36.1% 36.3% 36.1% Hydroxyisobutyric 0.45% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.73% n.d. n.d. n.d. n.d. methacrylate [%]

[0167] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 35

[0168] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0169] Method is distinguished in that the procedure is carried out analogously to Example 1 but 219.7 g of hydroxyisobutyric acid is used as carboxylic acid.

TABLE-US-00069 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.4% 83.0% 53.8% 49.5% 49.2% Triester content [%] max. 3.00  1.3%  4.4% 22.6% 26.8% 27.1% Hydroxyisobutyric 0.47% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.67% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00070 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.4% 49.8% 47.6% 47.9% 47.8% Triester content [%] max. 3.00  1.3% 25.7% 27.0% 27.2% 27.0% Hydroxyisobutyric 0.47% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.67% n.d. n.d. n.d. n.d. methacrylate [%]

[0170] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 36

[0171] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0172] Method is distinguished in that the procedure is carried out analogously to Example 1 but 224.1 g of hydroxyisobutyric acid is used as carboxylic acid.

TABLE-US-00071 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.1% 88.8% 88.6% 88.7% 88.1% Triester content [%] max. 3.00  1.7%  1.7%  1.7%  1.9%  2.1% Hydroxyisobutyric 0.50% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.60% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00072 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.1% 88.2% 88.1% 87.5% 86.0% Triester content [%] max. 3.00  1.7%  2.0%  2.3%  3.0%  3.4% Hydroxyisobutyric 0.50% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.60% n.d. n.d. n.d. n.d. methacrylate [%]

[0173] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 6 months.

Preparation Example 37

[0174] Method is distinguished in that the procedure is carried out analogously to Example 1 but 339.7 g of trichloroacetic acid is used as carboxylic acid.

[0175] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:0.985

TABLE-US-00073 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.5% 83.0% 53.9% 49.5% 49.2% Triester content [%] max. 3.00  1.4%  4.8% 25.0% 29.7% 30.0% Trichloroacetic 0.57% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.59% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00074 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 87.5% 49.8% 47.6% 47.9% 47.8% Triester content [%] max. 3.00  1.4% 28.4% 29.9% 30.1% 29.9% Trichloroacetic 0.57% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.59% n.d. n.d. n.d. n.d. methacrylate [%]

[0176] Conclusion: The product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition proved to be NOT storage-stable!

Preparation Example 38

[0177] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1

[0178] Method is distinguished in that the procedure is carried out analogously to Example 1 but 344.8 g of trichloroacetic acid is used as carboxylic acid.

TABLE-US-00075 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.0% 83.5% 54.2% 49.8% 49.5% Triester content [%] max. 3.00  1.7%  5.8% 29.9% 35.5% 35.9% Trichloroacetic 0.59% n.d. n.d. n.d. n.d. acid [%] Glycidyl 0.54% n.d. n.d. n.d. n.d. methacrylate [%]

TABLE-US-00076 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 88.0% 50.1% 47.9% 48.2% 48.0% Triester content [%] max. 3.00  1.7% 34.1% 35.8% 36.0% 35.8% Trichloroacetic acid [%] 0.59% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.54% n.d. n.d. n.d. n.d. [%]

[0179] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition proved to be NOT storage-stable!

Inventive Example 39

[0180] Molar stoichiometry (glycidyl methacrylate: carboxylic acid) 1:1.02

[0181] Method is distinguished in that the procedure is carried out analogously to Example 1 but 351.7 g of trichloroacetic acid is used as carboxylic acid.

TABLE-US-00077 Storage stability at 30° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 86.3% 86.1% 86.2% 85.6% Triester content [%] max. 3.00  1.6%  1.6%  1.6%  1.8%  2.0% Trichloroacetic acid [%] 0.64% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.48% n.d. n.d. n.d. n.d. [%]

TABLE-US-00078 Storage stability at 50° C. Start 1 month 3 months 6 months 8 months Diester content [%] min. 85.00 85.6% 85.7% 85.6% 85.1% 83.6% Triester content [%] max. 3.00  1.6%  1.9%  2.2%  2.8%  3.3% Trichloroacetic acid [%] 0.64% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.48% n.d. n.d. n.d. n.d. [%]

[0182] Conclusion: The product prepared with a molar stoichiometry of 1:1.02 at the end of the reactant addition had a storage stability of more than 3 months.

Inventive Example 40

[0183] Post-stablization with carboxylic acid endogenous to the system prior to storage

[0184] Method according to Example 1, distinguished in that 179 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) is 1:0.985.

[0185] Prior to storage, the crude product obtained is doped with 1.5 g of methacrylic acid.

[0186] Molar stoichiometry prior to storage: glycidyl methacrylate <carboxylic acid

TABLE-US-00079 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.10%  85.84%  86.47% 86.28% 86.39% 85.77% 85.00 Triester content [%] max. 1.60% 1.59%  1.58%  1.53%  1.69%  1.94% 3.00 Methacrylic acid [%] 0.40% 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%]

TABLE-US-00080 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.10%  85.84%  85.94% 85.81% 85.26% 83.81% 85.00 Triester content [%] max. 1.60% 1.59%  1.82%  2.10%  2.68%  3.12% 3.00 Methacrylic acid [%] 0.40% 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%]

[0187] Conclusion: The crude product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition, but post-stabilized, had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 1 was not storage-stable.

Inventive Example 41

[0188] Post-stablization with carboxylic acid endogenous to the system prior to storage

[0189] Method according to Example 2, distinguished in that 181.7 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) was 1:1.

[0190] Prior to storage, the crude product obtained is doped with 1.1 g of methacrylic acid.

[0191] Molar stoichiometry prior to storage: glycidyl methacrylate <carboxylic acid

TABLE-US-00081 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.00%  86.67% 86.49% 86.59% 85.97% 85.00 Triester content [%] max. 1.80% 1.80%  1.67%  1.62%  1.78%  2.05% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%]

TABLE-US-00082 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.00%  86.14% 86.01% 85.46% 84.00% 85.00 Triester content [%] max. 1.80% 1.80%  1.92%  2.22%  2.83%  3.30% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%]

[0192] Conclusion: The crude product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition, but post-stabilized had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 2 was not storage-stable.

Inventive Example 42

[0193] Post-stabilization with a carboxylic acid foreign to the system prior to storage

[0194] Method according to Example 1, distinguished in that 179 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) was 1:0.985.

[0195] Prior to storage, the crude product obtained is doped with 0.8 g of formic acid.

[0196] Molar stoichiometry prior to storage: glycidyl methacrylate <carboxylic acid

TABLE-US-00083 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.1% 86.0% 86.2% 86.0% 86.1% 85.5% 85.00 Triester content [%] max. 1.60% 1.59% 1.18% 1.15% 1.26% 1.45% 3.00 Methacrylic acid [%] 0.40% 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%] Formic acid [%] 0.00% 0.16% n.d. n.d. n.d. n.d.

TABLE-US-00084 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.1% 85.8% 85.6% 85.5% 85.0% 83.5% 85.00 Triester content [%] max. 1.60% 1.59% 1.36% 1.57% 2.01% 2.34% 3.00 Methacrylic acid [%] 0.40% 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%] Formic acid [%] 0.00% 0.16% n.d. n.d. n.d. n.d.

[0197] Conclusion: The crude product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition, but post-stabilized with formic acid as acid foreign to the system had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 1 was not storage-stable.

Inventive Example 43

[0198] Post-stablization with carboxylic acid foreign to the system prior to storage

[0199] Method according to Example 2, distinguished in that 181.7 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) was 1:1.

[0200] Prior to storage, the crude product obtained is doped with 0.6 g of formic acid.

[0201] Molar stoichiometry prior to storage: glycidyl methacrylate <carboxylic acid

TABLE-US-00085 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.06%  86.67% 86.49% 86.59% 85.97% 85.00 Triester content [%] max. 1.80% 1.79%  1.67%  1.62%  1.78%  2.05% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%] Formic acid [%] 0.00% 0.12% n.d. n.d. n.d. n.d.

TABLE-US-00086 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.00%  86.14% 86.01% 85.46% 84.00% 85.00 Triester content [%] max. 1.80% 1.79%  1.92%  2.22%  2.83%  3.30% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%] Formic acid [%] 0.00% 0.12% n.d. n.d. n.d. n.d.

[0202] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition, but the crude product post-stabilized with formic acid as acid foreign to the system had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 2 was not storage-stable.

Inventive Example 44

[0203] Post-stablization with a Broensted acid prior to storage

[0204] Method according to Example 1, distinguished in that 179 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) was 1:0.985.

[0205] Prior to storage, the crude product obtained is doped with 0.55 g of phosphoric acid.

[0206] Molar stoichiometry prior to storage: glycidyl methacrylate <acid

TABLE-US-00087 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.1% 86.0% 86.2% 86.0% 86.1% 85.5% 85.00 Triester content [%] max. 1.60% 1.59% 1.18% 1.15% 1.26% 1.45% 3.00 Methacrylic acid [%] 0.40% 0.40% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%] Phosphoric acid [%] 0.00% 0.11% n.d. n.d. n.d. n.d.

TABLE-US-00088 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.1% 86.0% 85.6% 85.5% 85.0% 83.5% 85.00 Triester content [%] max. 1.60% 1.59% 1.36% 1.57% 2.01% 2.34% 3.00 Methacrylic acid [%] 0.40% 0.71% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.78% 0.78% n.d. n.d. n.d. n.d. [%] Phosphoric acid [%] 0.00% 0.11% n.d. n.d. n.d. n.d.

[0207] Conclusion: The crude product prepared with a molar stoichiometry of 1:0.985 at the end of the reactant addition, but post-stabilized with phosphoric acid as inorganic acid foreign to the system had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 1 was not storage-stable.

Inventive Example 45

[0208] Post-stablization with a Broensted acid prior to storage

[0209] Method according to Example 2, distinguished in that 181.7 g of methacrylic acid is used as carboxylic acid and at the end of the reactant addition the molar stoichiometry (glycidyl methacrylate:carboxylic acid) was 1:1.

[0210] Prior to storage, the crude product obtained is doped with 0.25 g of phosphoric acid.

[0211] Molar stoichiometry prior to storage: glycidyl methacrylate <acid

TABLE-US-00089 Storage stability at 30° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.06%  86.67% 86.49% 86.59% 85.97% 85.00 Triester content [%] max. 1.80% 1.79%  1.67%  1.62%  1.78%  2.05% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%] Phosphoric acid [%] 0.00% 0.05% n.d. n.d. n.d. n.d.

TABLE-US-00090 Storage stability at 50° C. Product Start 1 month 3 months 6 months 8 months Diester content [%] min. 86.20%  86.06%  86.14% 86.01% 85.46% 84.00% 85.00 Triester content [%] max. 1.80% 1.79%  1.92%  2.22%  2.83%  3.30% 3.00 Methacrylic acid [%] 0.42% 0.65% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.72% 0.72% n.d. n.d. n.d. n.d. [%] Phosphoric acid [%] 0.00% 0.05% n.d. n.d. n.d. n.d.

[0212] Conclusion: The product prepared with a molar stoichiometry of 1:1 at the end of the reactant addition, but the crude product post-stabilized with phosphoric acid as inorganic acid foreign to the system had a storage stability of 6 months, whereas the non-stabilized reference sample of Example 2 was not storage-stable.