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. A method for preparing storage-stable glycerol (meth)acrylate carboxylic esters of formula (I): ##STR00007## wherein: R.sub.1=H or CH.sub.3; R.sub.2=hydrogen; a C1 to C30 aliphatic group optionally with a hydroxyl substituent; an aliphatic cyclic group with a C4 to C8 ring unsubstituted or substituted by N, S, O or P; a C1 to C8 halogenated aliphatic group; an aromatic group having a ring with five or six carbons and optionally with a hydroxyl substituent; a heteroaromatic group substituted by N, S, O or P and having a ring with five or six carbons; or a C2 to C30 unsaturated aliphatic group; said method comprising the steps of: a) reacting carboxylic acids of formula (II) with glycidyl (meth)acrylate at a temperature of 20-130° C. in the presence of a catalyst, by initially charging the carboxylic acids of formula (II) and adding glycidyl (meth)acrylate continuously, wherein the carboxylic acids of formula (II) have the structure: ##STR00008## wherein R.sub.2=hydrogen; a C1 to C30 aliphatic group optionally with a hydroxyl substituent; an aliphatic cyclic group with a C4 to C8 ring unsubstituted or substituted by N, S, O or P; a C1 to C8 halogenated aliphatic group; an aromatic group having a ring with five or six carbons and optionally with a hydroxyl substituent; a heteroaromatic group substituted by N, S, O or P and having a ring with five or six carbons; or a C2 to C30 unsaturated aliphatic group; b) optionally, after the reaction is complete and prior to storage, adding foreign carboxylic acids of formula (III) and/or foreign Broensted acids, wherein the carboxylic acids of formula (III) have the structure: ##STR00009## wherein R.sub.3 is defined as for R.sub.2; c) storing the storage stable glycerol (meth)acrylate carboxylic esters of formula (I) with the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula III and foreign Broensted acids; wherein, at the beginning of storage, the sum total of the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula (III) and foreign Broensted acids is in molar excess to the glycidyl (meth)acrylate present.

2. The method of claim 1, wherein the molar ratio of the sum total of the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula (III) and foreign Broensted acids to glycidyl (meth)acrylate is from 1.001:1 to 5:1.

3. The method of claim 1, wherein the molar ratio of the sum total of the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula (III) and foreign Broensted acids to glycidyl (meth)acrylate is from 1.01:1 to 2:1.

4. The method of claim 1, wherein the molar ratio of endogenous carboxylic acids of formula (II) to glycidyl (meth)acrylate at the end of the reaction is above 1:1 and neither foreign carboxylic acids of formula (III) nor foreign Broensted acids are added prior to storage.

5. The method of claim 1, wherein the molar ratio of endogenous carboxylic acids of formula (II) to glycidyl (meth)acrylate, at the end of the reaction is below 1:1 but is adjusted to greater than 1:1 by addition of foreign carboxylic acids (III) and/or Broensted acids prior to storage.

6. The method of claim 1, wherein the molar ratio of endogenous carboxylic acids of formula (II) to glycidyl (meth)acrylate, at the end of the reaction is below 1:1 but is adjusted to greater than 1:1 by addition of carboxylic acids (III) without Broensted acids.

7. The method of claim 1, wherein the molar stoichiometry (glycidyl methacrylate: carboxylic acid) during the reaction is at least 1.02:1.

8. The method of claim 1, wherein glycidyl (meth)acrylate and carboxylic acid (II) are reacted in the presence of catalytic amounts of a quaternary alkylammonium halide.

9. The method of claim 8, wherein the quaternary alkylammonium halide is benzyltriethylammonium chloride.

10. The method of claim 1, wherein, in step c), the glycerol (meth)acrylate carboxylic esters of formula (I) are stored for a period of at least three months at a temperature of up to 50° C. and maintain a diester content of 85% or greater and a triester content of 3% or less.

11. The method of claim 1, wherein, in step c), the glycerol (meth)acrylate carboxylic esters of formula (I) are stored for a period of at least six months at a temperature of up to 30° C. and maintain a diester content of 85% or greater and a triester content of 3% or less.

12. The method of claim 1, wherein R.sub.2 is a C1 to C30 aliphatic group, or an aliphatic cyclic group with a C4 to C8 ring, unsubstituted or substituted by N, S, O or P.

13. The method of claim 1, wherein R.sub.2 is an aromatic group having a ring with up to six carbons or a heteroaromatic group substituted by N, S, O or P and having a ring with up to six carbons, or a C2 to C30 unsaturated aliphatic group.

14. The method of claim 2, wherein glycidyl (meth)acrylate and endogenous carboxylic acids of formula (II) are reacted in the presence of catalytic amounts of a quaternary alkylammonium halide.

15. The method of claim 14, wherein the quaternary alkylammonium halide is benzyltriethylammonium chloride.

16. The method of claim 15, wherein, in step c), the glycerol (meth)acrylate carboxylic esters of formula (I) are stored for a period of at least three months at a temperature of up to 50° C. and maintain a diester content of 85% or greater and a triester content of 3% or less.

17. A method for preparing storage-stable glycerol (meth)acrylate carboxylic esters of formula (I): ##STR00010## wherein: R.sub.1=H or CH.sub.3; R.sub.2=hydrogen; a C1 to C30 aliphatic group optionally with a hydroxyl substituent; an aliphatic cyclic group with a C4 to C8 ring unsubstituted or substituted by N, S, O or P; a C1 to C8 halogenated aliphatic group; an aromatic group having a ring with five or six carbons and optionally with a hydroxyl substituent; a heteroaromatic group substituted by N, S, 0 or P and having a ring with five or six carbons; or a C2 to C30 unsaturated aliphatic group; said method comprising: a) making the storage-stable glycerol (meth)acrylate carboxylic esters of formula (I) by a procedure consisting essentially of reacting carboxylic acids of formula (II) with glycidyl (meth)acrylate at a temperature of 20-130° C. in the presence of a catalyst, wherein the carboxylic acids of formula (II) have the structure: ##STR00011## R.sub.2=hydrogen; a C1 to C30 aliphatic group optionally with a hydroxyl substituent; an aliphatic cyclic group with a C4 to C8 ring unsubstituted or substituted by N, S, O or P; a C1 to C8 halogenated aliphatic group; an aromatic group having a ring with five or six carbons and optionally with a hydroxyl substituent; a heteroaromatic group substituted by N, S, or P and having a ring with five or six carbons; or a C2 to C30 unsaturated aliphatic group; b) optionally, after the reaction of step a) is complete and prior to storage, adding foreign carboxylic acids of formula (III) and/or foreign Broensted acids, wherein the carboxylic acids of formula (III) have the structure: ##STR00012## wherein R.sub.3 is defined as for R.sub.2; c) storing the storage stable glycerol (meth)acrylate carboxylic esters of formula (I) with the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula III and foreign Broensted acids; wherein, at the beginning of storage, the sum total of the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula (III) and foreign Broensted acids is in molar excess to the glycidyl (meth)acrylate present.

18. The method of claim 1, wherein the carboxylic acids of formulas II and III are selected from the group consisting of: acetic acid, butyric acid, stearic acid, benzoic acid, salicylic acid, nicotinic acid, proline, acrylic acid, oleic acid, lactic acid, hydroxyisobutyric acid, trichloroacetic acid, or methacrylic acid.

19. The method of claim 1, wherein the molar ratio of the sum total of the endogenous carboxylic acids of formula (II), foreign carboxylic acids of formula (III) and foreign Broensted acids to glycidyl (meth)acrylate is from 1.01:1 to 5:1.

20. The method of claim 1, wherein foreign carboxylic acids of formula (III) and/or foreign Broensted acids are added in step b) prior to storage.

Description

EXAMPLES

(1) 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 1 l 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

(2) Method is distinguished in that 179 g of methacrylic acid is used as carboxylic acid.

(3) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(4) 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. [%]

(5) 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. [%] 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

(6) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(7) 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.

(8) 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. [%]

(9) 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. [%] 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

(10) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(11) 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.

(12) 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. [%]

(13) 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. [%] 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

(14) 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.

(15) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(16) 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. [%]

(17) 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. [%] 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

(18) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(19) 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.

(20) 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. [%]

(21) 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. [%] 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

(22) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(23) 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.

(24) 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. [%]

(25) 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. [%] 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

(26) 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.

(27) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(28) 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. [%]

(29) 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. [%] 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

(30) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(31) 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.

(32) 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. [%]

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

(34) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(35) 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.

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

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

(38) 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.

(39) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(42) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(43) 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.

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

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

(46) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(47) 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.

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

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

(50) 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.

(51) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(54) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(55) 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.

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

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

(58) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(59) 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.

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

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

(62) 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.

(63) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(66) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(67) 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.

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

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

(70) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(71) 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.

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

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

(74) 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.

(75) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(78) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(79) 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.

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

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

(82) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(83) 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.

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

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

(86) 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.

(87) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(90) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(91) 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.

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

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

(94) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(95) 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.

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

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

(98) 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.

(99) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(102) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(103) 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.

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

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

(106) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(107) 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.

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

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

(110) 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.

(111) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

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

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

(114) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(115) 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.

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

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

(118) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(119) 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.

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

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

(122) 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.

(123) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(124) 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 methacrylate 0.77% n.d. n.d. n.d. n.d. [%]

(125) 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 methacrylate 0.77% n.d. n.d. n.d. n.d. [%] 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

(126) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(127) 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.

(128) 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 methacrylate 0.71% n.d. n.d. n.d. n.d. [%]

(129) 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 methacrylate 0.71% n.d. n.d. n.d. n.d. [%] 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

(130) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(131) 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.

(132) 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 methacrylate 0.64% n.d. n.d. n.d. n.d. [%]

(133) 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 methacrylate 0.64% n.d. n.d. n.d. n.d. [%] 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

(134) 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.

(135) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(136) 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 acid [%] 0.45% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.73% n.d. n.d. n.d. n.d.

(137) 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 acid [%] 0.45% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.73% n.d. n.d. n.d. n.d. 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

(138) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(139) 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.

(140) 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 acid [%] 0.47% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.67% n.d. n.d. n.d. n.d.

(141) 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 acid [%] 0.47% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.67% n.d. n.d. n.d. n.d. 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

(142) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(143) 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.

(144) 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 acid [%] 0.50% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.60% n.d. n.d. n.d. n.d.

(145) 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 acid [%] 0.50% n.d. n.d. n.d. n.d. Glycidyl methacrylate [%] 0.60% n.d. n.d. n.d. n.d. 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

(146) 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.

(147) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:0.985

(148) 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 acid [%] 0.57% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.59% n.d. n.d. n.d. n.d. [%]

(149) 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 acid [%] 0.57% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.59% n.d. n.d. n.d. n.d. [%] 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

(150) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1

(151) 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.

(152) 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 acid [%] 0.59% n.d. n.d. n.d. n.d. Glycidyl methacrylate 0.54% n.d. n.d. n.d. n.d. [%]

(153) 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. [%] 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

(154) Molar stoichiometry (glycidyl methacrylate:carboxylic acid) 1:1.02

(155) 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.

(156) 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. [%]

(157) 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. [%] 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

(158) Post-Stablization with Carboxylic Acid Endogenous to the System Prior to Storage

(159) 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.

(160) Prior to storage, the crude product obtained is doped with 1.5 g of methacrylic acid.

(161) Molar stoichiometry prior to storage: glycidyl methacrylate<carboxylic acid

(162) TABLE-US-00079 Storage stability at 30° C. 1 3 6 Product Start month months 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. [%]

(163) TABLE-US-00080 Storage stability at 50° C. 1 3 6 Product Start month months 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. [%] 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

(164) Post-Stablization with Carboxylic Acid Endogenous to the System Prior to Storage

(165) 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.

(166) Prior to storage, the crude product obtained is doped with 1.1 g of methacrylic acid.

(167) Molar stoichiometry prior to storage: glycidyl methacrylate<carboxylic acid

(168) TABLE-US-00081 Storage stability at 30° C. 3 Product Start 1 month 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. [%]

(169) TABLE-US-00082 Storage stability at 50° C. 3 Product Start 1 month 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. [%] 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

(170) Post-Stabilization with a Carboxylic Acid Foreign to the System Prior to Storage

(171) 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.

(172) Prior to storage, the crude product obtained is doped with 0.8 g of formic acid.

(173) Molar stoichiometry prior to storage: glycidyl methacrylate<carboxylic acid

(174) TABLE-US-00083 Storage stability at 30° C. 1 3 8 Product Start month months 6 months 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.

(175) TABLE-US-00084 Storage stability at 50° C. 1 3 8 Product Start month months 6 months 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. 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

(176) Post-Stablization with Carboxylic Acid Foreign to the System Prior to Storage

(177) 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.

(178) Prior to storage, the crude product obtained is doped with 0.6 g of formic acid.

(179) Molar stoichiometry prior to storage: glycidyl methacrylate<carboxylic acid

(180) 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.

(181) 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. 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

(182) Post-Stablization with a Broensted Acid Prior to Storage

(183) 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.

(184) Prior to storage, the crude product obtained is doped with 0.55 g of phosphoric acid.

(185) Molar stoichiometry prior to storage: glycidyl methacrylate<acid

(186) 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.

(187) 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. 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

(188) Post-Stablization with a Broensted Acid Prior to Storage

(189) 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.

(190) Prior to storage, the crude product obtained is doped with 0.25 g of phosphoric acid.

(191) Molar stoichiometry prior to storage: glycidyl methacrylate<acid

(192) TABLE-US-00089 Storage stability at 30° C. 1 8 Product Start month 3 months 6 months 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.

(193) TABLE-US-00090 Storage stability at 50° C. 1 8 Product Start month 3 months 6 months 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. 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.