One pot synthesis of urea (meth)acrylates

Patent metadata

Field	Value
Publication number	US-12338202-B2
Application number	US-202217930717-A
Country	US
Kind code	B2
Filing date	Sep 8, 2022
Priority date	Sep 10, 2021
Publication date	Jun 24, 2025
Grant date	Jun 24, 2025

Abstract

A one-pot synthesis of polymerizable and acyclic urea (meth)acrylates, preferably mono(meth)acrylates, can be performed via in-situ synthesis of urea alcohols or amines followed by direct reaction with a (meth)acrylate reactive diluent. The urea alcohol/amine is obtained from isocyanates and alcohols, amines, or hydroxyamines. Subsequently, the reaction with the (meth)acrylate reactive diluent takes place and the urea (meth)acrylate is directly obtained either in solution with the reactive diluent, or as a pure material after removal of the reactive diluent.

First claim

The invention claimed is:

1. A one pot process for preparing at least one (meth)acrylate of the general formula (I)

wherein
R 1 is selected from the group consisting of —H and -Me;
R 2 is selected from the group consisting of —H and a C 1 -C 20 linear, branched or cyclic alkyl or aryl group;
R 2′ is —H;
R 3 is selected from the group consisting of —H; a C 1 -C 20 linear, branched or cyclic alkyl or aryl group; benzene-sulfonyl; tosyl; p-chlorophenyl; adamantyl; 2,6-dimethyl phenyl; 3,5-dimethyl phenyl; and 2,6-dipropyl phenyl;
R 2 and R 3 are the same or different;
X is selected from the group consisting of —O— and —NH—; and
L is a C 2 -C 20 linear, branched or cyclic alkyl or aryl group, in which optionally, one or more carbon atoms within the carbon chain is replaced by one or more —O—, —NH— or —S— heteroatoms,

the process comprising:
reacting, in an initial reaction phase, an aminoalcohol or diamine of the general formula (V)

wherein X, R 2 , L are as defined above,
with an isocyanate of the general formula (VI)

wherein R 3 is as defined above,
in the presence of a reactive diluent of the general formula (III)

wherein R 4 is C 1 to C 4 alkyl,
to obtain, in situ, an intermediate compound of the general formula (II)

wherein X, R 2 , R 2′ , R 3 , L are as defined above; and

immediately reacting, in a second reaction phase, the intermediate compound with the reactive diluent, to form the at least one (meth)acrylate.

2. The process according to claim 1 , wherein
R 1 is methyl,
R 2 is selected from the group consisting of hydrogen and a C 1 to C 8 linear or branched alkyl,
R 3 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, ethyl hexyl, cyclohexyl, and phenyl,
X is oxygen; and
L is selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethoxyethyl.

3. The process according to claim 1 , wherein the process is carried out in the presence of at least one catalyst selected from the group consisting of Zr(acac) 2 , LiOH, CaO, dioctyltin oxide, dibutyltin laurate, titanium isopropoxide, and a combination thereof.

4. The process according to claim 1 , wherein the process is carried out in the presence of at least one catalyst selected from the group consisting of titanium isopropoxide, CaO/LiOH, CaO/LiCl, dioctyltin oxide, and dibutyltin laurate.

5. The process according to claim 3 , wherein the at least one catalyst is present in an amount of between 0.01 and 5 wt. %, based on an amount of the aminoalcohol or diamine.

6. The process according to claim 1 , wherein the reaction temperature in the initial reaction phase is kept between 0° C. and 80° C.

7. The process according to claim 1 , wherein the reaction temperature in the second reaction phase is kept between 30° C. and 180° C.

8. The process according to claim 1 , wherein the reactive diluent is at least one alkyl (meth)acrylate selected from the group consisting of propyl (meth)acrylate, ethyl (meth)acrylate, i-propyl (meth)acrylate, i-butyl (meth)acrylate, n-butyl (meth)acrylate, and methyl (meth)acrylate.

9. The process according to claim 1 , wherein the reactive diluent is methyl(meth)acrylate.

10. The process according to claim 1 , wherein an amount of reactive diluent used is between 1 and 50 moles per mole of the aminoalcohol or diamine.

11. The process according to claim 1 , wherein an amount of the isocyanate is 0.80 to 1.20 eq. per eq. of the aminoalcohol or diamine.

12. The process according to claim 1 , wherein the process is carried out in the presence of at least one polymerization inhibitor selected from the group consisting of hydrochinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methyl-phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, and a mixture thereof.

13. The process according to claim 12 , wherein the at least one polymerization inhibitor is hydrochinone monomethyl ether.

14. The process according to claim 12 , wherein an amount of the at least one polymerization inhibitor at the beginning of the process is adjusted to between 0 and 5,000 ppm, based on an amount of theoretically expected product at full conversion.

15. The process according to claim 1 , wherein the at least one (meth)acrylate is obtained via precipitation.

16. The process according to claim 6 , wherein the reaction temperature in the initial reaction phase is kept between 0° C. and 30° C.

17. The process according to claim 7 , wherein the reaction temperature in the second reaction phase is kept between 80° C. and 130° C.

18. The process according to claim 10 , wherein the amount of reactive diluent used is between 3 and 10 moles per mole of the aminoalcohol or diamine.

19. The process according to claim 11 , wherein the amount of the isocyanate is 0.95 to 1.05 eq. per eq. of the aminoalcohol or diamine.

20. The process according to claim 12 , wherein the at least one (meth)acrylate is obtained via precipitation, and wherein the at least one polymerization inhibitor is co-precipitated with the at least one (meth)acrylate.

Assignees

• Evonik Operations Gmbh

Inventors

• Bestgen Sebastian
• Beyer Silvia

Classifications

• C07C2531/22

  Organic complexes · CPC title

• C07C2523/04

  Alkali metals · CPC title

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title

• C07C2521/00

  Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium · CPC title

• C07C273/1854

  by reactions not involving the formation of the N-C(O)-N- moiety · CPC title