Method for preparing urethane (meth)acrylates

Patent metadata

Field	Value
Publication number	US-9738597-B2
Application number	US-201414892027-A
Country	US
Kind code	B2
Filing date	May 16, 2014
Priority date	May 27, 2013
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

Described herein is a process for preparing urethane (meth)acrylates. In a first step, a hydroxyalkyl (meth)acrylate is reacted with a lactone (B) in the presence of at least one zinc compound and/or bismuth compound (C) to produce a resulting zinc-containing product and/or a bismuth-containing product, and, in a further step, the zinc-containing product and/or the bismuth-containing product is reacted with at least one cycloaliphatic or asymmetric aliphatic diisocyanate (D).

First claim

What is claimed is:

1. A process for preparing urethane (meth)acrylates of the formula (I)

comprising, in a first step, reacting a hydroxyalkyl (meth)acrylate (A) of the formula (A)

with a lactone of the formula (B)

in the presence of only one zinc compound or bismuth compound (C) and in the absence of an acid to produce a corresponding resulting zinc-containing product or a bismuth-containing product,
and, in a further step, reacting the zinc-containing product or the bismuth-containing product with at least one cycloaliphatic or asymmetric aliphatic diisocyanate (D),
wherein
R 1 is a divalent alkylene radical having 2 to 12 carbon atoms and which may optionally be substituted by C1 to C4 alkyl groups and/or interrupted by one or more oxygen atoms,
R 2 in each case independently of any other is methyl or hydrogen,
R 3 is a divalent alkylene radical having 1 to 12 carbon atoms and which may optionally be substituted by C1 to C4 alkyl groups and/or interrupted by one or more oxygen atoms,
R 4 is a divalent organic radical which is formed by abstraction of both isocyanate groups from a cycloaliphatic or asymmetric aliphatic diisocyanate, and
n and m independently of one another are positive numbers from 1 to 5.

2. The process of claim 1 , wherein R 1 is selected from the group consisting of 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3-, or 1,4-butylene, 1,1-dimethyl-1,2-ethylene, 1,2-dimethyl-1,2-ethylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene, and 1,12-dodecylene.

3. The process of claim 1 , wherein R 3 is selected from the group consisting of methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,5-hexylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene, 2-oxa-1,4-butylene, 3-oxa-1,5-pentylene, and 3-oxa-1,5-hexylene.

4. The process of claim 1 , wherein (A) is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, 1,5-pentanediol mono(meth)acrylate, and 1,6-hexanediol mono (meth)acrylate.

5. The process of claim 1 , wherein (B) is selected from the group consisting of beta-propiolactone, gamma-butyrolactone, gamma-ethyl-gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, epsilon-caprolactone, 7-methyloxepan-2-one, 1,4-dioxepan-5-one, oxacyclotridecan-2-one, and 13-butyl-oxacyclotridecan-2-one.

6. The process of claim 1 , wherein the bismuth compound (C) is present and is a compound of bismuth in the +3 oxidation state with an anion selected from the group consisting of F, Cr, Cl − , ClO 3 − , ClO 4 − , Br − , I − , IO 3 − , CN − , OCN − , NO 2 − , NO 3 − , HCO 3 − , CO 3 2− , S 2− , SH − , HSO 3 − , SO 3 2− , HSO 4 − , SO 4 2− , S 2 O 2 2− , S 2 O 5 2− , S 2 O 6 2− , S 2 O 7 2− , S 2 O 8 2 , H 2 PO 2 − , H 2 PO 4 − , HPO 4 2− , PO 4 3− , P 2 O 7 4− , (OC x H 2x+1 ), (C x H 2x−1 O 2 ) − , (C x H 2x−3 O 2 ) − , and (C x+1 H 2x−2 O 2 ) 2− , wherein x is a number 1 to 20.

7. The process of claim 1 , wherein the bismuth compound (C) is present and is a bismuth carboxylate.

8. The process of claim 1 , wherein the bismuth compound (C) is present and is selected from the group consisting of bismuth formate, acetate, propionate, hexanoate, neodecanoate, 2-ethylhexanoate, octoates, or pivalate.

9. The process of claim 1 , wherein the zinc compound (C) is present and is a compound of zinc in the +2 oxidation state with an anion selected from the group consisting of F, Cr, Cl − , ClO 3 − , ClO 4 − , Br − , I − , IO 3 − , CN − , OCN − , NO 2 − , NO 3 − , HCO 3 − , CO 3 2− , S 2− , SH − , HSO 3 − , SO 3 2− , HSO 4 − , SO 4 2− , S 2 O 2 2− , S 2 O 6 2− , S 2 O 7 2− , S 2 O 8 2− , H 2 PO 2 − , H 2 PO 4 − , HPO 4 2− , PO 4 3− , P 2 O 7 4− , (OC x H 2x+1 ) − , (C x H 2x+1 ) − , (C x H 2x−1 O 2 )−, (C x H 2x−3 O 2 ) − , and H 2 PO 2 − , H 2 PO 4 − , HPO 4 2− , PO 4 3− , P 2 O 7 4− , (OC x H 2x+1 ) − , (C x H 2x−1 O 2 ) − , (C x H 2x-3 O 2 ) − , and (C x+1 H 2x−2 O 2 ) 2− , wherein x is a number 1 to 20.

10. The process of claim 1 , wherein the first step is carried out at a temperatures from 50 to 150° C. over a period from 3 to 48 hours.

11. The process of claim 1 , wherein components (A) and (B) in the first step are present in a stoichiometric ratio of 1:1.5 to 3.

12. The process of claim 1 , wherein the catalyst (C) is added to the reaction mixture in an amount from 0.001 to 2 wt %, based on the sum of components (A) and (B).

13. The process of claim 1 , wherein the second step is carried out at 40 to 100° C.

14. The process of claim 1 , wherein the bismuth-containing product of the first step contains hydroxyl groups, and wherein the second step is carried out at a stoichiometry from 1.2:1 to 1:1.2 of hydroxyl groups in the bismuth-containing product to isocyanate groups in component (D).

15. A process for preparing urethane (meth)acrylates of the formula (I)

comprising, in a first step, reacting a hydroxyalkyl (meth)acrylate (A) of the formula (A)

with a lactone of the formula (B)

in the presence of only one zinc compound (C) to produce a zinc-containing product,
and, in a further step, reacting the zinc-containing product with at least one cycloaliphatic or asymmetric aliphatic diisocyanate (D),
wherein
R 1 is a divalent alkylene radical having 2 to 12 carbon atoms and which may optionally be substituted by C1 to C4 alkyl groups and/or interrupted by one or more oxygen atoms,
R 2 in each case independently of any other is methyl or hydrogen,
R 3 is a divalent alkylene radical having 1 to 12 carbon atoms and which may optionally be substituted by C1 to C4 alkyl groups and/or interrupted by one or more oxygen atoms,
R 4 is a divalent organic radical which is formed by abstraction of both isocyanate groups from a cycloaliphatic or asymmetric aliphatic diisocyanate, and
n and m independently of one another are positive numbers from 1 to 5.

16. The method of claim 15 , wherein the zinc compound (C) is zinc ethyhexanoate.

Assignees

• Basf Se

Inventors

• Schwalm Reinhold
• Neumann Susanne
• Kimpel Delphine

Classifications

• C09D4/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} · CPC title

• C08G18/6725

  containing ester groups other than acrylate or alkylacrylate ester groups · CPC title

• C08G18/672 Primary

  Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen · CPC title

• C08G18/227

  of antimony, bismuth or arsenic · CPC title

• C08G18/222

  metal compounds not provided for in groups C08G18/225 - C08G18/26 · CPC title