Terminally unsaturated, oxetane-based macromonomers, and methods for the production thereof

• US 8,883,942 B2
• Filed: 05/03/2010
• Issued: 11/11/2014
• Est. Priority Date: 05/19/2009
• Status: Active Grant

• Current Assignee: BYK-Chemie GmbH (Susanne Klatten, MBA)
• Original Assignee: BYK-Chemie GmbH (Susanne Klatten, MBA)
• Inventors: Frank, Albert, Jaunky, Wojciech, Issberner, Jrg
• Primary Examiner(s): Truong, Duc
• Application Number:
  US13/321,345
• Publication Number:
  US 20120142888A1
• Time in Patent Office: 1,653 Days
• Field of Search: 526/75, 526/279, 526/320, 524/544, 524/558, 528/417, 528/408
• US Class Current: 526/75
• CPC Class Codes: C08G 65/18 Oxetanes

Abstract

A process for preparing a macromonomer by cationic ring-opening polymerization of at least one hydroxyoxetane with a terminally ethylenically unsaturated starter molecule free of allyl groups in a molar ratio (hydroxyoxetane(s):starter molecule) of (100:1) to (1:1) in the presence of at least one suitable catalyst; macromononomers obtainable therefrom and use thereof.

Claims

1. A process for preparing a macromonomer, wherein at least one hydroxyoxetane of the formula (I)

2. The process as claimed in claim 1, wherein the reaction is effected in the presence of at least one inhibitor of free-radical polymerization.

3. The process as claimed in claim 1, wherein the molar ratio (hydroxyoxetane(s) of the formula (I):

starter molecule) is from (50;

1) to (2;

1).

4. The process as claimed in claim 1, wherein the at least one hydroxyoxetane of the formula (I) is

a 3-alkyl-3-(hydroxyalkyl)oxetane [i.e. R¹=alkyl, R²=hydroxyalkyl, all R³═

H],

a 3,3-di(hydroxyalkyl)oxetane [i.e. R¹, R²=hydroxyalkyl, all R³═

H],

a 3-alkyl-3-(hydroxyalkoxy)oxetane [i.e. R¹=alkyl, R²=hydroxyalkoxy, all R³═

H],

a 3-alkyl-3-(hydroxyalkoxyalkyl)oxetane [i.e. R¹=alkyl, R²=hydroxyalkoxyalkyl, all R³═

H],

or a mixture of these hydroxyoxetanes.

5. The process as claimed in claim 1, wherein the at least one hydroxyoxetane is

3-methyl-3-(hydroxymethyl)oxetane [i.e. R¹=methyl, R²=hydroxymethyl, all R³═

H],

3-ethyl-3-(hydroxymethyl)oxetane [i.e. R¹=ethyl, R²=hydroxymethyl, all R³═

H] (=trimethylolpropane oxetane),

derivatives of trimethylolpropane oxetane which have been ethoxylated and/or propoxylated on the hydroxyl group and have 1-20 ethylene oxide and/or propylene oxide units which may be arranged randomly, in blocks or in the manner of a gradient,

3,3-di(hydroxymethyl)oxetane [i.e. R¹=R²=hydroxymethyl, all R³═

H], or a mixture of these hydroxyoxetanes.

6. The process as claimed in claim 1, wherein the ethylenically unsaturated head group is U=acryloyl [H₂C═

CH—

C(═

O)—

] or methacryloyl [H₂C═

C(CH₃)—

C(═

O)—

].

7. The process as claimed in claim 1, wherein the divalent organic L radical has the structure —

O-L′

where —

O—

is an oxygen atom and L′

is selected from the group consisting of alkylene radicals and polyalkylene oxide radicals.

8. The process as claimed in claim 1, wherein the X—

H group is a hydroxyl group O—

H or a thiol group S—

H.

9. The process as claimed in claim 1, wherein the starter molecule U-L-X—

H is selected from the group consisting of hydroxyalkyl esters of methacrylic acid [H₂C═

C(CH₃)—

C(═

O)—

O—

(CH₂)_a—

OH] and polyethylene oxide esters of methacrylic acid [H₂C═

C(CH₃)—

C(═

O)—

O—

(CH₂—

CH₂—

O)_a—

H] where a=1-20.

10. The process as claimed in claim 1, wherein the starter molecule U-L-X—

H is hydroxyethyl methacrylate or hydroxybutyl methacrylate.

11. The process of claim 4, wherein the at least one hydroxyoxetane of the formula (I) is a 3-alkyl-3-(hydroxyalkyl)oxetane [i.e. R¹=alkyl, R²=hydroxyalkyl, all R³═

H] and/or a 3-alkyl-3-(hydroxyalkoxy)oxetane [i.e. R¹=alkyl, R²=hydroxyalkoxy, all R³═

H] or a mixture thereof.

12. The process of claim 5, wherein the at least one hydroxyoxetane is 3-ethyl-3-(hydroxymethyl)oxetane (=trimethylolpropane oxetane) and/or at least one derivative of trimethylolpropane oxetane which has been ethoxylated and/or propoxylated on the hydroxyl group and has 1-20 ethylene oxide and/or propylene oxide units which may be arranged randomly, in blocks or in the manner of a gradient.