METHOD FOR CLEAVING (POLY)URETHANES

Abstract

The invention relates to a method for cleaving urethanes, in particular polyurethanes, by means of chemolysis (alcoholysis, hydrolysis, or hydroalcoholysis) in the presence of a catalyst. The chemolysis is characterized in that a salt of an oxyacid of an element of the fifth, fourteenth, or fifteenth group of the periodic table of elements or a mixture of two or more such salts is used as the catalyst, the pKb value of the anion of said salt of the oxyacid ranging from 0.10 to 6.00, preferably 0.25 to 5.00, particularly 0.50 to 4.50, wherein the catalyst does not comprise carbonate when the chemolysis is carried out as an alcoholysis (Ia), and the catalyst does not contain carbonate, orthophosphate, or metaphosphate when the chemolysis is carried out as a hydroalcoholysis.

Claims

1. A method of cleaving urethanes by chemolysis (I), comprising (A) providing a urethane based on an isocyanate component and an alcohol component, followed by (B) chemolysis (I) of the urethane with a chemolysis reagent to obtain a chemolysis product, wherein the chemolysis (I) is conducted with addition of a catalyst as one of the following conversions: (Ia) alcoholysis of the urethane, where the chemolysis reagent is an alcohol, (Ib) hydrolysis of the urethane, where the chemolysis reagent is water, or (Ic) hydroalcoholysis of the urethane, where the chemolysis reagent comprises alcohol and water, wherein the catalyst comprises a salt of an oxoacid of an element from the fifth, fourteenth or fifteenth group of the Periodic Table of the Elements or a mixture of two or more such acids, where the pK.sub.B of the anion of the salt of the oxoacid is in the range from 0.10 to 6.00, and wherein the catalyst in the case of performance of the chemolysis as alcoholysis (Ia) does not comprise any carbonate and the catalyst in the case of performance of the chemolysis as hydroalcoholysis (Ic) does not comprise any carbonate, any orthophosphate or any metaphosphate.

2. The method as claimed in claim 1, further comprising: (C) working up (II) the chemolysis product to obtain a first product phase comprising mono- and/or polyols and a second product phase comprising: (i), in the case of performance of the chemolysis as alcoholysis (Ia), carbamates, or (ii), in the case of performance of the chemolysis as hydrolysis (Ib) or hydroalcoholysis (Ic), amines.

3. The method as claimed in claim 2, in which step (C) comprises a phase separation of the chemolysis product into the first product phase and the second product phase.

4. The method as claimed in claim 2, in which (i) in the case of performance of the chemolysis as hydrolysis (Ib), step (C) comprises blending the chemolysis product with an organic solvent and phase separation into the first product phase and the second product phase, or (ii) in the case of performance of the chemolysis as alcoholysis (Ia) or hydroalcoholysis (Ic), step (C) comprises blending the chemolysis product with an organic solvent incompletely miscible with the alcohol used in step (B), and phase separation into the first product phase and the second product phase, or (iii) in the case of performance of the chemolysis as alcoholysis (Ia) or hydroalcoholysis (Ic), step (C) comprises: (C.I) mixing the chemolysis product with an organic solvent miscible with the alcohol used in step (B) to obtain a product mixture, and (C.II) washing the product mixture with an aqueous washing liquid and phase separation into the first product phase and the second product phase.

5. The method as claimed in claim 2, further comprising: (D) obtaining the mono- and/or polyols from the first product phase.

6. The method as claimed in claim 2, further comprising: (E) obtaining the amines from the second product phase.

7. The method as claimed in claim 6, in which (i) in the case of performance of the chemolysis as alcoholysis (Ia), step (E) comprises a hydrolysis of the carbamates to amines and a distillative removal of alcohol and water, followed by a distillative purification of the amines remaining after the distillative removal, or (ii) in the case of performance of the chemolysis as hydrolysis (Ib) or hydroalcoholysis (Ic), step (E) comprises a distillative removal of alcohol and water from the second product phase, followed by a distillative purification of the amines remaining after the distillative removal.

8. The method as claimed in claim 1, in which, in the case of performance of the chemolysis as alcoholysis (Ia) or hydroalcoholysis (Ic), the alcohol used in the chemolysis comprises methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methylglycol, triethylene glycol, glycerol, 2-methylpropane-1,3-diol or a mixture of two or more thereof.

9. The method as claimed in claim 1, in which the element from the fifth, fourteenth or fifteenth group of the Periodic Table of the Elements comprises vanadium, carbon, silicon orand phosphorus.

10. The method as claimed in claim 9, in which (i) in the case of performance of the chemolysis as alcoholysis (Ia), the salt of the oxoacid comprises an anion comprising orthovanadate, orthophosphate, diphosphate, triphosphate, tetraphosphate, metaphosphate, alkylphosphonate, arylphosphonate, hydrogenorthosilicate, metasilicate, hydrogenmetasilicate, dihydrogenorthosilicate, trihydrogenorthosilicate, alkylsilanolate or arylsilanolate, (ii) in the case of performance of the chemolysis as hydrolysis (Ib), the salt of the oxoacid comprises an anion comprising orthovanadate, carbonate, orthophosphate, diphosphate, triphosphate, tetraphosphate, metaphosphate, alkylphosphonate, arylphosphonate, hydrogenorthosilicate, metasilicate, hydrogenmetasilicate, dihydrogenorthosilicate, trihydrogenorthosilicate, alkylsilanolate or arylsilanolate, or (iii) in the case of performance of the chemolysis as hydroalcoholysis (Ic), the salt of the oxoacid comprises an anion comprising orthovanadate, diphosphate, triphosphate, tetraphosphate, alkylphosphonate, arylphosphonate, hydrogenorthosilicate, metasilicate, hydrogenmetasilicate, dihydrogenorthosilicate, trihydrogenorthosilicate, alkylsilanolate or arylsilanolate.

11. The method as claimed in claim 9, in which the salt of the oxoacid comprises an anion comprising orthovanadate, diphosphate, triphosphate, tetraphosphate, alkylphosphonate, arylphosphonate, hydrogenorthosilicate, metasilicate, hydrogenmetasilicate, dihydrogenorthosilicate, trihydrogenorthosilicate, alkylsilanolate or arylsilanolate.

12. The method as claimed in claim 10, with the proviso that the salt of the oxoacid does not comprise any other anions.

13. The method as claimed in claim 1, in which the isocyanate component comprises phenyl isocyanate, tolylene diisocyanate a di- and/or polyisocyanate of the diphenylmethane series, pentane 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate, xylylene diisocyanate or a mixture of two or more thereof.

14. The method as claimed in claim 1, in which the mass of the salt of the oxoacid is 0.10% to 20% of the mass of the urethane.

15. The method as claimed in claim 1, in which a phase transfer catalyst is used in addition to the catalyst in the chemolysis.

16. The method as claimed in claim 1 in which the mass ratio of chemolysis reagent to the urethane is in the range from 0.05 to 90.

17. The method as claimed in claim 11, with the proviso that the salt of the oxoacid does not comprise any other anions.

18. The method of claim 1, in which the alcohol component comprises a monool or polyol selected from a polyether monool, a polyether polyol, a polyester polyol, a polyetherester polyol, a polyacrylate polyol, a polyethercarbonate polyol or a mixture of two or more thereof.

Description

EXAMPLES

[0228] The test reaction chosen was the cleavage of 2-(2-ethoxyethoxy)ethyl N-phenylcarbamate to (i) aniline or the carbamate formed from aniline and monoethylene glycol (MEG) and (ii) 2-(2-ethoxyethoxy)ethan-1-ol. In each case, 0.25 mmol of 2-(2-ethoxyethoxy)ethyl phenylcarbamate was converted in an autoclave. The catalysts and phase transfer catalysts used were commercially available products and were used without further purification.

[0229] The tables that follow summarize the experimental conditions and results:

TABLE-US-00001 TABLE 1 Overview of the test results for chemolysis in general Catalyst Conc. Chemolysis T Reaction time Conversion.sup.[b] Ex..sup.[a] Type [mol %] reagent [ C.] [h] [%] 1 (I) sodium 20 H.sub.2O (5.0 ml) 110 24 20 metasilicate hydrate 2 (I) sodium 10 H.sub.2O (5.0 ml) 110 24 18 metasilicate hydrate 3 (C) Bu.sub.4NCl 10 H.sub.2O (5.0 ml) 110 24 1 4 (I) Na.sub.3VO.sub.4 20 H.sub.2O (5.0 ml) 100 48 89 5 (I) Na.sub.3VO.sub.4 5 H.sub.2O (5.0 ml) 110 48 92 6 (I) Na.sub.3VO.sub.4 10 H.sub.2O (5.0 ml) 110 24 60 7 (I) Na.sub.2CO.sub.3 10 H.sub.2O (5.0 ml) 110 24 93 8 (I) Na.sub.3VO.sub.4 10 H.sub.2O (5.0 ml) 110 18 15 9 (I) Na.sub.3VO.sub.4 20 H.sub.2O (5.0 ml) 110 48 89 10 (I) Na.sub.3VO.sub.4 20 H.sub.2O (5.0 ml) 120 24 84 11 (I) Na.sub.2CO.sub.3 10 H.sub.2O (1.0 ml) 150 24 100 12 (I) K.sub.3PO.sub.4 10 MEG (1.0 ml) 110 24 78 13 (I) Na.sub.3PO.sub.4 10 MEG (0.5 ml) 110 24 20 14 (C) MEG (0.5 ml) 110 48 Traces 15 (I) Na.sub.3VO.sub.4 20 MEG (0.5 ml) 110 48 81 16 (I) Na.sub.3VO.sub.4 20 MEG (0.5 ml) 110 24 64 17 (I) Na.sub.2CO.sub.3 20 MEG (0.5 ml) 110 24 95 18 (I) K.sub.3PO.sub.4 20 MEG (0.5 ml) 110 24 96 19 (C) K.sub.2HPO.sub.4 20 MEG (0.5 ml) 110 24 18 20 (I) Na.sub.3PO.sub.4 20 MEG (0.5 ml) 110 24 96 21 (C) Na.sub.2HPO.sub.4 20 MEG (0.5 ml) 110 24 7 22 (C) MEG (0.5 ml) 150 24 Traces 23 (I) Na.sub.3VO.sub.4 10 MEG (0.5 ml) 150 24 100 .sup.[a](I) = inventive experiment; (C) = comparative experiment .sup.[b]conversion of 2-(2-ethoxyethoxy)ethyl N-phenylcarbamate, determined by gas chromatography

TABLE-US-00002 TABLE 2 Overview of the experimental results relating to the influence of phase transfer catalysts (PTC) PTC Reaction Type Conc. Conc. Chemolysis T time Conversion.sup.[a] Ex. Catalyst [mol %] Type [mol %] reagent [ C.] [h] [%] 24 K.sub.3PO.sub.4 20 H.sub.2O (1.0 ml) 110 17 21 25 K.sub.3PO.sub.4 20 H.sub.2O (1.0 ml) 110 24 29 26 K.sub.3PO.sub.4 20 Aliquat 336.sup.[b] 20 H.sub.2O (1.0 ml) 110 17 73 27 K.sub.3PO.sub.4 20 (1-propyl).sub.4NCl 20 H.sub.2O (1.0 ml) 110 17 23 28 K.sub.3PO.sub.4 20 (1-butyl).sub.4NCl 20 H.sub.2O (1.0 ml) 110 17 30 29 K.sub.3PO.sub.4 20 (1-pentyl).sub.4NCl 20 H.sub.2O (1.0 ml) 110 17 55 30 K.sub.3PO.sub.4 20 (1-hexyl).sub.4NCl 20 H.sub.2O (1.0 ml) 110 17 81 31 K.sub.3PO.sub.4 20 MEG (1.0 ml) 110 17 75 32 K.sub.3PO.sub.4 20 Aliquat 336.sup.[b] MEG (1.0 ml) 110 17 85 .sup.[a]conversion of 2-(2-ethoxyethoxy)ethyl phenylcarbamate, determined by gas chromatography .sup.[b]methyltri(1-octyl)ammonium chloride