Catalysts for making oxazolidinone materials

Abstract

A catalyst composition comprising at least a catalyst compound selected from multi metal cyanide compounds for the selective production of oxazolidinone compounds by reacting an isocyanate compound with an epoxide compound and oxazolidinone comprising materials obtained using said catalyst compound.

Claims

1. A method for the production of oxazolidinone compounds, said method comprising combining and mixing at a temperature in the range 130-200° C. at least following compounds to form a reactive mixture: an isocyanate composition comprising at least one isocyanate compound; an epoxide composition comprising at least one epoxide compound; an oxazolidinone catalyst composition comprising at least an oxazolidinone catalyst compound selected from multi metal cyanide compounds corresponding to the formula
Zn.sub.3[Co(CN).sub.6].sub.2.fZnCl.sub.2.eL.hH.sub.2O  [II] wherein L=tBuOH or 1,2-dimethoxyethane e is the coordination number of the ligand or 0, f is a fraction or integer greater than or equal to 0, and h is a fraction or integer greater than or equal to 0.

2. The method according to claim 1, wherein the temperature is from 135 to 160° C.

3. The method according claim 1, wherein the amount of multi metal cyanide compounds in the reactive mixture is from 5 to 5000 parts by weight per million (ppm) parts by weight of the reactive mixture.

4. The method according to claim 1, wherein the isocyanate composition is added to the epoxide composition in a continuous or step-wise manner with two or more individual addition steps in the step-wise addition.

5. The method according to claim 1, wherein the isocyanate compounds in the isocyanate composition are selected from a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition comprising a methylene diphenyl diisocyanate or a mixtures thereof.

6. The method according to claim 3, wherein the amount of multi metal cyanide compounds in the reactive mixture is from 10 to 500 parts by weight per million (ppm) parts by weight of the reactive mixture.

7. The method according to claim 3, wherein the amount of multi cyanide compounds in the reactive mixture is from 25 to 200 ppm by weight per million (ppm) parts by weight of the reactive mixture.

Description

FIGURES

(1) FIG. 1 illustrates the Infrared spectrum for an oxazolidinone comprising materials made using the process according to the invention making use of the oxazolidinone catalyst disclosed in the present invention at different reaction temperatures, 156° C. and 90° C.

EXAMPLES

(2) Chemicals Used:

(3) Suprasec® 3056 polyisocyanate ex Huntsman, in the examples indicated as S3056 Araldite® DY-D/CH epoxide compound Zn.sub.3[Co(CN).sub.6].sub.2.2L.2H.sub.2O, in the examples indicated as DMC Cyclohexyltriphenylphosphonium bromide, C.sub.24H.sub.26BrP (comparative catalyst)

(4) Suprasec® and Araldite® are trademarks of the Huntsman Corporation or an Affiliate thereof and have been registered in one or more but not all countries. The DMC catalyst used is ordered from Hongkong Huarun Int'l Industrial Co., LTD. The comparative catalyst, C.sub.24H.sub.26BrP is ordered from VWR International.

(5) Preparation of DMC Catalyst

(6) The catalyst is dried under vacuum in a rotating drying flask. The vacuum is gradually built up. Once the vacuum (15 mbar) is reached, the temperature can be built up gradually with a maximum temperature of 50° C. After 4 hours the oven will cool down to room temperature under vacuum conditions. After the oven is cooled down, the vacuum will be interrupted with nitrogen inlet and the catalyst can be taken out under nitrogen environment.

(7) Preparation of Oxazolidinone Comprising Material

(8) A three neck reaction flask equipped with mechanical stirrer, thermometer, reflux condenser and nitrogen inlet is used. An oil bath is used as heating source. Araldite® DY-D/CH is weight into the three neck flask. When the desired temperature is reached, the dry catalyst is loaded into the flask. Followed by a slow addition (1 gram/minute) of S3056 into the flask. When the addition is completed, the cook time starts and samples are taken on regular times and analysed by infrared spectroscopy and nuclear magnetic resonance spectroscopy.

(9) Analyses

(10) The composition of the reaction mixture was followed with a Bruker Tensor 27 spectrometer (average of 16 scans). The spectra were analysed with the software OPUS. The 13C-NMR measurements were recorded on a Bruker 500 MHz Avance III spectrometer, operated at a frequency of 125.77 MHz. The experiments were carried out on 50% (w/w) solutions in acetone-d6, at ambient temperature in 10 mm NMR glass tubes spinning at circa 20 Hz. For 13C-NMR an inverse gated 1H-decoupling pulse program was used in combination with a pulse delay of 12.6 seconds, in order to make sure that all carbon nuclei were fully relaxed to their equilibrium states.

(11) TABLE-US-00001 Example No Comparative No 1 2 3 4 1 2 Composition Ratio Araldite 2.5/1 1.7/1 1.4/1 2.5/1 2.5/1 2.5/1 DY-D/CH-S3056 DMC catalyst, ppm 34 30 28 34 0 0 C.sub.24H.sub.26BrP 0 0 0 0 0 34 catalyst, ppm Process conditions Temperature, ° C. 156 145 145 90 150 156 Cook time (min) 5 5 5 60 40 40 Characteristics C-NMR ✓ Oxazolidinone 100 100 100 8.6 86.9 85.2 (%)(*) ✓ Isocyanurate 0 0 0 91.4 13.1 14.8 (%)(**) (*)% = oxazolidinones/(oxazolidinones + isocyanurates) * 100%, (**)% = isocyanurates/(oxazolidinones + isocyanurates) * 100%

Example 1

(12) To a suitable flask equipped with a stirrer, temperature control, reflux condenser and nitrogen purge was charged 70.8 gram of 121 equivalent weight Araldite DY-D/CH. The glass flask was immersed into an oil bath and heated to 156° C. under stirring. When temperature is reached, 34 ppm DMC catalyst (calculated on total weight) is loaded into the flask. Subsequently, 29.2 gram S3056 was loaded stepwise with a pipet into the reaction mixture. From this moment, the cook time starts. A sample was taken after a cook time from 5 minutes and analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. This test indicates the formation of oxazolidinone rings, the complete disappearance of the isocyanate groups and the absence of isocyanurate groups.

Example 2

(13) This experiment is repeated according to the procedure described in example 1 except 30 ppm DMC catalyst and 43.27 gram S3056 was loaded into the reaction mixture.

(14) A sample was analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. This test indicates the formation of oxazolidinone rings, the complete disappearance of the isocyanate groups and the absence of isocyanurate groups.

Example 3

(15) This experiment is repeated according to the procedure described in example 1 except 28 ppm DMC catalyst and 51.03 gram S3056 was loaded into the reaction mixture. A sample was analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. This test indicates the formation of oxazolidinone rings, the complete disappearance of the isocyanate groups and the absence of isocyanurate groups.

Example 4

(16) This experiment is repeated with the same procedure as example 1 except now a process temperature of 90° C. is applied. A sample was taken after a cook time from 5 minutes and 60 minutes and analyzed by infrared spectroscopy. This test indicates the formation of significant quantities of isocyanurate groups and formation of oxazolidinone. Nuclear magnetic resonance spectroscopy verifies the existence of high quantities of isocyanurate groups.

(17) Comparative 1:

(18) This experiment is repeated according to the procedure described in example 1 except 0 ppm DMC catalyst was loaded. A sample was taken after a cook time from 40 minutes and analyzed by nuclear magnetic resonance spectroscopy. This test indicates the formation of oxazolidinone groups and the formation of isocyanurate groups.

(19) Comparative 2:

(20) This experiment is repeated according to the procedure described in example 1 except 34 ppm C.sub.24H.sub.26BrP catalyst was loaded instead of DMC catalyst. A sample was taken after a cook time from 40 minutes and analyzed by nuclear magnetic resonance spectroscopy. This test indicates the formation of oxazolidinone groups and the formation of isocyanurate groups.