METHOD FOR PRODUCING COMPOUNDS HAVING OXAZOLIDINONE GROUPS

Abstract

Described herein are processes for producing moldings comprising oxazolidinone groups, where polyisocyanate (a) is mixed with at least one organic compound (b) having two or more epoxide groups, at least one catalyst (c) for the isocyanate/epoxide reaction, and optionally auxiliary and additive materials (d) to form a reaction mixture, which is introduced into or applied to a mold and reacted to give moldings including oxazolidinone groups, where the catalyst (c) for the isocyanate/epoxide reaction includes a compound of the general formula [M(R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)].sup.+ [X I.sub.n].sup., where M is a nitrogen atom or a phosphorus atom, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are an organic radical, X is fluorine, chlorine, bromine or iodine, I is iodine, and n stands for rational numbers from 0.1 to 10.

Claims

1. A process for producing moldings comprising oxazolidinone groups, wherein: a) polyisocyanate is mixed with b) at least one organic compound having two or more epoxide groups, c) at least one catalyst for the isocyanate/epoxide reaction, and d) optionally auxiliary and additive materials to form a reaction mixture, which is introduced into or applied to a mold and reacted to give moldings comprising oxazolidinone groups, wherein the at least one catalyst c) for the isocyanate/epoxide reaction comprises a compound of the general formula [M(R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)].sup.+ [X I.sub.n].sup., and wherein: M is a nitrogen atom or a phosphorus atom, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each an organic radical, in each case selected independently of one another from the group consisting of linear or branched-chain alkyl radicals having 1 to 22 carbon atoms and being possibly substituted by heteroatoms or substituents comprising heteroatoms, and of alkyl-bridged cycloaliphatic or aromatic groups having 3 to 22 carbon atoms and being possibly substituted by heteroatoms or by groups comprising heteroatoms, and of aryl radicals having 6 to 18 carbon atoms and being possibly substituted by alkyl groups having 1 to 10 carbon atoms and/or heteroatoms, X is fluoride, chloride, bromide or iodide, I is iodine, and n stands for a rational number from 0.1 to 10.

2. The process according to claim 1, wherein n stands for a rational number from 0.5 to 3.

3. The process according to claim 1, wherein X is chlorine or bromine.

4. The process according to claim 1, wherein the molar ratio of polyisocyanate groups in the polyisocyanate (a) to epoxide groups in the at least one organic compound (b) having two or more epoxide groups is 1:10 to 10:1.

5. The process according to claim 1, wherein the at least one organic compound b) having two or more epoxide groups is selected from the group consisting of polyglycidyl ether of bisphenol A, bisphenol F and novolacs and mixtures thereof.

6. The process according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each an organic radical in each case selected independently of one another from the group consisting of phenyl, cyclohexyl and linear or branched-chain alkyl groups having 1 to 6 carbon atoms.

7. The process according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical.

8. The process according claim 1, wherein the mold in the reaction of the reaction mixture to give the melding moldings comprising oxazolidinone groups has a temperature of 140 C. to 280 C.

9. The process according to claim 1, wherein a polyol component comprising the at least one organic compound b) and the at least one catalyst c) is mixed with an isocyanate to form the reaction mixture.

10. The process according to claim 1, wherein an isocyanate component comprising the polyisocyanate a) and the at least one organic compound b) is mixed with the at least one catalyst c) to form the reaction mixture.

11. The process according to claim 1, wherein the polyisocyanate a) used is at least one isocyanate selected from the group consisting of dodecane 1,12-diioscyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, and hexamethylene 1,6-diisocyanate; cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate and also any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, dicyclohexylmethane 4,4-, 2,2- and 2,4-diisocyanate and also the corresponding isomer mixtures, tolylene 2,4- and 2,6-diisocyanate and the corresponding isomer mixtures, diphenylmethane 4,4-, 2,4- and 2,2-diisocyanate and the corresponding isomer mixtures, mixtures of diphenylmethane 4,4- and 2,2-diisocyanates, polyphenylpolymethylene polyisocyanates, mixtures of diphenylmethane 4,4-, 2,4- and 2,2-diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI), and mixtures of crude MDI and tolylene diisocyanates.

12. A molding comprising oxazolidinone groups, obtainable by a process according to claim 1.

13. A method for producing moldings comprising oxazolidinone groups, the method comprising using a catalyst of the general formula
[M(R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)].sup.+[X I.sub.n].sup., wherein M is a nitrogen atom or a phosphorus atom, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each an organic radical, in each case selected independently of one another from the group consisting of linear or branched-chain alkyl radicals having 1 to 22 carbon atoms and being possibly substituted by heteroatoms or substituents comprising heteroatoms, and of alkyl-bridged cycloaliphatic or aromatic groups having 3 to 22 carbon atoms and being possibly substituted by heteroatoms or by groups comprising heteroatoms, and of aryl radicals having 6 to 18 carbon atoms and being possibly substituted by alkyl groups having 1 to 10 carbon atoms and/or heteroatoms, X is fluoride, chloride, bromide or iodide, I is iodine, and n stands for a rational number from 0.1 to 10, for producing moldings comprising oxazolidinone groups.

Description

EXAMPLES

[0041] The invention is illustrated below using examples.

[0042] Raw Materials:

[0043] Epoxy 1: Bisphenol A-based diglycidyl ether (Lupranate Epilox A19-03 from LEUNA-Harze GmbH), with an epoxide equivalent weight (g/equiv.) of 190.

[0044] Epoxy 2: o-Cresyl glycidyl ether (Grilonit RV 1805 from EMS-Griltech) with an epoxide equivalent weight (g/equiv.) of 168.

[0045] Iso 1: Uretonimine-modified 4,4MDI (Lupranate MM103 from BASF).

[0046] Iso 2: 4,4-MDI-based prepolymer with an NCO value of 23% (Lupranate MP102 from BASF).

[0047] Iso 3: 4,4-MDI (Lupranate ME from BASF)

[0048] Mesamoll: (C10-C21) Alkanesulfonic acid phenyl ester from Lanxess.

[0049] Tetrabutylammonium chloride, tetrabutylammonium bromide,

[0050] Tetraphenylphosphonium bromide and iodine from Sigma-Aldrich.

Examples

[0051] Preparation of the Catalysts:

[0052] Catalyst 1:

[0053] 27.8 g of tetrabutylammonium chloride (0.1 mol) and 25.4 g of I.sub.2 (0.1 mol) are weighed out into a 100 mL glass flask. The vessel is closed and heated at 130 C. in an oven for 2 hours. Thereafter the temperature is reduced from 90 C. The flask is taken from the oven and the reaction product is mixed directly with 79.8 g of Mesamoll, heated briefly to 90 C. beforehand. The flask is subsequently closed and the mixture is further cooled, stored at 55 C. and used as it is. The mixing ratio of reaction product and Mesamoll was 0.4:0.6. The catalyst is called catalyst 1 below.

[0054] Catalyst 2:

[0055] For the preparation of the catalyst 2, the molar ratio of tetrabutylammonium chloride to iodine (I.sub.2) is reduced to 1:0.5. This is done by amending the amounts of the reactants to 27.8 g of tetrabutylammonium chloride and 12.7 g of iodine. The synthesis and addition of Mesamoll are carried out as described for catalyst 1; the amount of Mesamoll added is 60.8 g. This corresponds to a mixing ratio of reaction product and Mesamoll of 0.4:0.6.

[0056] Catalyst 3:

[0057] For the preparation of the catalyst 3, tetrabutylammonium bromide is reacted with iodine (I.sub.2) in a molar ratio of 1:1. This is done by reacting 32.2 g of tetrabutylammonium bromide and 25.4 g of iodine with one another. The synthesis and addition of Mesamoll are carried out as described for catalyst 1; the amount of Mesamoll added is 86.4 g. This corresponds to a mixing ratio of reaction product and Mesamoll of 0.4:0.6.

[0058] Catalyst 4:

[0059] For the preparation of the catalyst 4, the molar ratio of tetrabutylammonium bromide to iodine (I.sub.2) is reduced to 1:0.5. This is done by amending the amounts of the reactants to 32.2 g of tetrabutylammonium bromide and 12.7 g of iodine. The synthesis and addition of Mesamoll are carried out as described for catalyst 1; the amount of Mesamoll added is 67.4 g. This corresponds to a mixing ratio of reaction product and Mesamoll of 0.4:0.6.

[0060] Catalyst A:

[0061] 20.0 g of tetrabutylammonium chloride and 30.0 g of Mesamoll are weighed out into a 100 mL glass flask. The vessel is closed and is heated at 130 C. in an oven for 2 hours. This gave a liquid component which was stable even on cooling to room temperature.

[0062] Catalyst B:

[0063] 20.0 g of tetrabutylammonium bromide and 30.0 g of Mesamoll are weighed out into a 100 mL glass flask. The vessel is closed and is heated at 130 C. in an oven for 2 hours. This gave a liquid component which was stable even on cooling to room temperature.

[0064] Detection of Formation of Oxazolidinone Groups

[0065] Catalysts 1 to 4 and catalysts A and B are used for preparing polymers containing oxazolidinone groups. This is done by preparing the polymers from epoxy 1 and iso 1, with the molar ratio of the reactive groups being calculated at one to one and with the nominal molar amount of catalyst, based on the tetrabutylammonium halide content, being kept constant. For this purpose the specified components were heated at 55 C. and mixed in a Speedmixer at 1600 rpm for half a minute. Then the mixture was introduced into an aluminum mold with dimensions of 15200.2 cm, open at the top and at a temperature of 200 C., and reacted fully over a period of 30 minutes.

[0066] The detection method used for the formation of oxazolidinone groups was IR spectroscopy. The IR analysis was carried out using an IR instrument from Bruker, model ALPHA-27, equipped with a diamond measuring head. A small sample of polymer (a few milligrams) was pressed against the diamond measuring head and a spectrum was recorded. The formation of the oxazolidinone and isocyanurate groups was detected by the presence of a band at 1749 and 1704 cm.sup.1, respectively. The ratio of oxazolidinone to isocyanurate was evaluated on the basis of the ratio of the height (in cm) of the two bands (height at 1749 cm.sup.1 divided by height at 1704 cm.sup.1). The higher this value, the more oxazolidinone and the fewer isocyanurate groups the polymer contains. It should be noted that the epoxy 1 and iso 1 raw materials have no absorptions in the relevant IR frequency range. The baseline was drawn through the absorption values at 1850 cm.sup.1 and a minimum which is found at an absorption of around 1550 cm.sup.1.

[0067] Table 1 describes the mixtures and the oxazolidinone:isocyanurate ratios (Ox/Is) measured on the plates. Table 1 also shows that the plates produced with the catalysts of the invention exhibit a much higher oxazolidinone content.

TABLE-US-00001 TABLE 1 Catalyst 1 [parts by weight] 4.0 2 [parts by weight] 3.0 3 [parts by weight] 4.3 4 [parts by weight] 3.3 A [parts by weight] 2.0 B [parts by weight] 2.4 Tg [ C.] 131 113 135 119 110 110 Shore hardness 86 86 85 85 86 87 Notched impact strength 71 24 41 42 8 14 [kJ/m.sup.2] Flexural strength [N/mm.sup.2] 134 141 147 146 104 119 Flexural elasticity modulus 2875 3345 2900 3317 3156 3230 [N/mm.sup.2] Ox/Is ratio 1.38 1.07 1.85 1.42 0.89 0.76

[0068] The mechanical properties here were determined as follows:

[0069] Shore D hardness: DIN ISO 7619-1

[0070] Tensile strength: DIN EN ISO 527

[0071] Elongation at break: DIN EN ISO 527

[0072] Elasticity modulus: DIN EN ISO 527

[0073] Notched impact strength: DIN EN ISO 179-1/1 eU

[0074] Flexural strength: DIN EN ISO 178

[0075] Flexural elasticity modulus: DIN EN ISO 178

[0076] The table shows that by using catalysts of the invention, a significantly increased level of oxazolidinone groups in comparison to isocyanurate groups is obtained in the solid. This has consequences for the mechanical properties. Hence, when using the catalysts of the invention, there are increases in particular in the glass transition temperature, the notched impact strength and the flexural strength, for constant hardness.