Stabilization of compounds comprising iodine

Abstract

Use of aziridines for stabilizing iodine-containing compounds, especially biocides.

Claims

1. A binder formulation comprising: at least one alkyd resin binder, at least one iodine containing compound, and at least one aziridine compound of the formula (I) ##STR00011## where R.sup.1 is hydrogen, alkyl or cycloalkyl, each of which are unsubstituted or substituted and/or mono- or polyethylenically unsaturated, or in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl or alkanoyl, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently of one another have the same definition as R.sup.1 and additionally independently are halogen, hydroxyl, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, and/or R.sup.2 and R.sup.4, or R.sup.3 and R.sup.5, together with the carbon atoms to which they are attached, form a 5- to 10-membered carbocyclic ring which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated.

2. The binder formulation according to claim 1, further comprising at least one transition metal dryer.

3. The binder formulation according w claim 1, further comprising at least one polar organic solvent.

4. The binder formulation according to claim 1, comprising 1% to 80% by weight of the alkyd resin binder(s), 0% w 50% by weight of colour pigments, 0.01% to 5% by weight of the iodine-containing compound, 0.001% to 5% by weight of the aziridine compound, 2% to 97% by weight of solvent(s), and 0.001% to 3% by weight of a transition metal dryer.

5. Industrial materials comprising the binder formulation according to claim 1.

6. The binder formulation according to claim 1, wherein the iodine-containing compound is selected from the group consisting of diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy-3(2H)-pyridazinone (CAS RN: 120955-77-3), iodofenfos, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl 3-iodopropargyl formal, 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-do-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (IPC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.

7. The binder formulation according to claim 1, wherein the iodine-containing compound is selected from the group consisting of 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-Iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (IPC), 3-bromo-23-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.

8. The binder formulation according to claim 1, wherein the iodine-containing compound is selected from the group consisting of N-alkyl-iodotetrazoles, N-aryl-iodotetrazoles, and N-aralkyl-iodotetrazoles.

9. A binder formulation comprising: at least one alkyd resin binder, at least one iodine containing compound, and at least one aziridine compound of the formula (II) ##STR00012## where the carbocyclic ring is unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, oxo, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile, isonitrile, alkyl or cycloalkyl, each of which is unsubstituted or substituted and/or mono- or polyethylenically unsaturated, or substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl, and n is a number from 0 to 6.

10. The binder formulation according to claim 9, further comprising at least one transition metal dryer.

11. The binder formulation according w claim 9, further comprising at least one polar organic solvent.

12. The binder formulation according to claim 9, comprising 1% to 80% by weight of the alkyd resin binder(s), 0% w 50% by weight of colour pigments, 0.01% to 5% by weight of the iodine-containing compound, 0.001% to 5% by weight of the aziridine compound, 2% to 97% by weight of solvent(s), and 0.001% to 3% by weight of a transition metal dryer.

13. Industrial materials comprising the binder formulation according to claim 9.

14. The binder formulation according to claim 9, wherein the iodine-containing compound is selected from the group consisting of diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone (CAS RN: 120955-77-3), iodofenfos, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl 3-iodopropargyl formal, 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (IPC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.

15. The binder formulation according to claim 9, wherein the iodine-containing compound is selected from the group consisting of 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (IPC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.

16. The binder formulation according to claim 9, wherein the iodine-containing compound is selected from the group consisting of N-alkyl-iodotetrazoles, N-aryl-iodotetrazoles, and N-aralkyl-iodotetrazoles.

Description

EXAMPLES

(1) In the examples below, stability tests accelerated by storage at elevated temperature are carried out. The IPBC was assayed in all cases by HPLC.

Examples 1-4

(2) Examples 1-4 use investigations to illustrate the sensitivity of IPBC with regard to transition metal dryers.

Example 1

IPBC

(3) IPBC (3.4900 g; 0.0124 mol) is weighed out into a 50 ml volumetric flask and made up to 50 ml with tripropylene glycol monomethyl ether (Dowanol TPM), and the solution is transferred to an inertised (N.sub.2) 100 ml two-necked flask. After a sample has been taken to determine the initial IPBC content at time (t.sub.0), the flask is lowered into an oil bath set to a temperature of 60 C., and the solution is stirred under nitrogen. For determination of the IPBC content over time, a Hamilton syringe is used to take samples at intervals, which are cooled to room temperature and then subjected to defined dilution. For this purpose, 0.5 ml of the sample in the volumetric flask is made up to 10 ml with acetonitrile (MeCN) and subjected to direct measurement (HPLC). Table 1 shows the course of the IPBC fractions as a function of time.

(4) TABLE-US-00001 TABLE 1 Determination of IPBC content (measurement error approx. 10%). Relative IPBC Time [h] content [%] 0 100 0.5 94 1 100 2 93 4 99 7 93

Example 2

IPBC+Co Dryer

(5) IPBC (3.532 g; 12.60 mmol) is weighed out into a 50 ml volumetric flask and made up to 50 ml with tripropylene glycol monomethyl ether (Dowanol TPM), and the solution is transferred to an inertised (N.sub.2) 100 ml two-necked flask, which has been charged beforehand with 1.260 g of Octasoligen-Cobalt 12 from Borchers (cobalt(II) carboxylates of branched C.sub.6-C.sub.19 fatty acids, in solution in white spirit, 12% Co content; 2.566 mmol of Co). After 1 minute of stirring and the taking of a sample for determination of the initial IPBC content at time (t.sub.0), the flask is lowered into an oil bath set to a temperature of 60 C., and the solution is stirred under nitrogen. The IPBC content is determined as in Example 1. Table 2 shows the course of the IPBC content as a function of time.

(6) TABLE-US-00002 TABLE 2 Determination of IPBC content (measurement error approx. 10%). Relative IPBC Time [h] content [%] 0 100 0.5 87 1 82 2 72 4 55 7 37

Example 3

IPBC+Aziridine Comp.+Co Dryer

(7) IPBC (3.741 g; 13.31 mmol) is weighed out into a 50 ml volumetric flask and made up to 50 ml with tripropylene glycol monomethyl ether (Dowanol TPM), and the solution is transferred to an inertised (N.sub.2) 100 ml two-necked flask, which has been charged beforehand with 1.252 g of Octasoligen-Cobalt 12 from Borchers (cobalt(II) carboxylates of branched C.sub.6-C.sub.19 fatty acids, in solution in white spirit, 12% Co content; 2.549 mmol of Co). Following addition of 7.551 g (16.64 mmol) of trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate] (Crosslinker CX-100 from DSM), 1 minute of stirring and the taking of a sample for determination of the initial IPBC content at time (t.sub.0), the flask is lowered into an oil bath set to a temperature of 60 C., and the solution is stirred under nitrogen. The IPBC content is determined as in Example 1. Table 3 shows the course of the relative IPBC content as a function of time.

(8) TABLE-US-00003 TABLE 3 Determination of IPBC content Relative IPBC Time [h] content [%] 0 100 0.5 109 1 101 2 105 4 97 7.5 93

(9) Within the bounds of measurement error (approx. 10%), no degradation of IPBC is found.

Example 4

IPBC+Aziridine Comp.+Co Dryer

(10) IPBC (1.3583 g, 4.832 mmol) is weighed out into a 20 ml volumetric flask and made up to 20 ml with tripropylene glycol monomethyl ether (Dowanol TPM), and the solution is transferred to an inertised (N.sub.2) 50 ml two-necked flask, which has been charged beforehand with 0.5123 g of Octasoligen-Cobalt 12 from Borchers (cobalt(II) carboxylates of branched C.sub.6-C.sub.19 fatty acids, in solution in white spirit, 12% Co content; 1.043 mmol of Co). Following addition of 5.018 g (19.97 mmol) of 7-tolylsulphonyl-7-azabicyclo[4.1.0]heptane, 1 minute of stirring and the taking of a sample for determination of the initial IPBC content at time (t.sub.0), the flask is lowered into an oil bath set to a temperature of 60 C. and the solution is stirred under nitrogen. The IPBC content is determined as in Example 1. Table 4 shows the course of the relative IPBC content as a function of time.

(11) TABLE-US-00004 TABLE 4 Determination of IPBC content Relative IPBC content Time [h] [%] 0 100 0.5 88 1 86 2 80 4 64 7 58

(12) Within the bounds of measurement error (approx. 10%), a level of IPBC degradation significantly lower by comparison with Example 2 is found.

Example 5

(13) This example demonstrates the stabilizing effect of the aziridine trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate](Crosslinker CX-100 from DSM) and also of the aziridine trimethylolpropane tris[3-(1-aziridinyl)propionate](Corial Hrter AN from BASF) on the IPBC in the presence of a transition metal dryer (Co) and of a metal oxide pigment (iron oxide) in a typical, alkyd-based coating system (alkyd stain A). The coating system was equipped using compositions as per Table 5:

(14) TABLE-US-00005 TABLE 5 Concentrate I Concentrate II IPBC 30% by weight IPBC 30% by weight Rhodiasolv 70% by weight Crosslinker 15% by weight DIB* CX-100** Rhodiasolv DIB* 55% by weight Concentrate III IPBC 30% by weight Corial Harter 10% by weight AN*** Rhodiasolv DIB* 60% by weight *Mixture of diisobutyl adipate, diisobutyl glutarate and diisobotyl succinate, from Rhodia. **Trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate] ***Trimethylolpropane tris[3-(1-aziridinyl)propionate]

(15) The formula of the alkyd stain used is shown in Table 6 (alkyd stain A).

(16) The stabilization is determined by implementation of an accelerated ageing test. For this purpose the additised paint system is charged to tightly sealing 200 ml glass bottles, with only a minimum amount of air remaining in the container, and subjected to storage at 40 C. The results can be seen from Table 7.

(17) TABLE-US-00006 TABLE 6 Formula of a pigmented alkyd-based stain. Ingredients of alkyd Ingredients of alkyd Ingredients stain A-I [%] stain A-II [%] Alkyd stain A Vialkyd VAF 4349, 80 SD 60, 22.5 22.5 from Cytec Polar solvent Texanol, from 5.0 5.0 Eastman Rheology additive BYK E411, 0.4 0.4 from BYK Shellsol D60, from Shell 65.47 65.47 Chemicals MK-Solcolor red iron oxide 4.0 4.0 130M (pigment preparation), from MK Chemicals Octa-Soligen 69 (contains 0.3 0.3 6% Co), from Borchers Concentrate I 2.33 Concentrate II 2.33 Alkyd stain A-III = 97.67% alkyd stain A + 2.33% concentrate III.

(18) TABLE-US-00007 TABLE 7 Stability of IPEC in alkyd stains A-I and A-II at 40 C. Stain IPBC [%], initial IPBC [%], 2 weeks IPBC [%], 4 weeks A-I (aziridine-free) 0.71 0.11 0 A-II (containing aziridine) 0.69 0.67 0.62 A-III (containing aziridine) 0.67 0.67 0.63

Example 6

(19) This example demonstrates the stabilizing effect of the aziridine trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate] (Crosslinker CX-100 from DSM) on the IPBC in a commercial high-build woodstain alkyd stain B (containing alkyd resin, white spirit, iron oxide pigment, dryer, butanone oxime, UV absorbers and additives) in comparison to epoxides of the kind described, for example, in EP 1115287 B1. The coating system is equipped using compositions as per Table 8:

(20) TABLE-US-00008 TABLE 8 Concentrate I Concentrate II IPBC 30% by weight IPBC 30% by weight Rhodiasolv 70% by weight Crosslinker 15% by weight DIB* CX-100** Rhodiasolv DIB* 55% by weight Concentrate III Concentrate IV IPBC 30% by weight IPBC 30% by weight DTGE.sup.1) 30% by weight EEC.sup.2) 15% by weight Rhodiasolv 40% by weight Rhodiasolv DIB* 55% by weight DIB* For definition of * and ** see Table 5; .sup.1)Mixture containing the epoxides 2-[(dodecyloxy)methyl]oxirane and 2-[(tetradecyloxy)methyl]oxirane (CAS No. 68609-97-2), e.g. from Aldrich. .sup.2)(3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate (CAS No. 2386-87-0), e.g. from Aldrich.

(21) In addition, a commercially available IPBC formulation (Troy Polyphase 920, containing 20% IPBC) was used which is referred to below as concentrate V. The high-build woodstains under investigation, equipped with 0.7% by weight of IPBC (alkyd stain B-I to alkyd stain B-V), were prepared by mixing 97.67% of the aforementioned alkyd stain B with 2.33% by weight of each of concentrates I to V, respectively.

(22) The stabilization is determined by implementation of an accelerated ageing test. For this purpose, the additised paint system was charged to tightly sealing 200 ml glass bottles, with only a minimum amount of air remaining in the container, and subjected to storage at 40 C. The results are apparent from Table 9, according to which only the alkyd stain B-II equipped with the aziridine Crosslinker CX-100 shows no significant IPBC degradation after 4 weeks of storage at 40 C.

(23) TABLE-US-00009 TABLE 9 Stability of IPBC in alkyd stains B-I to B-V at 40 C. Alkyd Residual IPBC content [%] relative to initial level stain B Initial 2 weeks 4 weeks 8 weeks 12 weeks 16 weeks -I 100 24 0 -II 100 95 95 86 56 7 -III 100 9 0 -IV 100 30 3 0 -V 100 52 0

Example 7

(24) This example shows that the addition of the aziridine trimethylolpropane tris[3-(2-methyl-1-aziridinyl)propionate](Crosslinker CX-100 from DSM) to the commercial high-build woodstain alkyd stain B (see Example 6) is able to prevent the unwanted prolongation of the drying time of the coating material that is caused by its additisation with IPBC. The stains investigated are set out in Table 10.

(25) TABLE-US-00010 TABLE 10 Alkyd Alkyd stain Alkyd stain stain B B-VI B-VII Constituent Fraction [%] Fraction [%] Fraction [%] Alkyd stain B 100.0 99.50 99.20 IPBC (e.g. Preventol 0.50 0.50 MP 100) Crosslinker CX-100* 0.30 For definition of * see Table 5.

(26) The drying times were determined with the freshly prepared stains and with the stains stored at 40 C. for 2 weeks (accelerated ageing test). For drying time determination, a film applicator was used to apply a 90 m film of the respective stain to glass, and the drying times were determined using a drying time measuring instrument (e.g. BYK-Gardner), with measurements of the times required for initial drying and for through-drying of the film. The results of these investigations are set out in Table 11.

(27) TABLE-US-00011 TABLE 11 Determination of drying times. Fresh sample 2 weeks of storage at 40 C. Initial Through- Initial Through- drying [h] drying [h] drying [h] drying [h] Alkyd stain B 3.2 3.7 3.7 4.3 Alkyd stain B-VI 3.3 3.8 10.6 >12 Alkyd stain B-VII 3.2 3.4 4.4 4.6