ISOCYANATE COMPOSITION AND BINDER SYSTEM CONTAINING SAID ISOCYANATE COMPOSITION

Abstract

What is described are isocyanate compositions comprising -dicarbonyl compounds and a binder system, especially for use in a process from the group consisting of polyurethane cold-box process and polyurethane no-bake process, with this isocyanate composition as polyisocyanate component.

Claims

1. A process comprising the steps of: producing a molding material mixture by mixing a phenolic resin component (i) and a polyisocyanate component (ii) of a binder system with a molding material base, so as to form a molding material mixture, molding the molding material mixture, curing the binder system in the molded molding material mixture to form a molding, applying a coating composition comprising particles of one or more refractories dispersed in a carrier fluid to the molding, forming a coated molding, the surface of which has regions provided with the coating composition, subjecting the coated molding to thermal treatment at a temperature above 40 C., forming an article from the group consisting of foundry molds and foundry cores, the surface of which has regions in which a coating comprising particles of one or more refractories is disposed, wherein the phenolic resin component (i) comprises: e) 40% to 60% of one or more phenolic resins; and f) a solvent, where the concentration of component e) is based on the total mass of the phenolic resin component. wherein the polyisocyanate component (ii) comprises: a) 60% to 89% of one or more isocyanates having at least two isocyanate groups per molecule; b) 1% to 38% of one or more -dicarbonyl compounds; and c) a solvent which is not an isocyanate, a -dicarbonyl compound or an aldehyde, where the concentration of components a) to c) are based in each case on a total mass of the isocyanate composition, and wherein the one or more phenolic resins comprise an ortho-fused resol represented by the general formula (III): ##STR00010## wherein: X is selected from the group consisting of hydrogen, the methyl group CH.sub.3, the methylol group CH2OH and etherified methylol groups, R is hydrogen or a substituent in the meta or para position to the phenolic hydroxyl group, m is 1 or an integer >1, n for each of the m+1 groups (IIIa) ##STR00011## is independently selected from 0 and 1, where the number of groups (IIIa) with n=1 is greater than the number of groups (IIIa) with n=0.

2. The process as claimed in claim 1, wherein the binder system is cured by contacting the molded molding material mixture with a gaseous tertiary amine or with a mixture of two or more gaseous tertiary amines or with a liquid tertiary amine or with a mixture of two or more liquid tertiary amines.

3. The process as claimed in claim 1, wherein the phenolic resin component (i) further comprises: h) one or more -dicarbonyl compounds and reaction products formed by reaction of these -dicarbonyl compounds with formaldehyde, where the total concentration of unreacted -dicarbonyl compounds and those bound in reaction products with formaldehyde is 0.1% to 14%, based on the total mass of the phenolic resin component (i)

4. The process as claimed in claim 3, wherein the phenolic resin component (i) further comprises g) molecular formaldehyde in a concentration of less than 0.1%, and wherein the concentration of the -dicarbonyl compounds b) in the polyisocyanate component (ii) is present in a molar excess relative to the amount of molecular formaldehyde g) introduced into the molding material mixture with the phenolic resin component (i).

5. The process as claimed in claim 1, wherein the subjecting step comprises subjecting the coated molding to thermal treatment at a temperature in the range from 50 C. to 200 C.

6. The process as claimed in claim 1, wherein the molding is an article from the group consisting of feeders, foundry molds and foundry cores.

7. The process as claimed in claim 1, wherein multiple moldings are formed and combined to give an article from the group consisting of foundry molds and foundry cores.

8. The process as claimed in claim 1, wherein: the molding step comprises, producing two or more moldings, each by molding the molding material mixture, the curing step comprises curing each of the two or more moldings; the applying steps comprises applying a coating composition comprising particles of one or more refractories dispersed in a carrier fluid to the one, more than one or all moldings, forming coated moldings, the surfaces of which have regions provided with the coating composition, the method further comprises combining the moldings, where one, more than one or all moldings are coated moldings, to give a combined molding, and the subjecting step comprises subjecting the combined molding to thermal treatment at a temperature above 40 C. giving an article from the group consisting of foundry molds and foundry cores, the surface of which has regions in which a coating comprising particles of one or more refractories is disposed.

9. The process as claimed in claim 8, wherein the subjecting step comprises subjecting the combined molding to thermal treatment at a temperature in the range from 50 C. to 200 C.

10. The process as claimed in claim 1, wherein a) the isocyanates having at least two isocyanate groups per molecule are selected from the group consisting of methylenebis(phenyl isocyanates), polymethylene polyphenyl isocyanates, aliphatic isocyanates, cycloaliphatic isocyanates, isocyanates having at least two isocyanate groups and one carbodiimide group per molecule, isocyanates having at least two isocyanate groups and one uretonimine group per molecule, and/or b) the -dicarbonyl compounds are selected from the group of the dialkyl esters of malonic acid, and/or c) the solvent is selected from the group consisting of dialkyl esters of C.sub.4-C.sub.6 dicarboxylic acids, saturated and unsaturated fatty acid alkyl esters, alkylene carbonates, liquid hydrocarbons, compounds from the group of the alkylsilanes, alkyl/alkoxysilanes, alkoxysilanes, alkylsiloxanes, alkyl/alkoxysiloxanes and alkoxysiloxanes of the formula (I) ##STR00012## where n is an integer from 0 to 20, and each R, independently of the other R, is selected from the group of the alkyl groups having one to 6 carbon atoms and the alkoxy groups having one to 6 carbon atoms.

11. The process as claimed in claim 1, wherein, in the phenolic resin component (i), e) the phenolic resin is a ortho, ortho'-fused resol having unetherified terminal methylol groups and/or etherified terminal methylol groups and/or f) the solvent is selected from the group consisting of dialkyl esters of C.sub.4-C.sub.6 dicarboxylic acids, saturated and unsaturated fatty acid alkyl esters, alkylene carbonates, substances from the group consisting of cashew nut shell oil, components of cashew nut shell oil and derivatives of cashew nut shell oil, liquid hydrocarbons, compounds from the group of the alkylsilanes, alkyl/alkoxysilanes, alkoxysilanes, alkylsiloxanes, alkyl/alkoxysiloxanes and alkoxysiloxanes of the formula (I) ##STR00013## where n is an integer from 0 to 20, and each R, independently of the other R, is selected from the group of the alkyl groups having one to 6 carbon atoms and alkoxy groups having one to 6 carbon atoms.

12. The process as claimed in claim 1, wherein the phenolic resin component (i) further comprises g) molecular formaldehyde in a concentration of less than 0.1%, and/or h) one or more -dicarbonyl compounds, and reaction products formed by reacting these -dicarbonyl compounds with formaldehyde, and/or i) monomeric compounds from the group of the phenols in a concentration of 10% or less, where the concentrations are each based on the total mass of the phenolic resin component (i).

13. A binder system comprising: (i) a phenolic resin component, and, separately, (ii) a polyisocyanate component, wherein the phenolic resin component (i) comprises: e) 40% to 60% of one or more phenolic resins; and f) a solvent, where the concentration of component e) is based on the total mass of the phenolic resin component. wherein the polyisocyanate component (ii) comprises: a) 60% to 89% of one or more isocyanates having at least two isocyanate groups per molecule; b) 1% to 38% of one or more -dicarbonyl compounds; and c) a solvent which is not an isocyanate, a -dicarbonyl compound or an aldehyde, where the concentration of components a) to c) are based in each case on a total mass of the isocyanate composition, and wherein at least one of the following is true: (1) the phenolic resin component (i) comprises h) one or more -dicarbonyl compounds and reaction products formed by reaction of these -dicarbonyl compounds with formaldehyde, where the total concentration of unreacted -dicarbonyl compounds and those bound in reaction products with formaldehyde is 0.1% to 14%, based on the total mass of the phenolic resin component (i); or (2) the one or more phenolic resins comprise an ortho-fused resol represented by the general formula (III): ##STR00014## wherein: X is selected from the group consisting of hydrogen, the methyl group CH.sub.3, the methylol group CH.sub.2OH and etherified methylol groups, R is hydrogen or a substituent in the meta or para position to the phenolic hydroxyl group, m is 1 or an integer >1, n for each of the m+1 groups (IIIa) ##STR00015## is independently selected from 0 and 1, where the number of groups (IIIa) with n=1 is greater than the number of groups (IIIa) with n=0.

14. The binder system as claimed in claim 13, wherein the phenolic resin component (i) further comprises: h) one or more -dicarbonyl compounds and reaction products formed by reaction of these -dicarbonyl compounds with formaldehyde, where the total concentration of unreacted -dicarbonyl compounds and those bound in reaction products with formaldehyde is 0.1% to 14%, based on the total mass of the phenolic resin component (i)

15. The binder system as claimed in claim 14, wherein the phenolic resin component (i) further comprises g) molecular formaldehyde in a concentration of less than 0.1%, and wherein the concentration of the -dicarbonyl compounds b) in the polyisocyanate component (ii) is present in a molar excess relative to the amount of molecular formaldehyde g) introduced into the molding material mixture with the phenolic resin component (i).

16. The binder system as claimed in claim 13, wherein a) the isocyanates having at least two isocyanate groups per molecule are selected from the group consisting of methylenebis (phenyl isocyanates), polymethylene polyphenyl isocyanates, aliphatic isocyanates, cycloaliphatic isocyanates, isocyanates having at least two isocyanate groups and one carbodiimide group per molecule, isocyanates having at least two isocyanate groups and one uretonimine group per molecule, and/or b) the -dicarbonyl compounds are selected from the group of the dialkyl esters of malonic acid, and/or c) the solvent is selected from the group consisting of dialkyl esters of C.sub.4-C.sub.6 dicarboxylic acids, saturated and unsaturated fatty acid alkyl esters, alkylene carbonates, liquid hydrocarbons, compounds from the group of the alkylsilanes, alkyl/alkoxysilanes, alkoxysilanes, alkylsiloxanes, alkyl/alkoxysiloxanes and alkoxysiloxanes of the formula (I) ##STR00016## where n is an integer from 0 to 20, and each R, independently of the other R, is selected from the group of the alkyl groups having one to 6 carbon atoms and the alkoxy groups having one to 6 carbon atoms.

17. The binder system as claimed in claim 13, wherein, in the phenolic resin component (i), e) the phenolic resin is a ortho, ortho'-fused resol having unetherified terminal methylol groups and/or etherified terminal methylol groups and/or f) the solvent is selected from the group consisting of dialkyl esters of C4-C6 dicarboxylic acids, saturated and unsaturated fatty acid alkyl esters, alkylene carbonates, substances from the group consisting of cashew nut shell oil, components of cashew nut shell oil and derivatives of cashew nut shell oil, liquid hydrocarbons, compounds from the group of the alkylsilanes, alkyl/alkoxysilanes, alkoxysilanes, alkylsiloxanes, alkyl/alkoxysiloxanes and alkoxysiloxanes of the formula (I) ##STR00017## where n is an integer from 0 to 20, and each R, independently of the other R, is selected from the group of the alkyl groups having one to 6 carbon atoms and alkoxy groups having one to 6 carbon atoms.

18. The binder system as claimed in claim 13, wherein the phenolic resin component (i) further comprises g) molecular formaldehyde in a concentration of less than 0.1%, and/or h) one or more -dicarbonyl compounds, and reaction products formed by reacting these -dicarbonyl compounds with formaldehyde, and/or i) monomeric compounds from the group of the phenols in a concentration of 10% or less, where the concentrations are each based on the total mass of the phenolic resin component (i).

Description

1. PRODUCTION AND TESTING OF TEST SPECIMENS IN THE FORM OF FLEXURAL BARS

1.1 Composition of the Binder Systems

[0314] The figures in % by weight are respectively based on the total mass of the phenolic resin component (i) or of the polyisocyanate component (ii).

[0315] Binder system I

[0316] Phenolic resin component (i):

[0317] Phenolic resin e) ortho, ortho'-fused resol with terminal methylol groups CH.sub.2OH and methanol-etherified terminal methylol groups CH.sub.2OCH.sub.3, 54% by weight

[0318] Solvent f) mixture of tetraethyl silicate and dialkyl esters of C.sub.4-C.sub.6 dicarboxylic acids

[0319] Isocyanate component (ii)

[0320] Isocyanate: a) polymeric MDI, 85% by weight

[0321] Solvent c) mixture of rapeseed oil methyl ester and propylene carbonate

[0322] In a first noninventive variant of the binder system I, neither component (i) nor component (ii) contains a -dicarbonyl compound. In a second noninventive variant of the binder system I, component (i) contains diethyl malonate as -dicarbonyl compound h), where the total concentration of unreacted diethyl malonate and that bound in reaction products with formaldehyde is 6% by weight, and component (ii) does not contain any -dicarbonyl compound.

[0323] In a first inventive variant of the binder system I, component (i) does not contain any -dicarbonyl compound and component (ii) contains 5% by weight of diethyl malonate as -dicarbonyl compound b). In a second inventive variant of the binder system I, component (i) contains diethyl malonate as -dicarbonyl compound h), where the total concentration of unreacted diethyl malonate and that bound in reaction products with formaldehyde is 1% by weight, and component (ii) contains 5% by weight of diethyl malonate as -dicarbonyl compound b).

[0324] Binder system II

[0325] Phenolic resin component (i):

[0326] Phenolic resin e) ortho, ortho'-fused resol with terminal methylol groups CH.sub.2OH and methanol-etherified terminal methylol groups CH.sub.2OCH.sub.3, 54.5% by weight

[0327] Solvent f) mixture of dialkyl esters of C.sub.4-C.sub.6 dicarboxylic acids and rapeseed oil methyl ester

[0328] Isocyanate component (ii)

[0329] Isocyanate: a) polymeric MDI, 85% by weight

[0330] Solvent c) rapeseed oil methyl ester

[0331] In a noninventive variant of the binder system II, neither component (i) nor component (ii) contains a -dicarbonyl compound.

[0332] In an inventive variant of the binder system II, component (i) contains diethyl malonate as -dicarbonyl compound h), where the total concentration of unreacted diethyl malonate and that bound in reaction products with formaldehyde is 1% by weight, and component (ii) contains 3% by weight of diethyl malonate as -dicarbonyl compound b).

1.2 Production of Test Specimens (Cold-Box Method)

[0333] Molding material mixtures comprising H32 quartz sand as molding material base and one (inventive or noninventive) variant in each case of one of the binder systems I and II described in point 1.1 were used to produce test specimens in the form of flexural bars by the cold-box method.

[0334] For production of the molding material mixture, the molding material base (100 parts by weight) was initially charged in a mixing vessel. The phenolic resin component (i) (0.7 part by weight) and the polyisocyanate component (ii) (0.7 part by weight) of the respective binder system were then weighed into the mixing vessel in such a way that they do not mix directly. Subsequently, molding material base, phenolic resin component (i) and polyisocyanate component (ii) were mixed in a bull mixer for 120 seconds at level 4 to give a molding material mixture.

[0335] The molding material mixture was molded by means of a Multiserw core shooting machine at a shooting pressure of 4 bar (400 kPa). For curing of the binder system in the molded molding material mixture, sparging with dimethylpropylamine (in a carrier gas stream) at a temperature in the range from 20 to 30 C. was effected at a sparging pressure of 2 bar (200 kPa) by means of a Titronic 110 Plus sparging device.

1.3 Measurement of Formaldehyde Emissions on Thermal Treatment

[0336] Selected test specimens without coating on the basis of a refractory coating were subjected to a temperature of 177 C. in a tubular oven. One minute after the test specimens had been introduced into the oven heated to 177 C., measurement of the concentration of formaldehyde in the oven air commenced. For this purpose, air is drawn out of the tubular oven through a LpDNPH cartridge (LpDNPH cartridge S10 volume 3 mL from Supelco) at a volume flow rate of 1.5 L/min by means of a Xact 5000 pump (from Drger) for 10 minutes. The cartridge was analyzed by means of HPLC according to DIN 16000-3.

[0337] The results of the measurements are compiled in the following table:

TABLE-US-00003 Diethyl Formaldehyde concen- malonate tration in the oven air in binder [mg/m.sup.3] after 10 Binder system component minutes I First noninventive variant none 5 I Second noninventive variant (i) 2.2 I Second inventive variant (i), (ii) 1.1 II Noninventive variant none 6.0 II Inventive variant (i), (ii) 4.5

[0338] Under thermal stress, the test specimens that have been produced with a binder system of the invention release much less formaldehyde than the test specimens produced with a noninventive variant of the corresponding binder system.

1.4 Measurements of Flexural Strength

[0339] In order to ensure that the addition of diethyl malonate to the polyisocyanate component of the binder system does not have any adverse effect on the strength of moldings produced with this binder system, flexural strengths of the test specimens produced with various variants of the binder system I were ascertained as a function of various parameters (time after the end of curing, storage time of the molding material mixture prior to the molding, storage conditions of the test specimens produced, coating on the basis of a refractory coating). For details we refer to the table that follows. The terms in this table have the following meanings: [0340] B core (1 h): Test specimen dipped into refractory-coating composition immediately after curing, stored in a digester at room temperature, tested after 1 h. [0341] D core cold: Test specimen dipped into refractory-coating composition immediately after curing, dried in an oven at 150 C. for 1 h, cooled to room temperature and then tested. [0342] The refractory-coating composition contains water as carrier liquid, and particles of aluminum silicate as refractory. [0343] F core: Test specimen stored at 100% relative air humidity at room temperature for 1 day immediately after curing, and tested immediately after removal from storage.

[0344] Each determination was effected on a specially produced test specimen. The results of the measurements are compiled in the following table:

TABLE-US-00004 First nonin- First in- Second in- ventive ventive ventive Variant of binder system I variant variant variant Diethyl malonate in binder none (ii) (i) and (ii) component Flexural strengths No storage of the molding material mixture prior to molding 15 sec after end of curing 250 240 260 1 h after end of curing 390 410 410 24 h after end of curing 460 490 490 Storage of the molding material mixture for 1 h prior to molding 15 sec after end of curing 260 250 250 1 h after end of curing 400 400 390 24 h after end of curing 470 470 470 Test specimen with coating on the basis of a refractory coating B-1 d 420 470 450 D cold 520 520 530 Storage at 100% air humidity F-1 d 390 400 420

[0345] The test specimens produced with inventive variants of the binder system I, under all conditions, show similar flexural strengths to the test specimens produced with the noninventive variants of the binder system I.

2. Production of Cores for the Casting of Brake Disks

[0346] Molding material mixtures comprising H32 quartz sand as molding material base and one (inventive or noninventive) variant in each case of the binder system I described in point 1.1 were used to produce cores for the casting of brake disks by the cold-box method.

[0347] For production of the molding material mixture, the molding material base (100 parts by weight) was initially charged in a mixing vessel. The phenolic resin component (i) (1 part by weight) and the polyisocyanate component (ii) (1 part by weight) of the respective variant of binder system I were then weighed into the mixing vessel in such a way that they do not mix directly. Subsequently, molding material base, phenolic resin component and polyisocyanate component were mixed in a Glass mixer.

[0348] The molding material mixture was molded by means of a Laempe LL20 core shooting machine at a shooting pressure of 4 bar (400 kPa) and a shooting time of 2.5 sec. For curing of the binder system in the molded molding material mixture, sparging was effected with dimethylpropylamine (DMPA) at 120 C. at a sparging pressure of 3 bar (300 kPa) by means of a Lber sparging unit.

[0349] The cores were not provided with a coating on the basis of a refractory coating. In order to ascertain the influence of the binder composition on the amount of formaldehyde emissions under thermal stress, the cores were subjected to a thermal treatment under similar conditions to those in the production of coatings on the basis of a refractory coating.

[0350] 30 cores thus produced were placed into an Elpo drying oven (not identical to the oven that was used for the tests described in point 1.3) that had been preheated to 170 C. A stream of air was passed through the oven at a rate of 1600 m.sup.3/h.

[0351] Once the cores had been put into the oven and the oven had reached the target temperature of 170 C. again, the sampling for determination of formaldehyde was started. A Xact 5000 pump (from Drger) with a rod-shaped probe was used. For sampling, the rod-shaped probe was introduced into the offgas pipe of the drying oven, and a volume flow rate of 2 L/min was drawn from the offgas pipe and passed through LpDNPH cartridges (LpDNPH Cartridge S10 volume 3 mL from Supelco) for 15 minutes. The cartridges were analyzed according to DIN ISO 16000-3.

[0352] The results of the measurements (double determination; therefore two values in each case) are compiled in the following table:

TABLE-US-00005 Formaldehyde concen- Diethyl tration in the air output malonate in [mg/m.sup.3] after 15 binder component Inventive? minutes none no 0.846/0.781 (ii) yes 0.662/0.580 (i), (ii) yes 0.492/0.537

[0353] The cores that had been produced with an inventive variant of the binder system I release much less formaldehyde under thermal stress than the cores produced with the first noninventive variant of binder system I. The reduction in formaldehyde emissions is particularly significant when diethyl malonate has been added to both binder components.