Foundry binders on the basis of phenolic resins
United States Patent 1191 Vargiu et al.  
 [ 1 Apr. 15, 1975 1 FOUNDRY BINDERS ON THE BASIS OF PHENOLIC RESINS [75] Inventors: Silvio Vargiu; Silvestro Pezzoli, both of Milan, Italy [73] Assignee: Societa Italiana Resine S.I.R. S.p.A.,  
 Milan, Italy [22] Filed: June 12, 1973 [21] Appl. No.: 369,346  
 [30] Foreign Application Priority Data June 13, 1972 ltaly 25581/72 [52] U.S. c1. 260/38; 164/43; 260/DIG. 40 51 1m.c1 C08g 51/04 58 Field of Search 260/DIG. 40, 38-, 164/43 [56] References Cited UNITED STATES PATENTS 2,955,336 10/1960 Horn et al 260/D1G. 40  
 3,692,733 9/1972 Johnson 260/DlG, 40 3,720,642 3/1973 .lunger et al. .1 260/D1G. 40 3,745,139 7/1973 Kachur et al. 260/D1G. 40  
 Primary Examiner-Donald E. Czaja Assistant Examiner-S. M, Person Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn &amp; Macpeak [5 7 ABSTRACT 6 Claims, No Drawings FOUNDRY BINDERS ON THE BASIS OF PHENOLIC RESINS The invention relates to foundry binders based on phenolic resins and their use for the hot coating of core and moulding sands in the absence of solvents.  
  The use of phenolic&#39;resins of the novolak type for the coating of moulding sand is&#39;known. For this purpose, the phenolic resin is either used directly or a solution of the phenolic resin in a suitable organic solvent is used. In the latter case the novolak phenolic resin is dissolved in an organic solvent and the resulting solution is mixed with the moulding sand. The phenolic resin is usually used in a quantity of 3 to 5 wt.% with respect to the moulding sand. Hexamethylenetetramine is then added, the composition is homogenized, and the solvent is removed at temperatures between room temperature and about 100C by introduction of a stream of gas.  
  A modification of this process consists in mixing the moulding sand with powdered phenolic resin and hexamethylenetetramine and then dissolving the phenolic resin by addition of an organic solvent. After homogenization of the composition, the solvent is removed as described above.  
  However, these known processes have many disadvantages, which are associated inter alia with the harmfulness and flammability of the volatile solvents used. The processes are also expensive, since the coating of the moulding sands takes relatively long time (generally -20 minutes) and the solvent cannot usually be recovered.  
  In another known process, moulding sand is coated with a thermosetting resin, particularly a novolak phenolic resin, and hexamethylenetetramine without the use of solvents, the operating temperatures then being above room temperature. In this process, solid phenolic resin in flake form is mixed with the heated moulding sand thereby melting the resin. More particularly, the procedure is as follows. Moulding sand heated to temperatures of 130 to 170C is introduced into a suitable mixer, in which it is mixed with 2 to 5 wt.% of flake resin. Hexamethylenetetramine is then added, usually as an aqueous solution, and the resulting composition is heated for a certain time. Because of the temperature of the moulding sand, the phenolic resin melts and coats the sand grains with a thin film. The coated moulding sand produced in this way is generally flowable and can be stored for long periods. In the production of foundry cores and moulds, the film on the coated sand grains melts and cures so that parts having high mechanical strength are formed.  
  The hot coating of moulding sand in the absence of solvents requires binders having special properties, eg a low softening point, high fluidity in the molten state, and fast heat-curability. The melting point of the binder should preferably be 50 to 80 C, and the flowability should be 60 120 mm, the flowability being measured with the aid of a plate heated to 125C and inclined at 64. The flowability of the binder is particularly important for fast and uniform coating of the sand grains. Whereas working time can be saved on the one hand, smaller quantities of binder are required with uniform coating. Fast heat-curability of the binder not only allows the production of cores and moulds having high mechanical strength but also prevents scaling. Scaling is the removal of surface layers of the mould or core on removal of the heat source, with the result that moulds of nonuniform thickness are formed.  
  An object of the invention is therefore to provide new foundry binders on the basis of novolak phenolic resins that have a low softening point and high fluidity in the molten state, that are rapidly thermosetting at relatively high curing temperatures, and give cores or moulds having improved mechanical strength on hot coating of foundry sand in the absence of solvents.  
  It has been found that moulds and cores having improved mechanical strength can be obtained by coating foundry sand with a binder comprising a novolak and a silane. The mechanical properties can be still further improved by the use of diamide of a long-chain monocarboxylic acid in combination with the silane and the novolak. Finally, it has been found that the fluidity of mixtures of the phenolic resin and the diamide can be increased by addition of silanes.  
  The invention thus relates to foundry binders on the basis of phenolic resins, comprising a. a novolak prepared by condensation of phenols with aldehydes in a molar ratio of about 110.4 to 0.9 in the presence of an acid catalyst,  
 b. about 0.05 to about 1.0 wt.% of a silane, and  
 c. about 0.5 to about 8.0 wt.% of the diamide of a longchain monocarboxylic acid, and optionally d. about 1.0 to about 6.0 wt.% of an aromatic carboxylic acid.  
  Novolaks suitable for the purposes of the invention are prepared by condensation of a phenol with an aldehyde in a molar ratio of about 1:04 to 0.9 in the presence of an acid catalyst.  
  Specific examples of suitable phenolic compounds are phenol, which may be substituted in the oand/or p-position, o-, m-, and p-cresol, xylenols, and resorcinol, phenol being-preferred.  
  The preferred aldehyde is formaldehyde; it may be used either as aqueous formalin solution, in the form of oligomers such as paraformaldehyde, or in the form of compounds that liberate formaldehyde.  
  Organic or inorganic acids are used as catalysts, and are added to the reaction medium in a quantity of 0.1 to 5.0 wt.% with respect to the phenolic compound. Specific examples of such acid catalysts are mineral acids or sulfonic acids such as p-toluenesulfonic acid and phenolsulfonic acid, carboxylic acids, such as oxalic and maleic acids or other carboxylic acids having a dissociation constant greater than 1.76 X 10 It is absolutely essential to adhere to a molar ratio of aldehyde to phenolic compound of about 0.421 to about 0.9:1. Lower ratios are unfavourable on economic grounds, whereas higher ratios give binders that impart unsatisfactory properties to the foundry moulds.  
  The novolak condensation is carried out at temperatures of about to about C until the content of free formaldehyde in the reaction products reaches values lower than 3 wt.%.  
  Specific silanes that are suitable forthe purpose of the invention have the general formula where R is an ethyl or methyl group group and R may be a residue of any nature, preferably a vinyl group or an alkyl residue substituted with mercapto groups, optionally substituted amino residues, epoxyalkyl residues, or epoxycycloalkyl residues.  
 = hydroxyethyl)-&#39;y-aminopropyltriethoxysilane,  
  Specific examples of such silanes are &#39;y-aminopropyltriethoxysilane, B-aminoethyltrimethoxysilane, y-glycidoxypropyltrimethoxysilane, B-( 3 ,4-  
 ,epoxycyclohexyl)ethyltrimethoxysilane, &#39;y-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, N,N-bis-(B- and vinyltrimethoxysilane. The foundry binders of the invention contain the silane in a quantity of about 0.05  
 to about 1.0 wt.%. Specific diamides that are suitable for the purposes of the invention have the general formula where n is an integer from 2 to 6 and R is an alkyl residue having 1 l to 20 carbon atoms in the chain.  
  Specific examples of such diamides are bisstearoylethylenediamide, bispalmitoylethylenediamide, bislauroylethylenediamide, bisstearoylpropylenediamide, bis-stearoyltetramethylenediamide, bisstearoylpentamethylenediamide, bis-stearoylhexamethylenediamide, bispalmitoylpropylenediamide, bispalmitoyltetramethylenediamide, and bispalmitoylpentamethylenediamide. The foundry binders of the invention contain about 0.5 to 8.0 wt.%, preferably about 3.0 to 5.0 wt.%, of the diamide.  
  In the production of the foundry binders of the invention, the manner in which the silane and the diamide are added to the novolak is critical. The silane and the diamide are incorporated into the novolak only after completion of the condensation and after complete removal of the reaction water at temperatures of about 120 to 170C, i.e. the novolak should have a fluidity of about 90 to l10 mm, preferably 100 to 106 mm. With fluidity values outside these limits, the binder imparts unsatisfactory&#34; mechanical properties to the foundry moulds or cores produced.  
  The foundry binders of the invention may contain conventional aromatic carboxylic acids in a quantity of about 1.0 to 6.0 wt.%. Special examples of such acids are benzoic&#39;acid, salicylic acid, and p-tert-butylbenzoic acid. In the production of the binders, the aromatic carboxylicacidsare incorporated into the novolak in the same way as the diamide and the silane.  
 The inventionis illustrated by the following non- 1 limiting examples. All parts and percent are by weight.  
 Preparation of a Novolak Phenolic Resin A three-&#39;neck flask fitted with a reflux condenser, a thermometer, and a stirrer, is charged with phenol, an aqueous 36 formaldehyde solution, an oxalic acid in a quantity of 1 part per 100 parts of phenol. The resulting mixture is heated under reflux until the aqueous phase contains 1 to 3&#39; of formaldehyde. The reaction time required is about 2 hours. The water is then distilled off at 150 to 160C and normal pressure at the bottom of the column. The novolak obtained has a fluidity of 100 mm.  
 Preparation of Core-Sand and Moulding-Sand Binders The novolak obtained is mixed with diamides, si-&#39; lanes, androptionally aromatic carboxylic acids in the proportions indicated in the following examples. The binders prepared in this way are removed from the reaction vessel in flake form, and their softening point,  
 , Electrothermal Engineering Ltd., London, i.e. the temperature at which the binder starts softening is measured. v  
  The flowability and fluidity is determined at 125C by means of a plate inclined at 64 by the following procedure. 9.2 g of the binder are ground in a mortar and mixed with 0.8 g of hexamethylenetetramine. After homogenization, 0.5 g of the powder is compressed into a tablet having a diameter of 100 mm with the aid of a hand-operated tablet press. The tablet is placed on the small side of a 60 X 150 mm glass plate, which is placed horizontally in an oven kept at a constant temperature of 125C by a thermostat. After 5 minutes, the plate is inclined to 64 with the aid of an external operating device, so that the tablet remains at the upper end. The tablet is left in this position for minutes, the entire arrangement is taken from the oven, and the traces of the molten binder remaining on the glass plate are measured. The value obtained (mm) is defined as the flowability.  
 The curing time was determined with the aid of a steel plate with depressions 18 mm in diameter on its mixture is immediately stirred with a glass rod 4 mm in flowability or fluidity, and curing time are determined.  
  The softening point&#39;is determined by the capillary method using a melting-point apparatus produced by diameter until the resin filament formed when the glass rod is raised breaks as soon as the rod is withdrawn from the depression. The time (sec) that has elapsed up to this instant is referred to as the curing time.  
 EXAMPLE 1 With a formaldehyde/phenol molar ratio of 0.611, a novolak is prepared from 300 parts of phenol and 160 parts of a 36 aqueous formaldehyde solution. After removal of the reaction water, 16 parts of bisstearoylethylenediamide, 0.9 part of &#39;y-aminopropyltriethoxysilane, and 9.6 parts of benzoic acid are added.  
 The binder obtained has the following properties:  
 softening point 58C flowability 90 mm curing time seconds EXAMPLE 2 With a formaldehyde/phenol molar ratio of 0.75:1 a novolak is prepared from 300 parts of phenol and 200 parts of a 36% aqueous formaldehyde solution. After removal of the reaction water, 16 parts of the diamide, 0.9 part of the silane, and 0.6 parts of the aromatic carboxylic acid of Example 1 are added.  
 The binder obtained has the following properties:  
 softening point 60C flowability mm curing time 65 seconds EXAMPLE 3 .parts of a 36% formaldehyde solution. After removal of the reaction water, 16 parts of the diamide, 0.9 part of the silane, and 9.6 parts of the aromatic carboxylic acid of Example 1 are added.  
 The binder obtained has the following properties: ifififggfi y 3% g curing time 64 seconds 5 softening point 62C I flowabll ty 84 mm Preparation of Coated Moulding Sand curing time 65 seconds The binders of Examples 1 to 8 are used in the following formulation for the coating of moulding sand:  
  EXAMPLE 4 10 1000 g of French quartz sannd quality 65 AFA A novolak is prepared in accordance with Example 30 g of binder I 2 with a formaldehyde/phenol molar ratio of 0.75:1. g of hexalflethyleneletfamlne The resin is then mixed with 0.9 part of the silane and T mouldomg lml&#39;oducffd 11119 a ble 9.6 parts of the aromatic carboxylic acid of Example 1. mlxer at 130 to 160 and the bmdel&#39; 15 added and The binder obtained has the following properties. 15 mixed for 1 minute. An aqueous solution of hexamethylenetetramine is then added and mixing is continued for a further 90 seconds; the moulding composition is softening point 61C then removed and cooled. Test specimens are prepared gg zs g 2g g g from the coated moulding sand in accordance with the g DIN 52 404 standard. The specimens are prepared with a shooting machine of the type Dependable Model EXAMPLE 5 100 at a shooting pressure of 4 kg/cm The coated moulding sand is shot into a mould held at 230 to 240C, the shooting time being 10 seconds and the baking time 150 seconds. The specimens are then removed and cooled to 25C. The bending strength (kg/cm and the mould release properties of the specimens are determined. The results are shown in the following table:  
  A novolak is prepared in accordance with Example 2 with a formaldehyde/phenol molar ratio of 0.75:1. The resin is then mixed with 3 parts of the diamide, 0.9 part of the silane, and 9.6 parts of the aromatic carboxylic acid of Example 1.  
 The binder obtained has the following properties:  
  Table softening point 61C 8 $2 d5 Example Bending strength Scaling Release from mould l 62 good 2 62 good EXAMPLE 6 3 48 good 4 inadequate A novolak is prepared in accordance with Example g2 Inadequate 2 with a formaldehyde/phenol molar ratio of 0.75: 1. 7 58 I 2885 The resin is then mixed with 9 parts of the diamide, 0.9 8 good part of the silane, and 9.6 parts of the aromatic carbox- 40 ylic acid of Example 1.  
 The binder obtained has the following properties: What we claim is:  
 l. Foundry binders on the basis of phenolic resins,  
  comprising softening point 60C 45 a. a novolak prepared by condensation of phenol flowflbility mm with formaldehyde in a molar ratio of about 110.4  
 curing time 64 Seconds to 0.9 in the presence of an acid catalyst and having a fluidity of about -110 mm, EXAMPLE 7 b. about 0.05 to about 1.0 wt.% of a silane having the 1f 1 A novolak is prepared in accordance with Example 50 genera Ormu a 2 with a formaldehyde/phenol molar ratio of 0.75:1. R&#39;Si(OR) The resin is then mixed with 16 parts of the diamide where R is amethyl or ethyl group and is a residue and 9.6 parts of the aromatic carboxylic acid of examwhich is a vinyl group or an alkyl residue substi- P 55 tuted with mercapto groups, optionally substituted amino residues, epoxyalkyl residues, or epoxycycloalkyl residues, and  
  mm 2 3. 5 c. about 0.5 to about 8.0 wt.% of the diamide of a Curing time 65 Seconds long-chain monocarboxylic acid having the general 60 formula EXAMPLE 8 (RCO .N CH. .NH.  
  A novolak is prepared in aCCOr C With Example where n is an integer from 2 to 6 and R is an alkyl res- 2 with a formaldehyde/phenol molar ratio of 0.75:1. id with 11 t 20 carbon at i th h i and When the novolak has a fluidity of mm, 16 parts d. about 1.0 to about 6.0 wt.% of an aromatic carboxof the diamide, 0.9 part of the silane, and 9.6 parts of ylic acid. the aromatic carboxylic acid of Example 1 are added. 2. Foundry binders in accordance with claim 1, char- The binder obtained has the following properties: acterized in that they contain about 3.0 to about 5.0  
 wt.% of the diamide of a long-chain monocarboxylic acid.  
  3. Process for the production of the foundry binders in accordance with claim 1, characterized in that a. phenol and formaldehyde are allowed to react at temperatures of about 80 to 160C in a molar ratio of about 120.4 to 0.9 in the presence of about 0.1 to about 5.0 wt.%, based on the phenol, of an acid catalyst, until the content of free aldehyde is-less than 3 wt.%, b. the water liberated is separated from the reaction medium, and c. the novolak obtained, with a fluidity of about 90 to 1 mm is mixed with a silane having the general formula R&#39;Si(OR) where R is a methyl or ethyl group and R is a residue