Alkaline resol phenol-aldehyde resin binder compositions

Abstract: A binder composition for producing articles of bonded particulate material such as foundry moulds or core comprises an alkaline aqueous solution of a resol phenol-aldehyde resin, an oxyanion which can form a stable complex with the resin, and an ethylene glycol monoalkyl ether. The binder composition has an alkali to phenol molar ratio of from 1.5:1 to 2.5:1 and the amount of alkali present in the solution is sufficient to substantially prevent stable complex formation between the resin ad the oxyanion. Bonded articles are produced by passing carbon dioxide gas through articles formed from a mixture of particulate material and the binder composition so as to produce stable complex formation and curing of the resin.

Description: This invention relates to alkaline resol phenol-aldehyde binder compositions and their use in the production of articles of bonded particulate material such as foundry moulds or cores. European Patent Application Publication No. 0323096A describes a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex formation between the resin and the oxyanion. EP 0323096A also describes a process for the production of an article of bonded particulate material, such as a foundry mould or core, in which a mixture of particulate material and the binder composition is formed to a desired shape, and carbon dioxide gas is then passed through the formed shape so as to cause the oxyanion to form a stable complex with the resin and thereby to cure the resin. It has now been found that the performance of the binder composition can be improved if the binder composition also contains an ethylene glycol monoalkyl ether. According to the present invention there is provided a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex with the resin, the amount of alkali present in the solution being sufficient to substantially prevent stable complex formation between the resin and the oxyanion, wherein the molar ratio of alkali to phenol is from 1.5:1 to 2.5:1 and the binder composition also contains an ethylene glycol monoalkyl ether. According to a further feature of the invention there is provided a process for the production of an article of bonded particulate material comprising forming to the desired shape a mixture of particulate material and a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin having an alkali to phenol molar ratio of from 1.5:1 to 2.5:1, an oxyanion which can form a stable complex with the resin, and an ethylene glycol monoalkyl ether, and passing carbon dioxide gas through the formed shape so as to cause the oxyanion to form a stable complex with the resin, and thereby to cure the resin. The binder composition and the process of the invention are of particular value for making foundry moulds and cores and it is with reference to that application that the invention will be described. Suitable phenol-aldehyde resins and oxyanions for use in the binder compositions of the invention, and suitable methods for producing the phenol-aldehyde resin are described in EP 0323096A the disclosure of which is incorporated herein by reference. Examples of suitable ethylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether and polyethylene glycol monomethyl ethers. Diethylene glycol monoalkyl ethers and triethylene glycol monoalkyl ethers are preferred. The optimum amount of ethylene glycol monoalkyl ether contained in the binder composition will vary depending on the composition of the resin and on the particular ethylene glycol monoalkyl ether used, but will usually be within the range of 1% -10% by weight, preferably 2 - 5%, based on the weight of the binder composition. The presence of the ethylene glycol monoalkyl ether may have one or more beneficial effects on the performance of the binder composition as a binder for making foundry moulds and cores, depending on the composition of the particular resin and the particular ethylene glycol monoalkyl ether used. The beneficial effects include:- (i) improved mould or core strength immediately after gassing with carbon dioxide gas. (ii) improved strength after gassed moulds or cores have been stored before use, for example for up to 24 hours or longer. (iii) improved strength of moulds or cores which have been coated with an alcohol based coating which has been dried by burning off the alcohol, prior to storage of the moulds or cores (iv) improved mixed sand flowability. (v) improved mould or core surface finish and edge hardness. The binder composition of the invention preferably also contains a silane such as gamma-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, phenol trimethoxysilane or gammaglycidoxypropyltrimethoxysilane usually in an amount of 0.2% to 1.0% by weight based on the weight of the binder composition. The following Examples will serve to illustrate the invention:- EXAMPLE 1 A resol phenol-formaldehyde resin was synthesised having the following composition:- phenol 800.00g 91% W/W paraformaldehyde 642.20g 50% W/W sodium hydroxide solution 40.85g F:P molar ratio 2.3:1 OH :P molar ratio 0.06:1 Water in starting composition 5.2% W/W The following procedure was used:- 1. Charge and melt phenol 2. Charge paraformaldehyde and part of the sodium hydroxide solution and heat to 60 - 65°C at a rate of 1°C per minute 3. Cool to counteract exothermic reaction and maintain at 60 - 65°C while adding the remainder of the sodium hydroxide solution over a period of 1 hour 4. Heat to 75°C at a rate of 1°C per minute 5. Maintain at 75°C for 30 minutes 6. Heat to 85°C at a rate of 1°C per minute 7. Maintain at 85°C for sufficient time for the resin to reach a viscosity of 4000 - 6000 cp at 25°C as measured on a 25g sample diluted with 15g of 50% w/w potassium hydroxide solution using Paint Research Association Bubble Viscosity Tubes. The resin was used to produce a base binder (1A) having the following composition by weight:- resin 25 parts 50% W/W potassium hydroxide solution 35 parts borax 5.5 parts gamma aminopropyltriethoxysilane 0.39 parts The potassium hydroxide solution was added to the resin, the temperature rise due to exothermic reaction was controlled and the resin was cooled. The borax was added and mixed into the resin until it had dissolved. The silane was then added at a temperature of below 30°C. The molar ratio of alkali to phenol in the base binder was approximately 2:1. Using some of the base binder 1 a series of binders 2 - 5 was produced consisting of 98% by weight base binder 1 and 2% by weight of an ethylene glycol monoalkyl ether as follows:- Binder Ethylene glycol monoalkyl ether 2 Monoethylene glycol monomethyl ether 3 Monoethylene glycol monoethyl ether 4 Monoethylene glycol monobutyl ether 5 Diethylene glycol monomethyl ether. Binders 1 - 5 were tested as binders for foundry sand using the following procedure:- 3% by weight of the binder based on the weight of sand was mixed with Chelford 60 sand (AFS Fineness No. 62) and the mixture was used to prepare standard AFS 50 mm X 50 mm diameter cylindrical cores. The sand temperature was 19 - 20°C. The cores were hardened by the passage of carbon dioxide gas for various times at 0.35 kg/cm² line pressure and a 6.0 litres per minute flow rate. Some of the cores were tested immediately after gassing on a George Fischer Universal Strength Machine Type PFA fitted with a High-Dry Compressive Strength Attachment Type PHD. Some were tested after storage for 3 days in dry storage conditions (temperature 18 - 20°C, relative humidity 40 - 45%) and others were tested after storage for 3 days in humid storage conditions (temperature 24 - 26°C, relative humidity 75 - 80%). The results obtained are tabulated in Tables 1 and 2 below. BINDER COMPRESSION STRENGTH (kg/cm²) FOR GASSING TIME 30S 60S 120S 1 13.8 15.9 18.8 2 15.4 19.8 20.6 3 16.2 21.3 23.9 4 17.8 18.6 23.0 5 18.3 21.4 24.5 BINDER COMPRESSION STRENGTH (kg/cm²) AFTER DRY STORAGE FOR GASSING TIME COMPRESSION STRENGTH (kg/cm²) AFTER HUMID STORAGE FOR GASSING TIME 30S 60S 120S 30S 60S 120S 1 20.7 21.3 20.5 20.3 20.3 20.3 2 20.5 23.6 25.0 22.5 23.8 24.7 3 23.9 25.0 25.7 24.6 22.8 23.8 4 28.0 28.6 28.3 22.9 26.9 25.9 5 31.0 32.7 33.6 30.0 29.4 29.4 As Tables 1 and 2 show, all the resins containing an ethylene glycol monoalkyl ether gave improved strength results overall compared with the base resin and diethylene glycol monomethyl ether was better than the monoethylene glycol monoalkyl ethers. EXAMPLE 2 A series of binders 6 - 9 was prepared, similar to binders 2 - 4 but each containing 5% by weight of the ethylene glycol monoalkyl ether instead of 2%. The binders were tested together with base binder 1 as described in Example 1 and the results obtained are tabulated in Tables 3 and 4 below. BINDER COMPRESSION STRENGTH (kg/cm²) FOR GASSING TIME 30S 60S 120S 1 14.3 16.5 18.7 6 17.8 20.5 22.9 7 20.5 21.5 22.6 8 18.2 19.3 21.2 9 19.3 21.4 22.6 BINDER COMPRESSION STRENGTH (kg/cm²) AFTER DRY STORAGE FOR GASSING TIME COMPRESSION STRENGTH (kg/cm²) AFTER HUMID STORAGE FOR GASSING TIME 30S 60S 120S 30S 60S 120S 1 20.2 22.2 21.1 18.8 20.7 20.5 6 26.2 25.2 25.8 20.8 21.6 20.8 7 31.5 32.0 31.9 26.0 26.4 26.6 8 32.4 34.1 34.3 26.9 26.6 28.9 9 39.5 40.0 41.0 32.7 31.4 31.5 The as-gassed strengths obtained at the 5% by weight addition level were similar to those obtained at the 2% by weight addition level, but the strength of cores which had been stored was improved at the 5% level compared with the 2% level. Diethylene glycol monomethyl ether again gave better results than the monoethylene glycol monoalkyl ethers. EXAMPLE 3 Using the base binder 1 of Example 1 a series of binders 10 -12 was prepared containing 98% by weight of base binder 1 and 2% by weight of an ethylene glycol monoalkyl ether as follows:- Binder Ethylene glycol monoalkyl ether 10 Diethylene glycol monoethyl ether 11 Triethylene glycol monomethyl ether 12 Polyethylene glycol monomethyl ether (Molecular weight 350) The binders were tested and compared with Binder 1 as described in Example 1 except that the cores were stored for 24 hours instead of 3 days. The sand temperature was 19°C, the dry storage conditions were 18 - 20°C and 30 - 35% relative humidity and the humid storage conditions were 24 - 26°C and 90 - 95% relative humidity. The results obtained are tabulated in Tables 5 and 6 below. BINDER COMPRESSION STRENGTH (kg/cm²) FOR GASSING TIME 30S 60S 120S 1 13.1 14.7 17.5 10 16.2 19.8 23.8 11 15.8 19.6 21.6 12 11.4 13.5 17.9 BINDER COMPRESSION STRENGTH (kg/cm²) AFTER DRY STORAGE FOR GASSING TIME COMPRESSION STRENGTH (kg/cm²) AFTER HUMID STORAGE FOR GASSING TIME 30S 60S 120S 30S 60S 120S 1 21.0 21.3 20.6 15.7 15.9 16.8 10 34.0 36.0 35.3 21.8 24.2 25.6 11 28.4 34.0 35.5 20.0 23.5 24.7 12 23.0 26.3 27.4 21.0 21.3 21.0 The polyethylene glycol monomethyl ether gave little or no improvement in as-gassed strength but the strength of stored cores was improved. The results show that for overall improvements in core strength relatively short chain length ethylene glycol monoalkyl ethers are preferable. EXAMPLE 4 Using the base binder 1 of Example 1 two binders, 13 and 14, were prepared containing respectively 5% by weight of diethylene glycol monoethyl ether and 5% by weight triethylene glycol monomethyl ether. Binders 13 and 14 were compared with binder 1 using the procedure of Example 1. Test cores were stored for 4 days and the test conditions were as set out in Example 3. The results obtained are tabulated in Table 7 below. BINDER COMPRESSION STRENGTH (kg/cm²) 1 13 14 AS GASSED GASSING TIME 30S 13.3 17.5 15.9 60S 15.4 19.0 17.9 120S 18.0 20.5 19.8 DRY STORAGE GASSING TIME 30S 16.8 48.0 44.0 60S 21.7 48.0 49.0 120S 24.1 48.5 47.0 HUMID STORAGE GASSING TIME 30S 15.8 25.5 26.1 60S 16.4 25.3 26.2 120S 16.0 27.3 24.1 The results show that at the 5% by weight addition level diethylene glycol monoethyl ether and triethylene glycol monomethyl ether give particularly high strengths on dry storage of the cores, and also significant improvements in strength on humid storage of the cores. EXAMPLE 5 A series of binders 15 - 30 was prepared from base binder 1 containing various proportions of various ethylene glycol monoalkyl ethers as follows:- Binder Ethylene glycol monoalkyl ether Amount (WT) 15 Diethylene glycol monomethyl ether 2% 16 Diethylene glycol monomethyl ether 4% 17 Diethylene glycol monomethyl ether 7.5% 18 Diethylene glycol monomethyl ether 10% 19 Diethylene glycol monoethyl ether 2% 20 Diethylene glycol monoethyl ether 4% 21 Diethylene glycol monoethyl ether 7.5% 22 Diethylene glycol monoethyl ether 10% 23 Diethylene glycol monobutyl ether 2% 24 Diethylene glycol monobutyl ether 4% 25 Diethylene glycol monobutyl ether 7.5% 26 Diethylene glycol monobutyl ether 10% 27 Triethylene glycol monomethyl ether 2% 28 Triethylene glycol monomethyl ether 4% 29 Triethylene glycol monomethyl ether 7.5% 30 Triethylene glycol monomethyl ether 10%. Binders 15 - 30 were tested using the procedure of Example 1. The test conditions and the results obtained are tabulated in Tables 8, 9 and 10 below. BINDERS CONDITIONS COMPRESSION STRENGTH (kg/cm²) FOR GASSING TIME 30S 60S 120S 15 Sand Temp 19°C 15.2 18.0 21.2 16 15.8 18.6 23.1 17 11.9 13.9 16.3 18 9.5 12.7 14.6 19 Sand Temp 17°C 13.4 17.4 21.5 20 15.0 18.3 21.2 21 12.8 14.9 17.0 22 10.7 14.3 15.6 23 Sand Temp 18°C 15.6 17.6 20.6 24 17.2 20.0 22.5 25 15.1 17.4 18.6 26 10.9 13.9 16.9 27 Sand Temp 17-18°C 13.1 16.5 19.2 28 15.1 18.5 22.7 29 13.4 15.1 17.3 30 10.1 13.1 15.9 BINDER CONDITIONS COMPRESSION STRENGTH (kg/cm²) AFTER DRY STORAGE FOR GASSING TIME 30S 60S 120S 15 Sand Temp 19°C 26.0 30.0 32.1 16 Storage Temp 30.0 31.2 34.0 17 18 - 20°C 29.7 32.5 33.0 18 Relative Humidity 40 - 45% 29.2 31.7 29.0 19 Sand Temp 17°C 31.0 29.7 32.0 20 Storage Temp 17-19°C 31.1 32.6 34.0 21 Relative Humidity 34.0 33.0 34.0 22 45 - 50% 27.8 32.3 33.6 23 Sand Temp 18°C 28.0 29.2 29.8 24 Storage Temp 18-20°C 35.0 34.5 34.5 25 Relative Humidity 24.0 30.0 31.2 26 40 - 45% 31.0 29.5 31.5 27 Sand Temp 17-18°C 27.0 27.1 28.5 28 Storage Temp 17-19°C 32.0 31.6 35.5 29 Relative Humidity 34.0 35.0 34.5 30 40 - 45% 30.0 33.0 39.0 BINDER CONDITIONS COMPRESSION STRENGTH (kg/cm²) HUMID STORAGE FOR GASSING TIME 30S 60S 120S 15 Sand Temp 18-20°C 25.0 25.8 28.9 16 Storage Temp 26-28°C 26.0 27.7 27.4 17 Relative Humidity 26.4 26.2 28.0 18 65 - 70% 28.0 27.1 28.6 19 Sand Temp 17°C 21.6 21.2 23.4 20 Storage Temp 26-28°C 24.5 25.2 25.8 21 Relative Humidity 25.0 25.5 26.4 22 85 - 90% 24.9 25.9 25.4 23 Sand Temp 18°C 22.0 22.2 20.8 24 Storage Temp 25-26°C 26.0 26.6 27.3 25 Relative Humidity 28.5 29.3 29.7 26 75 - 85% 27.5 27.4 28.2 27 Sand Temp 17-18°C 20.8 22.0 23.2 28 Storage Temp 25-26°C 24.0 25.2 25.9 29 Relative Humidity 24.6 25.9 25.5 30 80 - 95% 25.9 26.0 26.0 The results show that for all the additives the optimum amount for gassed strength improvement is about 4% by weight. Although gassed strength tends to decrease as the amount of additive is increased to 7.5 to 10% by weight, cores still have good storage properties at these high addition levels. The diethylene glycol monobutyl ether gave a somewhat sticky sand composition and for that reason would be less suitable than the other additives.

Claims: A binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex with the resin, wherein the amount of alkali present in the solution is sufficient to substantially prevent stable complex formation between the resin and the oxyanion characterised in that the binder composition has a molar ratio of alkali to phenol of from 1.5:1 to 2.5:1 and the binder composition also contains an ethylene glycol monoalkyl ether. A binder composition according to Claim 1 characterised in that the ethylene glycol monoalkyl ehter is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether or a polyethylene glycol monomethyl ether. A binder composition according to Claim 1 or Claim 2 characterised in that the ethylene glycol monoalkyl ether is present in an amount of 1% to 10% by weight based on the weight of the binder composition. A binder composition according to Claim 3 characterised in that the ethylene glycol monoalkyl ether is present in an amount of 2% to 5% by weight based on the weight of the binder composition. A binder composition according to any one of Claims 1 to 4 characterised in that the composition contains in addition a silane. A binder composition according to Claim 5 characterised in that the silane is gammaaminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, phenol trimethoxysilane or gammaglycidoxypropyltrimethoxysilane. A binder composition according to Claim 5 characterized in that the amount of silane present is from 0.25% to 1.0% by weight based on the weight of the binder composition. A process for the production of an article of bonded particulate material in which a mixture comprising particulate material and a binder composition is formed to a desired shape and the binder composition is cured by passing carbon dioxide gas through the formed shape, characterized in that the binder composition used is a composition according to any one of Claims 1 to 7.

Inventors: BRADLEY MARTIN, SMITH GARRY, BRADLEY, MARTIN, SMITH, GARRY
Applicants: FOSECO INT, FOSECO INTERNATIONAL LIMITED
Application year: 1992
Main classification: B22C1
IPC codes: B22C1, C08L61, C08K5, C08G8