GB2255341A - Alkaline resole phenolic resin compositions - Google Patents
Alkaline resole phenolic resin compositions Download PDFInfo
- Publication number
- GB2255341A GB2255341A GB9201939A GB9201939A GB2255341A GB 2255341 A GB2255341 A GB 2255341A GB 9201939 A GB9201939 A GB 9201939A GB 9201939 A GB9201939 A GB 9201939A GB 2255341 A GB2255341 A GB 2255341A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resin
- binder
- binder composition
- phenol
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/12—Condensation polymers of aldehydes or ketones
- C04B26/122—Phenol-formaldehyde condensation polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/205—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of organic silicon or metal compounds, other organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores
Abstract
A water soluble particulate binder composition comprises a spray dried mixture of an alkaline resole phenol-aldehyde resin and a silane. The spray dried mixture may be readily dissolved in water and used as a binder for making foundry sand moulds or cores.
Description
ALKALINE RESOLE PHENOLIC
RESIN COMPOSITIONS
This invention relates to particulate alkaline resole phenolic resin compositions and their use in the production of foundry sand moulds and cores.
In recent years a number of processes have been developed for the production of foundry sand moulds or cores involving the use of a mixture of sand and an alkaline aqueous solution of a resole phenolformaldehyde resin, and curing the resin by means of an organic ester. In some of the processes a liquid ester such as a lactone or a dihydric glycol ester is mixed with the sand and resin prior to production of the moulds or cores and in one process a gaseous ester such as methyl formate is blown through the moulds or cores after their production.
In all these processes it is common to use as the binder an alkaline aqueous solution of a resole phenol-formaldehyde resin to which has been added during manufacture of the resin solution a small proportion of a silane in order to improve the strength of moulds and cores produced using the binder. During manufacture of the binder the resin solution must be cooled to a temperature of not more than about 350C 40"C before the addition of the silane.
The stability of such binders on storage is partially dependent on the degree of alkalinity of the aqueous resole phenol-formaldehyde resin solution, and although highly alkaline solutions have reasonably good long term stability it would be advantageous to minimise any possible problems due to instability or to utilise resin solutions of low alkalinity.
It has now been found that these advantages can be achieved by producing the binder in particulate form.
According to the invention there is provided a water soluble particulate binder composition comprising a spray dried mixture of an alkaline resole phenolaldehyde resin and a silane.
The binder composition can be made by producing an alkaline aqueous solution of a resole phenol-aldehyde resin, adding a silane at a temperature of below about 35"C - 40or, and then spray drying the solution. In spray drying the solution is converted to a fine spray, the water in the solution is evapourated by means of a stream of hot air usually at a temperature of 150"C - 1800C, and the dry powdered product which results is separated from the stream of hot air. The particle size of the powdered product produced varies with the degree of atomisation of the solution and with the solids content of the solution.
The particulate binder composition is soluble in water, and surprisingly even though during production of the binder the silane is subjected to a relatively high temperature the silane is not adversely affected and performance of the binder composition solution when used to make foundry sand moulds and cores is comparable to the performance of a binder of the same composition which has not been spray dried.
The spray dried binder composition of the invention is hygroscopic but provided it is stored in a sealed container it can be stored for a prolonged period of time and remains as a free-flowing powder.
The spray dried binder composition may be dissolved in water before being used in a foundry sand composition or alternatively it may be incorporated in the foundry sand composition as a powder. When the binder composition is used as a powder the sequence of addition to the sand should be liquid hardener, followed by spray dried binder composition, followed by water in order to ensure that a homogeneous mixture of all the components of the foundry sand composition is produced.
As stability of the resin is not a factor which needs to be taken into consideration the alkalinity of the binder composition can be reduced compared to previous practice. Sands which have been bonded with a binder composition of lower alkalinity may be more readily reclaimed.
A further advantage arises from the fact that the binder composition is supplied to the foundry as a powder. Foundries often purchase a resin binder solution of a particular solids content from a supplier and use that solution to produce moulds or cores for a wide range of castings. However for optimum results the ideal solids content of a resin binder solution for producing large castings differs from the ideal solids content for producing small castingo * o the usual practice is a compromise. As the binder composition of the invention is supplied as a powder the foundry can readily produce binder solutions of different solids contents to suit the production of particular castings.
The phenol used to produce the binder composition may be for example a monohydric phenol such as phenol itself or a cresol or a dihydric phenol such as resorcinol, or mixtures thereof. The aldehyde may be for example formaldehyde, butyraldehyde, glyoxal or furfuraldehyde. The preferred phenol is phenol itself and the preferred aldehyde is formaldehyde. The resin solution may be made alkaline by the addition of for example sodium hydroxide or potassium hydroxide.
Potassium hydroxide is preferred because for a given degree of polymerisation of the resin potassium hydroxide produces a binder composition of lower viscosity and better performance than does sodium hydroxide.
The molar ratio of formaldehyde to phenol may be for example 1:1 to 3:1 and is preferably 1.6:1 to 2.5:1. The molar ratio of alkali to phenol may be for example 0.3:1 to 1.1:1 and is preferably 0.5:1 to 0.9:1.
The silane may be any of the silanes which are known for use in foundry sand compositions containing a resin. A silane such as gamma-aminopropyltriethoxysilane or gamma-glycidyoxpropyltriemethoxysilane is preferred. The binder compositions will usually contain 0.05 - 1.0% by weight, preferably 0.1 - 0.6% by weigth, of silane based on the weigth of alkaline resole phenol-formaldehyde resin.
The following examples will serve to illustrate the invention:
EXAMPLE 1
A quantity of a commercially available potassium alkaline aqueous solution of a resole phenolformaldehyde resin, FENOTEC 500, sold by Foseco (F.S.)
Limited, was spray dried by atomising the solution, evaporating the water from the solution using a stream of air at a temperature of 1800C, and separating the resultant particles from the air stream.
The resin had a phenol to formaldehyde molar ratio of approximately 1:1.7 and a phenol to potassium hydroxide molar ratio of approximately 1:0.6. The resin solution contained 0.25% by weight of gammaaminopropyltriethoxy silane and had a solids content of approximately 50% by weight and a viscosity of 170 210 centipoise measured on a Brookfield viscometer at 25or.
The commercially available resin solution (Binder 1) was tested alongside the spray dried powder (Binder 2) as a binder for foundry sand. As the spray drying process does not remove all of the water contained in the solution it was necessary to dissolve 54.5 parts by weight of spray dried powder in 45.5 parts by weight of water to achieve a binder composition solution of the same solids content as that of the commercially available resin solution. The binder composition prepared from the spray dried resin had a viscosity of 180cP measured on a Brookfield viscometer at 25"C.
25% by weight of triacetin as curing agent for the resin based on the weight of binder were mixed with
Chelford 50 silica sand (AFS Fineness No. 47) and 1.5% by weight of the binder solution based on the weight of sand were then added and mixed with the sand and curing agent.
The sand-binder mixtures were used to prepare standard 50 mm x 50 mm diameter cylindrical AFS cores and the compression strength of the cores was determined after various time intervals by measuring the compressive force required to break the cores on a
Howden strength test machine Model No. 76EM15 and multiplying the result by 494. The "bench life" and "strip time" of the sand-binder mixtures were also determined. The "bench-life" was defined as the time taken in minutes after the addition of binder to the sand/curing agent mixture that the sand-binder mixture takes to lose one third of its ultimate available strength and was determined by producing standard 50 mm x 50 mm diameter cylindrical AFS cores at various time intervals after the completion of mixing and measuring the compression strength of the cores after 24 hours.
The "strip time" was defined as the time in minutes after the addition of the binder that it takes standard 50 mm x 50 mm diameter cylindrical AFS cores made from the resulting sand-binder mixture to reach a compression strength of 250 KNm'2.
The tests were carried out at an ambient temperature of 22"C and a humidity of 70%, and the sand temperature was 20"C.
The results obtained are shown in Table 1 below.
BINDER 1 BINDER 2
BENCH LIFE (MINUTES) 5 6
STRIP TIME (MINUTES) 8 8
COMPRESSION STRENGTH (KNm'2) AFTER i hour 1015 742
AFTER 1 hour 1456 1432
AFTER 2 hours 1792 1855
AFTER 4 hours 2226 2422
AFTER 24 hours 4620 4655
TABLE 1
EXAMPLE 2
The spray dried FENOTEC 500 resin powder of
Example 1 was compared with samples of the standard
FENOTEC 500 resin solution stored up to 22 days at temperatures of 21 - 24 0C and 31 - 33"C as a foundry sand binder. In each case the spray dried powder was dissolved in water so as to produce a solution of the same solids content as that of the FENOTEC 500 resin solution 24 hours before use.
25 by weight of triacetin as curing agent for the resin based on the weight of binder solution were mixed with Chelford 50 silica sand (AFS Fineness No.
47), and 1.5% by weight of the binder solution based on the weight of sand were then added and mixed with the sand and curing agent.
The resulting sand compositions were used to prepare standard 50 mm X 50 mm diameter cylindrical AFS cores and the compressive force required to break the cores was measured after various time intervals on a
Howden strength test machine Model No. 76EM15.
The results obtained are shown in Table 2 below.
STORAGE VISCOSITY SAND AMBIENT BREAKING FORCE (KN) PERIOD AT 25 C TEMP TEMP (DAYS) (cP) ( C) ( C) 0.5Hr 1Hr 2Hr 3Hr 4Hr 24Hr BINDER 3 - FENOTEC 500 RESIN SOLUTION STORED AT 21 - 24 C 1 195 21 23.5 2.0 3.1 4.25 4.4 4.8 6.9 8 196 21 23-24 2.0 3.2 3.95 3.9 4.35 5.0 15 218 23 24-24.5 2.2 3.5 4.25 4.25 - 5.5 22 238 21.5 22 1.75 3.3 - 4.15 4.75 5.2 BINDER 4 - FENOTEC 500 RESIN SOLUTION STORED AT 31 - 33 C 1 195 21 23.5 2.0 3.1 4.25 4.4 4.8 6.9 8 249 21 23-24 2.2 3.5 3.65 3.9 - 4.8 15 330 23 24-24.5 2.4 3.1 3.65 4.7 4.35 4.3 22 447* 21.5 22 1.9 3.6 3.65 4.0 4.5 BINDER 5 - SPRAY DRIED FENOTEC 500 RESIN REDISSOLVED IN WATER 1 182 21 23.5 1.85 3.0 4.1 3.95 5.1 5.4 8 174 21 23-24 1.65 3.85 4.0 4.2 6.1 15. 179 23 24-24.5 1.75 2.7 3.65 4.15 4.55 6.0 22 175 21.5 22 1.7 3.15 4.4 3.8 4.35 5.2 TABLE 2 In Table 2 all the viscosity measurements apart from the one marked * were done on a Viscolog viscometer using spindle R1 at 20 rpm. The measurement marked * was done on a Viscolog viscometer using spindle R2 at 20 rpm. In each case the compression strength of the core is the figure quoted for breaking force multiplied by 494.
EXAMPLE 3
The spray dried FENOTEC 500 resin powder of
Example 1 was used as a binder for foundry sand
(a) as an aqueous solution of the spray dried
resin (Binder 6) and
(b) as separate additions of resin powder and
water (Binder 7)
For Binder 6 54.5 parts by weight of the spray dried resin were mixed with 45.5 parts by weight of water to produce the solution. 0.375% by weight of triacetin as curing agent for the resin based on the weight of the sand were mixed with Chelford 50 silica sand and 1.5% by weight of Binder 6 based on the weight of the sand were then added and mixed with the sand and curing agent.
For Binder 7 0.3758 by weight of triacetin based on the weight of the sand were mixed with
Chelford 50 silica sand and 0.82% of the spray dried
FENOTEC 500 resin powder based on the weight of the sand were added and mixed with the sand and curing agent. Finally 0.68% of water based on the weight of the sand were added and thoroughly mixed with the sand, curing agent and resin so as to dissolve the resin.
Standard 50 mm X 50 mm diameter cylindrical
AFS cores were produced from the sand compositions, and tested as described in Example 2.
The tests were carried out at an ambient temperature of 23 C and the sand temperature was 20"C.
The results obtained are shown in Table 3 below.
BREAKING FORCE BINDER 6 BINDER 7 (KN)
AFTER 1 hour 2.85 2.85
AFTER 3 hours 3.75 3.25
AFTER 24 hours 4.8 5.0
TABLE 3
Claims (10)
- CLAIMS 1. A water soluble particulate binder composition comprising a spray dried mixture of an alkaline resole phenol-aldehyde resin and a silane.
- 2. A binder composition according to Claim 1 wherein the phenol is a monohydric phenol, a dihydric phenol or a mixture thereof.
- 3. A binder composition according to Claim 1 or Claim 2 wherein the aldehyde is formaldehyde, butyraldehyde, glyoxal or furfuraldehyde.
- 4. A binder composition according to any one of Claims 1 to 3 wherein the alkali is sodium hydroxide or potassium hydroxide.
- 5. A binder composition according to any one of Claims 1 to 4 wherein the silane is gammaaminopropyltriethoxysilane or gammaglycidoxypropyltrimethoxysilane.
- 6. A binder composition according to any one of Claims 1 to 5 wherein the resin has a molar ratio of formaldehyde to phenol of 1:1 to 3:1 and a molar ratio of alkali to phenol of 0.3:1 to 1:1.1.
- 7. A binder composition according to Claim 6 wherein the resin has a molar ratio of formaldehyde to phenol of 1.6:1 to 2.5:1 and a molar ratio of alkali to phenol of 0.5:1 to 0.9:1.
- 8. A binder composition according to any one of Claims 1 to 7 wherein the composition contains 0.05% to 1.0% by weight of silane based on the weight of the resin.
- 9. A binder composition according to Claim 8 wherein the composition contains 0.1% to 0.6% by weight of silane based on the weight of the resin.
- 10. A binder composition as claimed in Claim 1 substantially as hereinbefore described with reference to the specific examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9201939A GB2255341B (en) | 1991-02-21 | 1992-01-28 | Alkaline resole phenolic resin compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919103590A GB9103590D0 (en) | 1991-02-21 | 1991-02-21 | Alkaline resole phenolic resin compositions |
| GB9201939A GB2255341B (en) | 1991-02-21 | 1992-01-28 | Alkaline resole phenolic resin compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9201939D0 GB9201939D0 (en) | 1992-03-18 |
| GB2255341A true GB2255341A (en) | 1992-11-04 |
| GB2255341B GB2255341B (en) | 1994-06-01 |
Family
ID=26298469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9201939A Expired - Fee Related GB2255341B (en) | 1991-02-21 | 1992-01-28 | Alkaline resole phenolic resin compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2255341B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102632191A (en) * | 2012-05-08 | 2012-08-15 | 王海江 | Acid curing adhesive and preparation method of acid curing adhesive |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1404042A (en) * | 1971-10-30 | 1975-08-28 | Aisin Chem | Process of producing granular phenol formaldehyde resin composition |
| JPS5378924A (en) * | 1976-12-23 | 1978-07-12 | Sumitomo Durez Co | Preparation of sand grain for casting |
| US4196114A (en) * | 1976-12-23 | 1980-04-01 | Sumitomo Durez Company, Ltd. | Process for producing resin-coated foundry sand |
| US4424300A (en) * | 1981-12-07 | 1984-01-03 | Borden, Inc. | Powdered phenol-formaldehyde resin |
| GB2177408A (en) * | 1985-07-02 | 1987-01-21 | Catalin Limited | Foundry binder compositions |
| US4708967A (en) * | 1986-03-25 | 1987-11-24 | Reheis Chemical Company, Inc. | Thermosetting resin binder particles and methods for making waferboard |
| US4971132A (en) * | 1989-03-24 | 1990-11-20 | Acme Resin Corporation | Alkaline phenolic resole resin binders |
| EP0399635A2 (en) * | 1989-03-24 | 1990-11-28 | Borden, Inc. | Alkaline phenolic resole resin binders |
-
1992
- 1992-01-28 GB GB9201939A patent/GB2255341B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1404042A (en) * | 1971-10-30 | 1975-08-28 | Aisin Chem | Process of producing granular phenol formaldehyde resin composition |
| JPS5378924A (en) * | 1976-12-23 | 1978-07-12 | Sumitomo Durez Co | Preparation of sand grain for casting |
| US4196114A (en) * | 1976-12-23 | 1980-04-01 | Sumitomo Durez Company, Ltd. | Process for producing resin-coated foundry sand |
| US4424300A (en) * | 1981-12-07 | 1984-01-03 | Borden, Inc. | Powdered phenol-formaldehyde resin |
| GB2177408A (en) * | 1985-07-02 | 1987-01-21 | Catalin Limited | Foundry binder compositions |
| US4708967A (en) * | 1986-03-25 | 1987-11-24 | Reheis Chemical Company, Inc. | Thermosetting resin binder particles and methods for making waferboard |
| US4971132A (en) * | 1989-03-24 | 1990-11-20 | Acme Resin Corporation | Alkaline phenolic resole resin binders |
| EP0399635A2 (en) * | 1989-03-24 | 1990-11-28 | Borden, Inc. | Alkaline phenolic resole resin binders |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102632191A (en) * | 2012-05-08 | 2012-08-15 | 王海江 | Acid curing adhesive and preparation method of acid curing adhesive |
| CN102632191B (en) * | 2012-05-08 | 2015-06-10 | 邦尼化工（天津）有限公司 | Acid curing adhesive and preparation method of acid curing adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2255341B (en) | 1994-06-01 |
| GB9201939D0 (en) | 1992-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960128 |