AU752507B2 - Chemical binder - Google Patents

Description

Our Ref: 7462066/PS/KAD Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

(ORIGINAL)

a.

9 a.

a Name of Applicant: Mancuso Chemicals Limited 5725 Progress Street Niagara Falls, Ontario L2E 6X8

CANADA

DAVIES COLLISON CAVE, Patent Attorneys Level 10, 10 Barrack Street, Sydney, 2000 Address for Service: Invention Title: "Chemical binder" The following statement is a full description of this invention, including the best method of performing it known to me: CHEMICAL BINDER TECHNICAL FIELD The present invention relates to a chemical binder. More particularly, the present invention relates to a chemical binder for use in one or more of the foundry, abrasives, refractory and construction industries.

BACKGROUND ART In the foundry industry, one of the processes used for making metal parts is metal casting in sand moulds/cores. In sand casting, disposable foundry shapes (usually characterized as moulds and cores) are made by shaping and curing a foundry mix which is a mixture of sand and an organic or inorganic binder. The binder is used to strengthen the moulds and cores.

It is to be understood that the term "mould", when used throughout this S. specification, is intended to have a broad meaning and includes generally any 15 shaped article such as a foundry mould, a foundry core and the like.

One of the processes used in sand casting for making moulds and cores is known as the "no-bake" process. In this process, mixture or foundry mix comprising: a foundry aggregate, (ii) a binder, and (iii) a liquid curing catalyst is initially prepared. The mixture is then compacted to produce a 20 cured mould or core. In the no-bake process, it is important to formulate a foundry mix which will provide sufficient worktime to allow shaping before the onset of curing. Worktime is generally the time between when mixing begins and when the mixture can no longer be effectively shaped to fill a mould or core.

A binder commonly used in the no-bake process is a polyurethane binder derived by curing a polyurethane-forming binder with a liquid tertiary amine catalyst. Such polyurethane-forming binders used in the no-bake process have proven satisfactory for casting a variety of metals including iron and steel which are normally cast at temperatures exceeding about 1400*C.

The known polyurethane-forming binders are also useful in the casting of lightweight metals, such as aluminum, which have melting points of less than 700 0

C.

7-02;11:00AM; 4/ 7 -2- Another of the processes used in sand casting for making moulds and cores .is known as the "cold box" process. The chemistry involved in this process is generally similar to that of the no-bake process. The principal difference is that, in the cold box process, the foundry aggregate and the binder are initially mixed and shaped. Thereafter, a gaseous catalyst is diffused through the shaped mixture resulting in substantially immediate curing of the shaped mixture in the absence of applied heat. Suitable gaseous catalyst include tertiary amines such as triethyl amine and trimethyl amine.

SRegardless of whether the no-bake or cold box process is used, conventional polyurethane-forming binders usually consist of a phenolic resin component and polyisocyanate component which are mixed with sand prior to compacting and curing. The phenolic resin components generally contain approximately 5% to 12%'by weight of free phenol, free formaldehyde and organic solvent, all of which can are obnoxious to smell and, in some cases, can creat environmental and/or toxicological problems.

Accordingly, it would be desirable to have a chemical binder, preferably for use in a foundry mix, which was free of such disadvantages.

Ideally, the chemical binder would be free of one or more of phenol, formaldehyde and organic solvents. It would be advantageous if the chemical binder was readily adapted for use in a no-bake or cold box process.

DISCLOSURE OF THE INVENTION o In ope asect of the invention there is provided a chemical binder forts pr uction of a foundry shape, the binder comprising: a polyol; an :25 isocyanate and a catalyst capable of catalyzing a reaction between the polyol and the isocyanate; characterized in that: the polyol is an ester-based polyol, and (ii) the binder is substantially completely free of phenol and phenol-based polyols.

In yet another aspect of the present invention there is provided a mouldable mixture for use in production of a foundry shape, the mixture comprising: a particulate aggregate, a polyol, an isocyanate and a catalyst, capable of catalyzing a reaction between the polyol and the isocyanate; characterized in that: the polyol is an ester-based polyol, and (ii) the binder is substantially completely free of phenol and phenol-based polyols.

In yet another aspect of the present invention there is provided the mixture defined in the above mentioned invention, wherein the ester-based polyol is based on the reaction of an alcohol with an aromatic compound selected from the group comprising of polyethylene terphthalate, phthalic anhydride, isophthalic acid, dimethyl terphthalate and mixtures thereof.

BEST MODE FOR CARRYING OUT THE INVENTION Accordingly, an aspect of the present invention relates to the provision of a chemical binder comprising: an ester-based polyol; an isocyanate; and a catalyst capable of catalyzing a reaction between the ester-based polyol and the isocyanate. Preferably, components are kept separate until they are intended to be used. Thus, when the present chemical binder is used to manufacture, for example, a mould, the components of the chemical binder are mixed with a suitable aggregate, shaped into the mould and allowed to cure this is the no-bake process described hereinabove. Alternatively, the Scatalyst can be set aside while the polyol, isocyanate and aggregate are mixed 20 and shaped into the mould. Thereafter, the catalyst is diffused through the (the next page is shaped mould to effect curing thereof this is the cold box process described above.

As used throughout this specification, the term "ester-based polyol" is intended to have a broad meaning and encompasses polyols produced by a condensation reaction between hydroxyl-containing compound and a dicarboxylic-acid compound. Thus, such polyols are also known in the art as "polyesters" or "polyester resins". Such polyols are known and have been used for a number of years in the manufacture of polyurethane foams.

Applicant has discovered that a particular subset of ester-based polyols has unexpected utility in the production of foundry moulds or cores. Preferably, the ester-based polyol for use in the invention is substantially completely free of one or more of phenol-based polyols, phenol, formaldehyde and organic solvents such as C3-Co esters and C,-Co alcohols. Further, the ester-based S. polyol for use in the present invention should be substantially free of oil. As 15 is known in the art, oil-modified polyester resins are also known as "alkyd resins". It will, however, be appreciated by those of skill in the art that minor *OV amounts total of up to about 10% by weight) of these components may be present in the ester-based polyol without affecting the performance of the binder and departing from the spirit of the invention.

20 Thus, non-limiting examples of the ester-based polyol suitable for use in the present invention include: 1. Poly(ethylene adipates), 2. Lightly branched poly(diethyleneglycol adipates), 3. Adipates made with more than one aliphatic diol, 4. Mixed polyadipates from hydrogenated AGS (adipic, glutaric and succinic) acids, Aromatic polyester polyols, including those at least partly based scrap polyethylene terephthalate and/or dimethyl terephthalate process waste, 6. Polycaprolactone diols, 7. Polycarbonate dials, 8. Halogen-containing Polyester polyols, including those made from halogenated dials and diacids, 9. Pblyols based on phthalic anhydride, 10. Pblyols based on isophthalic acid, 11. Polyols; based on terphthbalic acid, 12. Mixturesof toor more ofthse The Preferred ester-based polyol for use in the present invention will have one or more, more Preferably all, of the following properties: a hydrOXYl number greater that about 200, more preferably in the range of from about 200 to about 600, most preferably in the range of from about 300 to 4about 600, (Hi) a viscosity in the range -of from about 100 to about 120,000 .:cps, more Preferably from about 100 to about 3000, most preferably from *15 about 1000 to about 1200 -rs, (iii) an acdnumber les than about 2.0, (iv) functionality in the range of from about 2.0 to about 2.5, and 0(v) an aroinaticity in the rang of from about 30 to about 40. More particularly, Applicant has discovered that ester-based polyols having a hydroxyl number *see.:in the range of from about 300 to about 600 are surprising and unexpectedly a ~20 useful topuc foundry moulds and core.

S The polyhydroxy functional group in the polyol may be derived from any suitable hYdroxyl-containing compound. Non-limiting examples of a suitable hydroxyl-containing compound may be selected from the group consisting of 1,3-butane dial, 1,4-butane dial, 1 2 -cyclohexanedimethanol, 1 3 -cyclohexanedimethanoli 1 4 -cyc-lohexnedimnethanol, dimethylol propionic acid, dipropylene glycol, diethylene glycol, ethylene glycol, 1 ,6-hexanediol, hexylene glycol, neopentyl glycol, l,5-penranediol, propylene glycol, tetraethylene glycol, triethylene glycol, trimethylene glycol, trimethylpentanediol, glycerine, trimethylol ethane, trimethylol propane, pentaerythritol and mixtures of two or more of these.

Preferably, the hydroxyl-containing compound is a polyhydroxyl compound with an average functionality of from 2 to 4. Non-limiting -7examples of such preferred polyhydroxyl compound include glycerine, trimethylol ethane, trimethylol propane, pentaerythritol and mixtures thereof.

More preferably, the ester-based polyol is an aromatic polyester polyol, ideally oil-free, produced by reacting an alcohol with an aromatic compound selected from the group consisting of polyethylene terphthalate (PET), phthalic anhydride, isophthalic acid, dimethyl terphthalate (DMT) and mixtures thereof. More preferably, the alcohol is a glycol. The most preferred ester-based polyol is an aromatic polyester polyol produced by reacting diethylene glycol with polyethylene terphthalate (PET) it has been surprisingly and unexpectedly found that the use of this particular combination of polyol results in particularly beneficial results when the binder is used to produce a foundry mould or core.

The ester-based polyol can be used neat or diluted with one or more suitable solvents such as an ester dibasic ester, propylene carbonate, 15 diacetone alcohol and mixtures thereof), a ketone or an alcohol isopropyl alcohol, methanol and mixtures thereof). The suitable solvent can be used alone or in admixture with one or more other solvents. Non-limiting examples of suitable solvents include propylene carbonate, toluene, xylene, kerosene, other high boiling aromatic solvents such as those commercially 20 available from Esso Chemical Canada under the tradenames Solvesso" 100, 0* 150, 200 and the like.

SThe isocyanate suitable for use in the chemical binder is not particularly restricted and the choice thereof is within the purview of a person skilled in the art. Generally, the isocyanate compound suitable for use may be represented by the general formula:

Q(NCO),

wherein i is an integer of two or more and Q is an organic radical having the valence of i. Q may be a substituted or unsubstituted hydrocarbon group (e.g.

an alkylene or arylene group). Moreover, Q may be represented by the general formula: -8- Q'-Z--Ql wherein Q 1 is an alkylene or arylngouad Z is choen from the group comprising and-SO 2 xmlso isocyanate compounds which fanl within the scope of this definition include hexamethylene diisocyanate, 1 ,84disocyanato-P-metIhni, xylyl diisocyanate,

(OCNCH

2

CH

2 CHc H 2 O)2 1-methyl-2,4-disoc ~qlohexanephenylene diisocyanates, tolylene dfisocyanate, chioruph ee diisocyanates, diphenylmethane-4,4 '-diisocyanate, napht halene- 1, S-diisocyanate, triPhenylmethane4,4' ,4"-triisocyanate and isop ropylbenzeneap-4dllsoqanate.

In another embodiment, QUmay'also rpresent a polyurethane radical having a valence of i. In this case Q(NCO)j is a compound which is commonly referred to in the Art as a prepolymer. Generally, a prepolymer may be prepared by reacting a stoichiometric excess of an isocyanate compound (as defined *hereinabove) with an active hykdrogen-containing compound (as defined herinaftr), pefrably the polyhydroxyl-contining ~mtrals or polyols described bel.i n I emoimeint, the polyisocyanate may be, for example, used in ppotnsof- from. abot 30 percent to about 200 percent stoichiometric ecess with respect to the pto0portion of hydroxyl in the polyol.

In another embodiment, the isocanat Compound suitable for use in the process Of the Present invention may be selected from dimers and trimers of isocyaates and diisocyanates, and from polymeric diisocyantes having the general formula: [Q-(NCO)jj polyfunctional organic radical, and/or, as additional components in the reaction mixture, compounds having the general formula: -9-

L(NCQ)

1 wherein i is an integer having a value of 1 or more and L is a monofunctional or polyfunctional atom or radical. Examples of isocyanate compounds which fall with the scope of this definition include ethyiphosphonic diisocyanate, phenyiphosphonic diisocyanate, compounds which contain a =;Si-NCO group, isocyanate compounds derived from suiphonamnides (QSO 2 NCO), cyanic acid and thiocyanic acid.

See also for example, British patent No. 1,453,258, the contents of which are incorporated herein by reference.

Non-limiting examples of suitable isocyanates include: 1,6hexamethylene diisocyanate, 1,4-butylene dilsocyanate, furfurylidene diisocyanate, 2,4-toluene -diisocyanate, 2,6-toluene diisocyanate, 2,4'diphenylmethane diisocyanate, 4 ,4'-diphenylmethane diisocyanate, 4,4'diphenylpropane diisocyanate, 4,4'-diphenyl-3,3'-dimethyl methane diisocyanate, 1,5-naphtlialene diisocyanate, l-methyl-2,4-diisocyaaate-5chlorobenzene, 2 ,4-diisocyanato-s-triazine, 1 -methyl-2,4-diisocyanato cyclohexane, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,4naphthalene diisocyanate, dianisidine -diisocyanate, bitolylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, bis-(4- 'socyanatophenyl)methane, bis-(3-methyl-4-isocyanatophenyl)methane, polymethylene polyphenyl polyisocyanates and mixtures thereof. A more preferred isocyanate is selected from the group comprising 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, for example, a mixture comprising from about 75 to about 85 percent by weight 2,4-toluene diisocyanate and from about 15 to about 25 percent by weight 2,6-toluene diisocyanate. Another more preferred isocyanate is selected from the group comprising 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmnethane diisocyanate and mixtures thereof. The most preferred isocyante is a mixture comprising from about 15 to about 25 percent by weight 2,4'-diphenylmethane diisocyanawe and from about 75 to about 85 percent by weight 4,4'diphenylmethane diisocyanate. Such isocyanates are readily available from a variety of known commercial sources. Thus, it is possible to utilize a mixture of commercially available isocyanates such as two or more of Mondur"

M,

Mr200 and Preferably, the isocyanate has an average functionality of from about 2.0 to about 2.9 and NCO conteit in the range of from about 18 to about 32. The isocyanate can be used neat or can be diluted with one or more suitable solvents such as an ester, an aliphatic hydrocarbon, aromatic hydrocarbon and mixtures thereof. Non-limiting examples of suitable solvents include propylene carbonate, toluene, xylene, kerosene, other high boiling aromatic solvents such as those commercially available from. Esso Chemical Canada under the tradenames Solvesso" 100, 150, 200 and the like.

Generally, the catalyst used in the present chemical binder is a compound capable of catalyzing a reaction between the ester-based polyol and the isocyanate. Such catalysts are known, and the choice and concentration 15 thereof is within the purview of a person skilled in the art. See for example United States patents 4,296,213 and 4,518,778, the contents of each of which is incorporated herein by reference.

In the embodiment of the invention relating to a chemical binder for use in manufacturing a foundry mould or core using the no-bake process, non- 20 limiting examples of suitable catalysts include tertiary amines and/or organometallic compounds. The preferred such catalyst is a tertiary amine which can be supplied alone and then mixed with the polyol and/or aggregate, or pre-mixed with the polyol. Non-limiting examples of a tertiary amine suitable for use in this embodiment the present chemical binder may be selected from the group consisting of N,N-dimethylaminoethanol,

N,N-

dimethylcyclohexylamine, N-methyldicyclohxylamine (commercially available under the tradename Polycat M 12), bis-(2-dimethylaminoethyl) ether, N,N,N',N',N"-pentamethyldiethylene triamine, N,N-dimethylbenzylamine, N,N-dimethylcetylamine, diaminobicyclooctane, potassium octoate, potassium acetate, stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylates, dioctyltin thiocarboxylates, phenylmercuric propionate, imidazoles, substituted imidazoles C,-Co alkyl and vinyl substituent -11imidazoles such as N-methyl imidazole and 1-methylbenzimidazole), lead octoate, alkali metal salts CH 3 COOK, K 2 CO,, NaHCO 3 and Na 2

CO

3 and the like), calcium carbonate, ferric acetylacetonate and 4-alkyl pyridines wherein the alkyl group as one to four carbon atoms. Non-limiting examples of such 4-alkyl pyridines suitable for use in the present binder include phenyl pyridine, acridine, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, 4,4-dipyridine, 1,4-thiazine and 4-phenylpropylpyridine. The preferred catalyst is 4-phenylpropylpyridine. The catalyst can be used neat or diluted with a suitable solvent such as an aromatic solvent, an aliphatic solvent or a mixture of such solvents. Of course, it will be understood by those skilled in the art that a combination of two or more catalysts may be suitably used.

When the present chemical binder is to be used in a no-bake foundry application, it is preferred that the binder comprise a ratio from about 35 to about 65 percent by weight ester-based polyol, from about 65 to about percent by weight isocyanate and from about 1 to about 10 percent by weight catalyst based upon the weight of total binder. More preferably, such a binder comprises a ratio from about 40 to about 60 percent by weight ester-based polyol, from about 60 to about 40 percent by weight isocyanate and from 20 about 1 to about 8 percent by weight catalyst based upon the weight of total binder. Most preferably, such a binder comprises from about 46 to about 54 percent by weight ester-based polyol, from about 54 to about 46 percent by weight isocyanate and from about 2 to about 6 percent by weight catalyst based upon the weight of the total binder.

In the embodiment of the invention relating to a chemical binder for use in manufacturing a foundry mould or core using the cold box process, non-limiting examples of suitable catalysts include gaseous compounds such as one or more of triethylamine (TEA), dimethylethylamine (DMEA), trimethyl amine (TMA) and the like. The choice the particular catalyst is within the purview of a person skilled in the art and will depend on factors such as the desired curing speed and the like. The catalyst can be used neat or diluted with a suitable carrier gas as dry air or an inert gas such as nitrogen, carbon dioxide and the like. If the catalyst is diluted with a carrier gas, it is preferred that the resulting composition comprise up to about by weight, more preferably from about 3% to about 15% by weight catalyst with the remainder being carrier gas. Of course it will be understood by those skilled in the art that a combination of two or more catalysts may be suitably used. More information on the choice and amount of catalysts for use in the cold box process may found in United States patents 3,409,579 and 3,919,162, the contents of which are hereby incorporated by reference.

When the present chemical binder is to be used in a cold box foundry application, it will be appreciated by those of skill in the art that the catalyst be kept out of contact with the combination of the ester-based polyol and isocyanate until such time as it is desired to produce the foundry mould or core. In this embodiment of the invention, the chemical binder can be viewed as a kit or system of components which, when combined with a suitable 15 aggregate, can be shaped and made into a foundry mould or core. Preferably, the kit or system may comprise the ester-based polyol and isocyanate as independent components which are combined just prior to production of the foundry mould or core. In either case, the catalyst is supplied independently until it is used to catalyze the should foundry mould or core. Accordingly, 20 in this embodiment of the invention, it is preferred that the binder comprise from about 35 to about 65 percent by weight ester-based polyol and from about 35 to about 65 percent by weight isocyanate and, independently, a catalyst as described in the previous paragraph. More preferably, such a binder comprises from about 40 to about 60 percent by weight ester-based polyol and from about 40 to about 60 percent by weight isocyanate and, independently, a catalyst as described in the previous paragraph. Most preferably, such a binder comprises from about 45 to about 55 percent by weight ester-based polyol and from about 45 to about 55 percent by weight isocyanate and, independently, a catalyst as described in the previous paragraph.

As will be clearly understood by those of skill in the art, it is contemplated that conventional additives in the isocyanate-based and/or polyol -13polymer art be used in the present chemical binder. Non-limiting examples of such additives include: release a s(e.g. silico silanes, waxes, fatty acids and the like), humidity re icones, cabodiimide, molecular sieve and the like), surfaci organo-silicone compounds such as those available under the tradename L-540 Union Carbide), extenders halogenated paraffins such as those commercially available as Cereclor cross-linkers low molecular weight reactive hydrogen-containing compositions), pigments/dyes, flame retardants halogenated organophosphoric acid compounds), inhibitors weak acids), anti-oxidants, and plasticizers/stabilizers sulphonated aromatic compounds). The amounts of these additives conventionally used would be within the purview of a person skilled in the art.

The manner by which the chemical binder is prepared is not particularly restricted as regards the order of addition of the components.

15 Generally, the manner by which the chemical binder is prepared will depend, at least in part, on the intended use thereof.

Thus, if the chemical binder is intended to be used in a foundry *'application, as described hereinabo, t w conventional techniques are the no-bake process and the cold box process.

20 When using the chemical binder in the no-bake process, it is preferred to initially mix the catalyst with a particulate aggregate. The ester-based polyol and the isocyanate are added in successive stages. The components are mixed well for a short period less than 10 mints, preferably less than minutes) in each stage prior to addition of each component. After the isocyanate has been added and mixed with the other components, the mixture is moulded and allowed to cure. Generally, the period of time to effect sufficient curing is from about 3 to about 20 minutes. It will be clear to those of skill in the art that modifications to the process are possible. For example, it is known in the art to supply polyol which is premixed with catalyst. In the context of the present chemical binder, it is possible to premix the ester-based polyol with a catalyst. Such a polyol would then be mixed, successively, with the particulate aggregate and the isocyanate.

-14- When using the chemical binder in the cold box process, to initially mix the ester-based polyol wi the aggregate followed by addition of the isocyanate. The components are mixed well for a short period (e.g.

less than 10 minutes, preferably less than 5 minutes). The mixture is moulded and the gaseous catalyst is diffused therethrough. The moulded mixture is then allowed to cure. Generally, the period of time to effect sufficient curing is from about 3 to about 25 seconds or more. More information on the cold box process may be found in United States patents 3,702,316, 3,919,162, 3,933,727, 3,937,272, 4,079,773 and 4,089,363, the contents of each of which are hereby incorporated by reference.

When use in, intrala, a foundry application, the mouldable mixture .f the present invention comprises a particulate aggregate and the chemical *binder described hereinabove. The choice of particulate aggregate is not specifically restricted. Ideally the particulate aggregate will be substantially inert to the rcon of c e t reaction of components in the chemical binder. A suitable particulate aggregate may be selected from the group consisting of sand, silica in the form of sand), silicon carbide, aluminum oxide A1 2 0 3 magnesium oxide, calcium carbonate, talc, zircon, olivine, aluminosilicat chrmite an ceamics such as refractory oxides, carbides, and nitrides, silicide such as aluminum oxide, lead oxide, chromic oxide, zirconium oxide, silicon carbide, titanium nitride, boron nitride, molybdenum Sisiicide and the like, and carbonaceous material such as graphite. Of course, it will be readily appreciated by those of skill in the art that mixtures of two or more of such aggregates can be used.

Foundry moulds made using the chemical binder and mouldable composition of the present invention may be used to cast virtually any metal such as iron, brass, stainless steel, aluminum, copper, bronze, magnesium, manganese alloy and gold. The manner by which this can be done is within the purview of a person skilled in the art.

The manner by which the mouldable mixture is prepared is not specifically restricted. It is contemplated that the particulate aggregate is initially mixed with one or more ingredients of the chemical binder.

Specifically, it is preferred that the particulate aggregate is initially mixed with the catalyst and the ester-based polyol of the chemical binder. Thereafter, the isocyanate of the chemical binder is added to the mixture which is then capable of being moulded to the desired shape.

As discussed hereinabove, in the embodiment of the invention relating to a chemical binder for use in manufacturing a foundry mould, it is especially preferred to use an ester-based polyol derived from the condensation reaction between diethylene glycol and polyethylene terephthalate (PET). A number of advantages accrue from such a chemical binder, including: 1. The polyol can be produced using recycled PET (e.g.

from X-ray film and soft drink bottles) thereby providing a net benefit to the environment. It will be appreciated, however, that some or even all of the PET 15 can be virgin PET.

2. Due to the relatively high aromaticity of mould based on such a chemical binder, at metal pouring temperatures, a higher hot strength is possible. This is 20 important since very few organic compounds can withstand metal pouring temperatures.

3. The polyol use to produce such a chemical binder is free of phenol and formaldehyde. This results in considerable improvement in the working environment, including elimination of exposure to the toxic fumes of phenol and formaldehyde.

4. Sand used as an aggregate with the chemical binder can be reclaimed and reused. Waste from moulds manufactured using the chemical binder can be recycled with minimal or no risk of toxicity in road works and -16as cement additives. Further, the present chemical binder is relatively non-toxic compared to binders currently being used in the foundry industries and abrasives industries.

The chemical binder can be use in existing phenolic poly-based urethane, no-bake and cold box equipment with minimal or no additional capital expense..

6. A mould manufactured using such a chemical binder may be characterized by significant reduced smoke emissions during metal pouring and thermal decomposition when compared to a mould manufactured using a chemical binder based on a phenolic S 15 polyol/isocyanate system. This results in a further environmental benefit associated with the present chemical binder.

S S Embodiments of the invention will be described with reference to the 20 following Examples. It should be clearly understood that the Examples are exemplary in nature and should not be used to limit the scope of the present invention.

In the Examples, the following terms have the meanings indicated: 1. Based on sand; 2. Based on binder; 3. Strip time; 4. Work time; Pounds per square inch; 6. Relative humidity; 7. Room/ambient temperature; and 8. PBW: Parts by weight.

In the Examples the following compounds were used: -17- 1. MANCU-SAT A-400 series, a polyol composition as detailed in Table 1; 2. MANCU-SAT A-700 series, a polyol composition as detailed in Table 3. MANCU-SAT B-500 series, a polymeric MDI composition as detailed in Table 2; 4. MANCU-SAT B-800 series, an isocyanate composition as detailed in Table 6; MANCU-SAT C-600 series, a catalyst composition as detailed in Table 3; 6. MANCU-SAT C-900 series, a gaseous catalyst composition consisting of dimethylethylamine; 7. Rubinate M, an MDI commercially available from ICI Americas Inc.; 8. Rubinate 1820, an MDI commercially available from ICI Americas Inc.; 9. PAPI 94, an MDI commercially available from the Dow Chemical Company; 10. Mondur" MR200, MR and MRS-5, isocyanates commercially "20 available from Bayer Corporation; 11. RAP-B-025, an MDI commercially available from Mancuso Chemicals Limited (Niagara Falls, Ontario); 12. T-500, an ester-based polyol having a hydroxyl number of 500; 13. Stepanol* PS 4002, an ester-based polyol having a hydroxyl number of 390-410 and commercially available from Stepan Company (Northfield, Illinois); 14. RAP-A-015, a phenolic polyol commercially available from Mancuso Chemicals Limited (Niagara Falls Ontario); Solvesso T 100, 150 and 200ND, hydrocarbon solvent commercially available from Esso Chemical Canada (a division of Imperial Oil Limited); 16. Triethyl amine, a catalyst; 17.' Dimethylbenzylamine, a catalyst; Designaton Component (PBW) AA-401 4402 403 A-406 A-407 T-500 90: 65 55 Diacetone alcohol Solvesso' 20OND 25 EPA 10 25 Solvesso m 150 10 20 20 31L op imzon Component (PW C401 C-602 C-603 4-Phenylpromir- 25 so pyridine Benzyldimetlam 100 Solvessol' 100 75 TABLE 2 4A a w

U

fm as Designation Component 8-501 8-502 8-503 B-504 1B-5O5 B-506 B-507 B-508 B-509 B-5 (Paw)1 IDAPI 94 100 90- Rubinaic 1820- 100 90 Rubinate M 100 Mondur' MR200 so0 Mondur m MR 80 Mondur MRS-S- Kerosene 5 5 Solvesso m 100 10 10 10 15 15 Is 18. dibasic ester, a methyl ester of adipate guterate succinate commercially available from E.I. DuPont de Numours and Company; 19. SY, Sylphat

T

a tall oil fatty acid commercially available from Hercules Chemicals; Diacetone alcohol, a solvent; and 21. IPA, isopropyl alcohol, a solvent.

EXAMPLES 1-15 The following no-bake procedure was used in each of Examples 1-15.

Initially, a mouldable composition was prepared by premixing an aggregate "..with a catalyst composition and a polyol composition. Mixing was effected for a period of about 1 n minutes. Thereafter an isocyanate composition was added to the mixture and mixing was continued for an additional 1 I minutes.

15 The type and amount of aggregate, catalyst composition, polyol composition and isocyanate composition are detailed in Table 4.

•The mouldable composition was dispensed in a No. 696 Tensile Core Box having 12 cavities. Generally the Core Box is designed for the study of self-curing or air-setting core binder systems. The Core Box was constructed 20 of four complete 3-cavity, 1-inch thick, tensile core boxes positioned side by side in a wooden frame. Each 3-cavity aluminum core box was split for easy removal of the core specimens.

As is known in the art, a No. 696 Tensile Core Box can be used to produce specimens to measure the early development of strength and the build-up of tensile strength over a period of time. By producing specimens over varying timeframes, after discharge from the mixer, the length of effective work life or work life of the mix as reflected by the tensile strength can be readily determined. Thus, measuring the tensile strength of the "dogbone" or "dumbbell" shaped specimens (American Foundrymen's Society (AFS) standard) enables one to predict the suitability of the chemical binder in actual application for preparing moulds and cores. Testing conducted in Examples 1-15 was in accordance with Section 15 of the AFS Mold and Core -21- Test Handbook (The American Foundrymen's Society, Des Plaines II), the contents of which are hereby incorporated by reference.

Thus, the tensile strength of each specimen was tested in using a No.

612 Tensile Tester. The particular apparatus used was a motor-driven Tester capable of testing up to 1200 psi on a one inch thick AFS standard specimen.

The loading rate was uniform and the Tester was able to load to full scale in seconds.

For Examples 1-10, the results of tensile testing of each specimen at various time periods after unloading from the mixer are reported (as an average of three tests) in Table 4A. For Examples 11-15, the results of tensile testing of each specimen at various time periods after unloading from the mixer are reported (as an average of three tests) in Table 4B.

The results in Tables 4A and 4B show that the Examples produced a composition useful to produce a foundry mould under a variety of 15 conventional foundry conditions. Indeed a series of useful foundry moulds and castings produced therefrom were made.

e EXAMPLE 16 In this Example the ester-based polyol was a composition comprising 20 90 PBW Stepanol* PS-4002 and 10 PBW diacetone alcohol. The isocyanate used was MANCU-SAT B-506 (see Table 2) and the catalyst used was MANCU-SAT C-602. The methodology described in Examples 1-15 was repeated using Lake AFS #50 sand to produce a number of dogbone or dumbbell shaped specimens. The components were used in the following amounts: Component Amount (g) Polyol composition 18.75 Isocyanate composition 18.75 Catalyst composition 2.25 Sand 3000 a 0

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m 0N TABLE 4A Example No/Type POIyoI Isocyanate Calaiyst W.T S.T TENSILE STRENGMlI (PSI) of Sand (wt. (wt. (wl. (min.) (min.) BOS) BOS) BOB) 15 min. I hour 24 hours I. lAke AFS #50 A-401 B-501 C-601 6 8 75 188 166 0.625 0.625 2. Lake AFS #50 A-401 B-501 C-601 6 9h 77 200 211 0.750 0.750 3.[ae AFS #50 A-401 0-502 C-602 5' 7Sh 94 170 184 0.750 0.750 4. Silica AIS #70 A-401 B-502 C-602 6 8 49 139 151 0.625 0.625 6.0 5.I adgcr FA554-5- A-401 B-502 C-602' 51 7 1 94 170 184 62651 0.625 0.625 6. Lake AFS #50 A-402 B-502 C-602 51h 6% 79 185 196 0.625 0.625 7. Lake AFS #50 A-401 8-503 C-60 6 7 79 157 109 0.625 0.625 8. Lake AFS #50 A402 B-504 C-602 7 9 1 21 127 237 0.625 0.625 6.0 1 9. Lake AFS I50 A-402 B-505 C-602 6h 9 29 150 230 0.625 0.625 6.0 I Lake AFS #50 A-402 0-506 C-602 6 7 32 155 207 0625 0625 6.0 1 1 1 h,

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TABLE 4B Example No./1Mpe Fblyol lucaucCatalyst W.T S.T TENSILE STRENani (psi) ofSand (Wt. (wt.%l (wt. (min.) '010M) 30:.mn Ibhour 24 hours WIS). VS). IM) I I IkeAFSDSM A-403 *E7 C-026 8 160- ISO .200 0.625 (12 12. Lake AFS15 -0 50 M-0 7 9 0 3S:~ B 13.Lke AFSD5O A-403 W-6 C02S 11 8 1:10 1 0.625 14. Lake AFS MS 40 dM C63 2/ 3 2 4 L-ake AFS #50 A-407 B-510 C-603 2 1 3 1 100) 130 184 0.625 10.625 6.0 II -24- Tensile testing of the specimens was conducted using the methodology described hereinabove in Examples 1-15. The results are as follows: Time Period Tensile Strength 15 minutes 135.3 1 hour 167.3 24 hours 173.3 These results demonstrate that a useful foundry mould can be produced based on a mouldable composition consisting of the components used in this Example.

EXAMPLE 17 In this Example, a cold box process was used. The ester-based polyol 15 was a composition comprising 70 PBW T-500, 13.7 PBW 14.7 PBW diacetone alcohol, 1.0 PBW SY and 0.3 PBW silane Z6040 (an epoxy silane) or silane A1120 (an amino silane). The isocyanate used was a composition comprising 100 PBW PAPI 94 and 0.6 PBW BPOD (benzene phosphorus oxydichloride). The catalyst composition used was triethyl amine diluted in 20 nitrogen gas. The aggregate used was Lake AFS #50 sand.

The ester-based polyol composition, isocyanate composition and sand were place in a mixer in the following amounts: Component Amount (g) Polyol composition Isocyanate composition Sand 4000 After adequate mixing of the components, they were dispensed into a cold box core adapted to include a gas injection jet in each specimen compartment.

Once mixed components were dispensed into the Core Box, mixture in each specimen compartment was diffused for 5 seconds with the gaseous catalyst composition. Thereafter, each specimen compartment was purged with air for seconds.

Tensile testing of the specimens was conducted using the methodology described hereinabove in Examples 1-15. The results, reported as the average tensile strength for two tests, are as follows: Time Period Immediate minutes 1 hour 24 hours Tensile Strength These results demonstrate that a useful foundry mould can be produced based on a mouldable composition consisting of the components used in this 15 Example.

EXAMPLES 18-22 In these Examples, a cold box process was effected using the general methodology described in Example 17. The polyol compositions used in these Examples were in the A-700 series and may be found in T'ble TABLE Designation Component (PBW) A-700 A-701 A-702 T-500 65 65 Solvesso T 200ND 25 25 IPA 10 9.8 4.8 Silane 6040 0.2 0.2 -26- The isocyanate compositions used in these Examples were in the B-800 series and may be found in Table 6.

TABLE 6 Designation Component B-800 B-801 B-802 B-803

(PBW)

Mondur MR200 100 Mondur" MR 80 Mondur MRS-5 100 Kerosene 5 Solvesso" 100 15 10 The type and amount of aggregate, catalyst composition, polyol copmosition and isocyanate composition used in these Examples are detailed in Table 7. The methodology and test procedures described in Example 17 were repeated for these Examples. The results of tensile testing may be found in Table 7 and demonstrate that a useful foundry mould can be produced based on a mouldable composition consisting of the components used in these Examples.

It should be understood that, while exemplary embodiments of the present invention have been described herein, the present invention is not limited to these exemplary embodiments, and that variations and other alternatives may readily occur to those of skill in the art without departing from the intended scope of the invention as defined by the attached claims.

For example, those of skill in the art will readily understand that foundry moulds or cores made using the present chemical binder may be subjected to a mould or core wash application, as appropriate.

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CE *a a a C U. *C TABLE 7 Example NO.I1pe PIiYOI Isoqcyaat Catalyst TENSILE STRENGFII (PSI) of Sand (wt. (wt. (wt. BOS) DOS) BOB) Inwmdiate I hour 24 hours 18. take AFS 150 A-700 B-801 C-900 47 104 109 0.75 19. Lake AFS 850 A-700 U-801 C-900 57 146 158 0.75 0.75__ Lak AFS #50 A-700 A-802 C-900 44 205 0.75 10.75 21. LAk AFS #50 A4702 0-802 C-900 69 75 101 0.75 0.75 22. Lake AFS #50 A701 0-803 C-900 61 220 194 0.825 0.675 P:NWPDOCS\MCCOCOMPRISE. 4/11/99 -27a- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

0 *o *0•o

Claims (13)

1. 7-02;11:00AM; 7/ 7 P:\WPDOCS1CRNSPEC7462066.do-2/07/02 -28- The claims defining the invention are as follows: 1. A chemical binder when used in the production of a foundry shape, the binder comprising: a polyol; an isocyanate; and a catalyst capable of catalyzing a reaction between the polyol and the isocyanate; characterized in that: the polyol is an ester-based polyol, and (ii) the binder is substantially completely free of phenol and phenol-based polyols. 2. The binder defined in claim 1, wherein the ester-based polyol has a hydroxyl number in the range from 200 to 600. i 3. The binder defined in claim 1 or claim 2, wherein the polyol contains a 15 polyhydroxy functional group derived from a hydroxyl-containing compound. 9 4. The binder as defined in claim 3, wherein the hydroxyl-containing compound is selected from the group consisting of 1,3-butane diol, 1,4-butane diol, 1,2- cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, dimethylol propionic acid, dipropylene glycol, ethylene glycol, 1,6-hexanediol, hexylene glycol, neopentyl glycol, 1,5-pentanediol, propylene glycol, tetraethylene glycol, triethylene glycol, trimethylene glycol, trimethylpentanediol, glycerine, trimethylol ethane, trimethylol propane, pentaerythritol and mixtures of two or more of these. The binder defined in anyone of claims 1 to 4 wherein the isocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof. P:\WPDOCS\CRN\SPECI\7462066.spe.doc-22/07/02 -29- 6. The binder defined in anyone of claims 1-5, wherein the catalyst is selected from the group consisting of N,N-dimethylaminoethanol, N,N- dimethylcyclohexylamine, N-methyldicyclohexylamine, bis-(2-dimethylaminoethyl) ether, N,N,N',N',N"-pentamethyldiethylene triamine, N,N-dimethylbenzylamine, N,N- dimethylcetylamine, diaminobicylooctane, potassium octoate, potassium acetate, stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylates, dioctyltin thiocarboxylates, phenylmercuric propionate, imidazoles, substituted imidazoles, lead octoate, alkali metal salts, calcium carbonate, ferric acetylacetonate and 4-alkyl pyridines wherein the alkyl group has one to four carbon atoms. 7. The binder defined in anyone of claims 1-5 wherein the catalyst is selected from the group consisting of triethylamine, dimethylethylamine, trimethyl amine and mixtures thereof.
2. 8. The binder defined in anyone of claims 1-7 wherein the ester-based polyol is based on diethylene glycol and polyethylene terphthalate.
3. 9. A mouldable mixture for use in production of a foundry shape, the mixture comprising: a particulate aggregate, a polyol, an isocyanate and a catalyst capable of catalyzing a reaction between the polyol and the isocyanate; characterized in that the polyol is an ester-based polyol, and (ii) the binder is substantially completely free of phenol and phenol-based polyols.
4. 10. The mixture defined in claim 9, wherein the ester-based polyol has a hydroxyl number in the range of from 200 to 600.
5. 11. The mixture defined in claim 9 or claim 10, wherein the polyol contains a 0 polyhydroxy functional group derived from a hydroxyl-containing compound. P:\WPDOCS\CRN\SPECI\7462066.spe.doc-2207/02
6. 12. The mixture defined in claim 11, wherein the hydoxyl-containing compound is selected from the group consisting of 1,3-butane diol, 1,4-butane diol, 1,2- cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, dimethylol propionic acid, dipropylene glycol, ethylene glycol, 1,6-hexanediol, hexylene glycol, neopentyl glycol, 1,5-pentanediol, propylene glycol, tetraethylene glycol, triethylene glycol, trimethylene glycol, trimethylpentanediol, glycerine, tirmethylol ethane, trimethylol propane, pentaerythritol and mixtures of two or more of these.
7. 13. The mixture defined in anyone of claims 9-12 wherein the isocyanate is selected from the group consisting of 2,4-toluene diiosycanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof.
8. 14. The mixture defined in anyone of claims 9-13 wherein the catalyst is selected from the group consisting of N,N-dimethylaminoethanol, N,N- :dimethylcyclohexylamine, N-methyldicyclohexylamine, bis-(2-dimethylaminoethyl) *:ether, N,N,N',N',N"-pentamethyldiethylene triamine, N,N-dimethylbenzylamine, N,N- S. dimethylcetylamine, diaminobicylooctane, potassium octoate, potassium acetate, stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylates, dioctyltin thiocarboxylates, phenylmercuric propionate, imidazoles, substituted imidazoles, lead octoate, alkali metal salts, calcium carbonate, ferric acetylacetonate and 4-alkyl pyridines wherein the alkyl group has one to four carbon atoms. The mixture defined in anyone of claims 9-14, wherein the ester-based polyol is based on diethylene glycol and polyethylene terphthalate
9. 16. The mixture defined in anyone of claims 9-14, wherein the ester-based polyol is based on the reaction of an alcohol with an aromatic compound selected from the Igroup comprising of polyethylene terphthalate, phthalic anhydride, isophthalic acid, P:\WPDOCS\CRNSPECI\746266.spe.do-22O7f2 -31- dimethyl terphthalate and mixtures thereof.
10. 17. A process for producing a free-standing mould comprising the steps of: (i) shaping the mouldable mixture defined in anyone of claims 9-16, and (ii) curing the mouldable mixture to produce the free-standing mould.
11. 18. A process for producing a free-standing mould using the mouldable mixture defined in anyone of claims 9-16, the process comprising the steps of: shaping a mixture comprising the polyol, the isocyanate and the aggregate to provide a mould, (ii) diffusing the catalyst through the mould, and (iii) curing the mouldable mixture to produce the free-standing mould.
12. 19. The chemical binder defined in anyone of claims 1-7, wherein the ester-based polyol is based on the reaction of an alcohol with an aromatic compound selected from 15 the group comprising of polyethylene terphthalate, phthalic anhydride, isophthalic •acid, dimethyl terphthalate and mixtures thereof. 0
13. 20. Binders, mouldable mixtures or processes for producing a free-standing mould, substantially as hereinbefore described with reference to the Examples. DATED this 22nd day of July, 2002 0 MANCUSO CHEMICALS LIMITED By its Patent Attorneys DAVIES COLLISON CAVE 00 0 0