DE2251888A1 - BINDERS FOR FOUNDRY UNITS - Google Patents

Description

Patent attorneys Dipl.-Ing. F. ¥ ειόϊ. «Ιανν,

Dipl.-Ing. H.Weickmann, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. F. A ₁ ^- WeICKMANn, Dipl.-Chem. B. Huber

8 MUNICH 86, POST BOX S60 820

MÖHLSTRASSE 22, CALL NUMBER 48 3921/22

<983921/22>

3079/3084/3125 / Dr.K

Hooker Chemical Corporation, Niagara EaIls, N.T. 14302

7.St.A.

Binders for foundry units

The invention is based on the object of providing a new resin binder for foundry units place. These binders should be curable at low temperatures, even at room temperature. the new binders for beads and molds should still be easy to remove.

The invention thus relates to new binders for foundry units and in particular binders for foundry units, which (1) a, phenolic compound, an organic polyisocyanate and an essentially

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contain anhydrous resin, soluble in organic solvents, which has been produced by, that (a) a condensation product of phenol with an aldehyde or ketone, which has condensate units with reactive phenolic hydroxyl groups, with (b) a substance has been implemented, which is reactive towards the phenolic hydroxyl groups, for example a Monooxirane ring compound, an alkylene halohydrin or an alkylene carbonate.

They contain a component with the general formula

r H

i ^{H !} 2

C t

R-

η has an average fourth of about 0.2 to 6, preferably from about 0.5 to 3 ,

x, y and ζ are integers from 1 to 25, preferably about 1 to 10,

R _{1 is} hydrogen, fluorine, chlorine and / or bromine as well as

a) alkyl and alkenyl groups with 1 to 18 carbon atoms in any isomeric forms, which is optionally substituted on the phenol nucleus in the ortho, meta or para position could be,

b) alicyclic groups with 5 to 18 carbon atoms, such as cyclohexyl, cyclopentyl, methyl

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cyclohexyl j butylcyclohexyl and the like,

c) aromatic or Äralkylgruppen having 6 to 18 carbon atoms, such as phenyl, Jj -Metlr / lbenzyl, benzyl, cumyl and the like;

-d) alkyl-j alkenyl, alicyclic, aryl · and Aralkyl ketones, wherein the hydrocarbon portion is as defined above and / or

e) alkyl-j alkenyl, alicyclic, A ^ l- and aralkylcarboxylic acid groups, wherein the hydrocarbon part has the given definition,

mean as well as their.Mixtures. As already stated, the hydrocarbon radicals preferably have 1 to 18 Carbon atoms.

The substituents Rp and R ₇ independently represent hydrogen, hydrocarbon radicals having 1 to 7 carbon atoms, and halogen-substituted hydrocarbon radicals having 1 to 7 carbon atoms. R ^ stands for a hydrocarbon radical with 2 to 6 carbon atoms.

They contain (2) a phenolic compound and an organic polyisocyanate, (3) a phenolic compound organic polyisocyanate and an essentially anhydrous condensation product which is soluble in organic solvents an aldehyde with a furan alcohol or (4) an organic polyisocyanate and an essentially anhydrous, in organic solvents soluble condensation product of an aldehyde with a furan alcohol, where the furan alcohol has the general formula on v / e:

R ₁

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where ν denotes 0 to h and R ^ denotes hydrogen, alkyl having 1 to 8 carbon atoms and / or halogen.

As a phenolic compound, compounds such as bisphenols, Biphenols, thiodiphenols, sulfonyldiphenols, mercaptodiphenols or / and triphenols, used v / ground. These phe.uolisehen · connections can be made by the general formula

HX

are expressed in which X is oxygen or sulfur, y is an alkylidene radical, an arylene radical, -S-, -SS-, or -S-, η is 0 or 1 and R ₁ - and Rg are hydrogen, alkyl with 1 to 6 Mean carbon atoms and / or halogen. The monomeric compound contains two or more active hydrogens which are capable of reacting with the organic polyisocyanates used according to the invention.

The invention also provides foundry molds and casting cores from the foundry units with the new binders are solidified, are composed.

The resin component of the given formula defined herein can be prepared by a process in which one implements together:

a) a fusible, organic solvent-soluble condensation product of a phenol and of an aldehyde or ketone, which is opposite to pbeno-

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Lischen hydroxyl groups has reactive condensate units and

b) a substance which is reactive towards the phenolic hydroxyl groups and which has a monooxirane ring compound, is an alkylene halohydrin, and / or an alkylene carbonate. The condensation product can can also be produced by first reacting the phenol with a substance that reacts with the phenolic Hydroxyl groups is reactive, and by hereafter the modified phenol with an aldehyde or condensed ketone.

The essentially anhydrous component of the invention Binder is made by adding a furan al-. kohol.mit an aldehyde is condensed.

The furan alcohol has the general formula

_ R

-CH ₂ (CH ₂ ) _v OH

where ν is 0 to 4 and R _{1 is} hydrogen, alkyl having 1 to 8 carbon atoms and / or halogen. Examples of suitable furan alcohols are furfuryl alcohol, 2- (2-furyl) ethyl alcohol, 3- (2-furyl) propyl alcohol, 4- (2-puryl) butyl alcohol, 5- (2-furyl) pentyl alcohol. Alkylfuran alcohols such as methylfuryl alcohol, ethyl furfuryl alcohol and the like, 3- (2-furyl-4-methyl) propyl alcohol, halofuran alcohols such as chlorofurfuryl alcohol, bromofurfuryl alcohol and fluorofurfuryl alcohol. Furfuryl alcohol is to be regarded as the preferred fural alcohol.

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The phenol-aldehyde or phenol-ketone condensate should in organic solvents, v / ie acetone, be soluble and it should not be up to the insoluble C-stage or have progressed to the stage of resistance. ΐ / hen the phenol itself is present and the aldehyde is formaldehyde, then contains a type of condensation which is very satisfactory is, condensation units, represented by the following formula:

OH

can be illustrated.

Therein η has an average of about 0.2 to 6 and often more, provided that the resin is fusible and is soluble in acetone or other organic solvent. Preferably the phenol-aldenyd condensate is a novolac containing more than one mole of phenol per mole of aldehyde or ketone.

Examples of phenols used in the production of phenol-aldehyde condensates for use according to the invention are phenol itself or substituted Phenols in which at least half of the substituted phenols have at least two of the ortho, - and para positions of the phenol nucleus for the condensation reaction (unsubstituted) are available.

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Such phenols have the following general formula:

wherein FL H, F, Cl or / and Br as well as

a) Alkyl and alkenyl groups with 1 to 18 carbon atoms in any isomeric forms, which are optionally on the phenol nucleus in ortho-, meta- or para position can be substituted,

b) alicyclic groups with 5 to 18 carbon atoms, such as cyclohexyl, cyclopentyl, methylcyclohexyl, butyl cyclohexyl and the like,

c) aromatic or aralkyl groups with 6 to 18 carbon atoms, such as phenyl, "o6 -methylbenzyl, benzyl, Cumyl and the like,

d) alkyl, alkenyl, alicyclic, aryl and aralkyl ketones, wherein the hydrocarbon part such as yorste-. is defined or / and

e) alkyl, alkenyl, alicyclic, aryl and aralkyl carboxylic acid groups, wherein the hydrocarbon portion has the definition given

means. As already stated, the hydrocarbon radicals preferably 1 to 18 carbon atoms.

Examples of suitable substituted phenols are paratert-butylphenol, para-chlorophenol, para-tert-hexylphe-

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nol, para-cyclohexylphenol, para-octadecylphenol, para-nonylphenol, para-ß-Naphty! phenol, para-Λ -naphthylphenol, Cetylphenol, para-cumylphenol, para-IIydroxyace tophe-. non, para-hydroxybenzophenone, phenols alkylated with limonene, Phenols alkylated with oleic acid sov.de the corresponding ortho- and mota derivatives, such as meta-butylphenol, and ortho * -butylphenol, as well as mixtures of these substances.

Aldehydes and ketones or their mixtures, which are able to react with a phenol or furan alcohol, are satisfactory provided that the aldehydes or ketones have no functional groups or structures which interfere with the condensation reaction or the oxyalkylation of the condensate. The preferred aldehyde is formaldehyde, which is in aqueous solution or in any low-polymer form, such as para-formaldehyde or trioxane. The aldehydes preferably contain 1 to 8 carbon atoms. More examples of suitable aldehydes are acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, furfural, 2-ethylhexanal, ethylbutyraldehyde, Heptaldehyde, pentaerythritol, glyoxal, chloral and the like.

Although it is not absolutely necessary because of the in situ formation of formaldehyde, an aldehyde to use, it is preferred to use a small amount of an aldehyde. The amount of used Aldehyde can be about 0.01 to about. 50 wt. Sa, based on the total weight of the mass, preferably about 3 to about 6% by weight. The furan alcohol and the aldehyde are grounded heated to reflux and held at that temperature until the (unsolvated) resin products one Refractive index of about 1.5300 to about 1.5600, preferably about 1.5300 to about 1.5400 when using shape

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have aldehyde. It is preferred to use an acidic catalyst during the condensation. Mineral acids, such as sulfuric acid, hydrochloric acid, zinc chloride, phosphorus pentoxide, chromic acid, QUeCkSiIbGr (II) chloride, and organic acids, such as oxalic acid, diethyl sulfate and the like, can be used. If the condensation reaction has proceeded to the desired extent, then. the resin is neutralized with an alkaline compound such as sodium hydroxide and dehydrated until it is essentially anhydrous, ie up to less than about 5% by weight of water, based on the "weight of the resin, preferably less than about Λ% If the furan alcohol is furfuryl alcohol and the aldehyde is formaldehyde, then the ■ condensation product has the formula:

. (CH ₂ ) y (CH ₂ GCH ₂ ).

.CH ₂ OH

where y and ζ are individually 0 to 1, the sum of y and ζ in each repeating unit is 1, the ratio of y to ζ is greater than 1 and η is 1 to 8, The preferred average molecular weight of the resin is from about 450 to about 500. The resin has an average molecular weight Hydroxyl reactivity from about 290 to about 310 at room temperature.

The condensation can take place with or without the addition of a diluent be performed. If the condensation is carried out without a diluent, then will the product is then preferably mixed with a suitable solvent. Suitable solvents or

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Diluents for the furan alcohol-aldehyde condensate are, for example, aromatic hydrocarbons having 6 to 10 carbon atoms, such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, ilonochlorobenzene and the like. Examples of suitable other solvents or diluents are ilonoester honey ethers of alkylene glycols having 2 to 10 carbon atoms, such as ethylene glycol (carbitol), diethylene glycol (Cellosolve), propylene glycol, butylene glycol and the like. Typical substances of the above class are, for example, cellosolve acetate, methyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and mixtures thereof. Mixtures of the representative classes of solvents or diluents can also be used. With the abovementioned classes of solvents and diluents, auxiliary solvents can also be mixed together, such as aliphatic hydrocarbons, for example hexane, octane, mineral fuel, petroleum naphtha and the like. The condensation product and solvent are mixed until a uniform homogeneous mixture is formed. The solvent is generally used in the proportion of about 10 to about 40 parts by weight per 100 parts of the resinous fusible condensation product, preferably in an amount range of about 20 to about 25 parts by weight of the solvent per 100 parts of the resinous product. The mass of the resinous condensation product and the solvent generally has a viscosity in the range from about 50 to about AOO cps at 25 ⁰ C and a hydroxyl number in the range from about 300 to about 500. The binder race, containing the condensation product, the organic polyisocyanate and a solvent, contains, after mixing, the solvent generally in an amount of about 10 to about 50 parts by weight of solvent per 100 parts by weight of the total mixed solids of the con-

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densation product together with the organic polyisocyanate, preferably in an amount of iron about 15 "to about 35 parts by weight of solvent per 100 parts of the mixture th total solids of the condensation product and the organic polyisocyanate ..

The ketones have the general formula

Il

R ₂ - C -

where Rp and FU are hydrogen or organic radicals. Examples of suitable ketones are acetone, methyl ethyl ketone, diethyl ketone, methyl benzyl ketone, methyl cyclohexyl ketone, dially! Ketone, dichloromethyl ketone and mixtures thereof. The substituents Rp and R ₇ preferably have 1 to 7 carbon atoms.

The ratio of aldehyde or ketone to the phenol (or to the oxyalkylated phenol) can be varied to produce condonsates of different molecular weights. The viscosity of the final condensation product can be determined by the molecular weight of the phenol-aldehyde or phenol-ketone condensate be regulated. The amount of the aldehyde or ketone preferably varies from 0.5 to 1.0 mole per mole Phenol (or oxyalkylated phenol) if a mono- or difunctional phenol is used. In cases when a trifunctional phenol is used, the preferred upper amount of the aldehyde or ketone is about -0.85 Moles per mole of phenol (or oxyalkylated phenol). It is preferred that the aldehyde or the ketone and the phenol using an acidic catalyst such as sulfuric acid, hydrochloric acid or oxalic acid. It can but basic catalysts can also be used. In

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in some cases no catalysts are necessary at all. Examples of alkaline catalysts are ammonia, Awine and quaternary ammonium bases. Wetting agents of anionic type, such as sodium alkylarylsulfonates, can be used to speed up the reaction when weak acids are used.

In cases where a resole is prepared, quantities of more than 1 mole of formaldehyde per mole of phenol (or oxyalkylated phenol). The specific phenols and aldehydes or ketones which can be used are described above. Also the alkaline ones described above Catalysts are suitable. The resols have carbinol groups as well as phenolic hydroxyl groups that are associated with the reagents mentioned below can be implemented.

According to the invention, improved condensation products can be produced, which preferably are essentially none free reactive phenolic groups, i.e. less than about 5%, but preferably less than about 0.5%, of the phenolic Contain hydroxyl groups originally present in the phenol-aldehyde or phenol-ketone condensate was.

The preferred method of hydroxyalkylation is done by reacting with compounds that form a Konooxiranring contain. Monomeric epoxides having 2 to 18 carbon atoms are preferred. Examples of usable monoepoxides are ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, 2,3 ~ - & poxyhexane, epichlorohydrin, styrene oxide, Allyl glycidyl ether, Ilethyl glycidyl ether, duty! Glycidyl sulfide, Glycidylinothylsulfon, Glyoirlylnethacrylat, Glycidylnfllylphthalat and the same. The preferred mono-

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Epoxides are the monoepoxy-substituted hydrocarbons, the monoepoxy-substituted ethers, sulfides, sulfones and esters, these compounds containing 2 to 18 carbon atoms. Smaller amounts of diepoxidone can also be incorporated into the masses. Typical diepoxides are 3,4-epoxy-6-methylcyclohexylmethyl-35,4 »epoxy-.6-methylcyclohexanecarboxylate, dicyclopentadiene dioxide, lime dioxide, 4,4 ^! (Diglycidyl) diphenylpropane, and vinylcyclohexane dioxide. Many other epoxides can be used, but alkylene oxides containing from 2 to 6 carbon atoms are generally used. Mixtures of the abovementioned compounds are also very suitable.

Catalysts for the reaction of the oxirane ring compounds and the phenolic hydroxyl groups are alkali or alkaline earth metal hydroxides, primary amines, secondary amines, tertiary amines, or basic alkali salts. Examples are sodium, potassium, lithium, calcium and barium hydroxides, amines such as methyl, dimethyl, diethyl, trimethyl, triethyl, tripropyl, dimethylbenzyl, dimethylhydroxyethyl, dimethyl-2-hydroxypropylamine and the like, as well as salts of strong bases and weak acids such as sodium acetate or benzoate. Combinations of the catalysts can also be used in order to obtain particular products with great advantages. For example, an amine catalyst such as triethylamine can be used to add 1 mole of propylene oxide to each phenolic hydroxyl group, followed by the hydroxyalkylation with ethylene oxide using an alkali metal hydroxide such as sodium hydroxide as the catalyst. In general, the hydroxyalkylation reaction may be carried out up to 250 ⁰ C at 50th The hydroxyalkylation of the phenols is carried out vorzugsv / else at 50 to 150 ⁰ C.

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3098 1 8/0785

The hydroxyalkylation of the phenolic condensates proceeds at 150 to 250 ^° C. at a better rate. Solvents are not normally preferred, although higher molecular weight resins can use solvents to reduce viscosity.

The phenolic hydroxyl groups of the phenols or the phenol condensates can also be hydroxyalkylated by using with the phenolic hydroxyl groups of equivalent amounts of an alkali metal hydroxide to allow the reaction to proceed with alkylene halohydrins implements. Suitable alkylene halohydrins are ethylene chlorohydrins or bromohydrins, propylene chlorohydrins or bromohydrins, 2,3-butylene chlorohydrins or bromohydrins and glyceryl chlorohydrins or bromohydrins.

Another method for the hydroxyalkylation of novolacs is by reaction with alkylene carbonates, such as ethylene carbonate and propylene carbonate, for example sodium or potassium carbonate being used as the catalyst.

In the production of a phenol-aldehyde or phenol-ketone condensation product should have at least one hydroxylalkyl group per phenol-aldehyde or phenol-ketone molecule to be available. It is preferred that at least about 1 mole of the hydroxyalkylating agent per mole of the phenolic Hydroxyl groups is used. Often, however, products are sought that can be achieved by implementing a number of units of the hydroxyalkylating agent have been produced per hol of the phenolic hydroxyl groups, since the physical properties of polyurethane compositions containing them can be adjusted by controlled the length of the ether chain. Can also

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The hydroxyl number of the modified phenol-aldehyde condensate can be adjusted by controlling the length of the ether chain. The length of the ether chain also influences the viscosity of the condensation product, as well as the physical properties of the deformable sand races, which are ultimately produced by reacting the resin component with an organic polyisocyanate. In general, it is not appropriate to use more than 10 Hol hydroxyalkylating agents per Hol phenolic hydroxyl groups. However, if desired, up to 25 units of the hydroxyalkylating agent can be used per hol phenolic hydroxyl groups.

The pheholi see compounds referred to as "bisphenols" comprise dihydric dijjhenols with a single carbon between the rings. These products are made of 'any aldehyde υχιά from many ketones available ■ that are implemented using any phenol which has an open ortho or para ~ position. The bisphenols contemplated herein have the general formula:

Rr R "

C I

R '

1 t iv— _0H

where R ¹ 'and R "are hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 5 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms. These substituents can be identical or different. R, and, Rp are hydrogen, Alkyl with 1 to 6 carbon atoms and / or halogen.Representative bisphenol isomers are ο, ο'-bisphenol, m, m'-bisphenol-, ρ, ρ'-bisphenol, m, p-bisphenol, ο, ρ-bisphenol and ο, ΐη-bisphenol, representative

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Biscrcsole are 4,4'-bis ~ o-cresol, 6,6'-bis-o-cresol and 4,4-bis ^f-m-cresol. These are usually prepared by using, for example, phenol, ortho-cresol, meta-cresol, ortho-isopropylphenol, ortho-tert-butylphenol, ortho-chlorophenol or various thio-substituted phenols and the like with a ketone, such as acetone, methyl ethyl ketone, as the phenol , Dibenzyl ketone, diethyl ketone, dibutyl ketone, cyclohexanone and the like, in the presence of a strong mineral acid such as sulfuric acid or hydrochloric acid. The reaction may be carried out at room temperature, but is usually carried out at temperatures of from 30 to 9O ⁰ C. As the reaction proceeds, the bisphenol product solidifies. Upon completion of the reaction, the mixture is a thick slurry or mass containing the bisphenol product, uncondensed phenol and the mineral acid used to accelerate the reaction. Alternatively, an aldehyde can also be used instead of a ketone to form the bisphenols used according to the invention. In addition to formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, furfuraldehyde and the like can also be used. Acetylene, which in many reactions behaves as if it were the anhydride of acetaldehyde, can also be used in place of an aldehyde or a ketone to produce a bisphenol which is useful as a phenolic compound in the invention. The reaction to form a bisphenol from an aldehyde can be carried out in a known manner, so that a detailed description of this reaction is not necessary. It can be noted, however, that a strong mineral acid in high concentration, such as sulfuric acid or hydrochloric acid, preferably the latter, is used to accelerate the condensation, and that the yield of the bisphenol then increases

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is highest when the phenolic reactant dimer • is used in a proportion that exceeds the theoretically required amount.

Representative "bisphenols" that can be used in accordance with the invention are bisphenols A ₅ F, C and 'H. The formulas of bisphenols G and H are given below:

Bisphenol C

f ^H 3
CH ₃ - C - CH ₃

CH,

ί ^Η 3

CH

₃ - C - CH3 /

CH,

Bisphenol H

By suitable selection of the halogenated phenol you can halogenated bisphenol A homologs are obtained. Consequently can by reacting acetone with ortho-chlorophenol the Dichlorobisphenol A compound can be obtained. Through implementation of ortho-ortho-dibromophenol with acetone can obtain the 4,4'-isopropylidene-bis (2,6-dibromophenol) compound will.

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A suitable bisphenol A ester, namely ^, A ' dendiphenol disalicylate, can be obtained by reacting bisphenol-A with salicylic acid.

Further bisphenols suitable for the invention are 2,2-bis (4-hydroxyphenol) -1,1,3,3-tetrafluoro-i, 3-dichloropropane, 2,2-bis (4-hydroxyphenol) -1,1,1,3,3-pentafluoro-3-chloropropane and their derivatives. These can be given by the following general formula:

are indicated in which Z is chlorine or fluorine and X and Y are hydrogen, chlorine, bromine and / or alkyl radicals with 1 to 4 carbon atoms.

2,2-bis (4-hydroxyphenyl) -1,1,3,3-tetrafluoro-1,3-dichloropropane and its derivatives can be given by the general formula:

specified v / earth.

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2,2 ~ bis (4-hydro>: yphenol) -1,1,1, 5 , 3-pentaf luoro-o-chloropropane and its derivatives can be given by the general formula

can be specified.

The halogenated bisphenols used according to the invention v / ground can easily be obtained by adding 1, 1,3,3-tetrafluoro-1,3-dichloroacetone or 1,1, 1,3,3-pentafluoro-3-chloroacetone with a phenolic compound of the formula:

wherein X and Y have the meanings given, in a molar ratio of at least about 1.5 hol phenolic compound per mole of ketone reactants in the presence of boron trifluoride converts as a catalyst.

1,1,3 »3-Tetrafluoro-1,3-dichloroacetone is a colorless liquid which has a freezing point below -10O ⁰ C and a boiling point of 45.2 ° C. 1,1,1,3,3-Pentafluoro ~ 3 - chloroacetone is a colorless gas with a boiling point of 7.8 ° C.

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Phenol itself or the alkylated, brominated or chlorinated derivatives can be used as phosphoric reactants. ^r crden in which these Subßtituenten .are Toggle ·· grensend cn the hydroxyl group *

The phenolic compound known as "biphenol" kftnii the general formula:

HU - R -R- OH

where R is an aryl group. Röpräöan-tetivö '· Biphenols are ο, ο' -Biphenol, η, m-Biphonöl »ρ, ρ ♦ -Bipheiiol, Bioresole, v / ie A, 4'-Bi-o-credol, 6,6 '- * J3i -.ö-oreöol. _t 4,4'-JjJ-m-crenol, Dibenzylbi.phenole, v / ie oC " oC " ~ Diphönal. "4, / + '" bi-O-Ci ¹ CSOl, diethylbiphenolG, like 2.2 * - Diathyl-p * p '-bipheilol, 5' 5 _'UiUthyl'-o) o ^l _f -biphenol Dipropylbiphenole as 5' 5 and '~ dipropyl "o, ο'-biphenol and 2.2 ^<-Dii8opt> öpyl -p * p'-biphöfo.öl. ', ■ diallylbiphonols, such as 2,2'-diallyl-p, p ^l -biphoenol, ttnd dihalogenophenols, v / le 4,4'-dibromo-o, ο'-biphenols.

The Ötölluiißen can be used for the Dibenaylblpheiiole. of the phenolic hydroxyl groups and the BGrt & ylradiktio varied in order to obtain other suitable compounds, which correspond, for example, to the bicresols given above with different positions of the substituents. In addition, the aryl radicals in the diallylbiphetiol compounds can be replaced by other groups, including all 1-methylalyl-y, 2-methylallyl and 2-chloroallyl groups. which serve as examples of the D.ilialogenbiphenole · can tuen the BromßUbstl th tucntöii by other Halogonsubstj such as chlorine, iio.in replaced, v / v obei / iederun dj ο positions d ^ r Huh ctituonton on the Biphcnolßtruktur-, v / ie at the bicronoles.

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varies. Furthermore, the biphenol can be more than contain a phenolic hydroxyl group on each benzene ring . The two phenolic rings can have a molecular structure by an arylene group, for example a Phenylene group interposed therebetween may be separated. An example of such a compound is p ~ terephenol ~ 4,4'-diol.

The phenolic compounds referred to as “thiodiphenols” can be illustrated by the following examples: 4.4 ^! -Thiodiphenol, 2,2'-thiodiphenol, 2,2'-thiabis- (4-chlorophenol) and 4,4'-thiobis (6-tert-butyl-m-cresol).

The designated as ^"11 SuIfonyldiphenole phenolic compounds may be exemplified by the compounds 4,4'-sulfonyldiphenol and 2,4'-sulfonyldiphenol as examples'. -

It can be seen that the sulfur in the thiodiphenols can be substituted by further sulfur without the reactivity of the compounds in the process of the invention ' is affected. ■

The mercaptophenols used according to the invention are the corresponding products which are obtained when using mercaptophenol instead of the phenol itself with the, correspond * the aldehydes and ketones, as described above with regard to the preparation of the bisphenols, implemented. Examples for representative mercaptophenols are the ortho- and para-non-alkyl-substituted mercaptophenols and other mercaptophenols with alkyl, alkyl, aryl or arylalkyl substituents, where the substituent is in the ortho- or pnra position. There can be up to four substituents in the Meroaptophc? Riolin molecule present. Examples of alkyl group

3098 18/0785 bad original

are methyl, ethyl, butyl, decyl, octadccyl. Examples for alkylaryi and arylalkyl groups aind Crexyl, xylyl, Tetrarue thy! Phenyl, dooylphenyl, dodecylphenyl and the like. Examples of typical compounds are phenyl mercaptopheyjole, Ksrcajjtonaphthole and I-jercaptocresole, 2 ~ Iiercapto ~ 6-octadecylphenol, 4 ~ mercaptophonol, 2-mercapto - / + ~ chlorphonol, 2-mercapto-4,6-di-tert. -buty! phenol and o-liercaptophonol. It should be noted that also polyvalent Kercaptophenols and mixtures of various mercaptophenols can be used. These compounds are equally suitable in comparison to the bisphenols by they yield active hydrogen for reaction with the organic polyisocyanate.

The two phenolic rings can be separated in the molecule by an aryl bi salicyl en radical placed in between. Such connections, useful in the process of the invention can be obtained by mixing phenol with divinylbenzene to form a three-ring structure that corresponds to the structural formula below. It will be seen that phenols other than those described herein are also used in conjunction with the divinylbenzene can be to get to other triphenols.

CH ₂ Q ₁₂

Examples of suitable solvents or diluents for the phenolic compounds are aliphatic ketones with 3 to 8 carbon atoms, such as acetone, Kethyläthylkoton, Lethyl-n-prcpylkoton, Diethylketori, Hexagon, Cyclo-

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hexanone etc., the monoenter-I-fonoa'ther of А1 kylene glycols with 2 to 10 carbon atoms, such as ethylene glycol (Carbitol), Dietylene glycol (Cellosolve), ■ propylene glycol, butylene glycol and the same. Examples of typical members of the understanding class are Cellosolvoacetat, Kethyleello «· solvcfcetatj butylcellosolve acetate, carbitol acetate, butyl « carbitol acetate and mixtures thereof. There can also be mixtures of the aforementioned classes of solvents or diluents "With the aforementioned classes of solvents or diluents", auxiliary « solvents are mixed, such as aromatic hydrocarbons, * Substances with β to .10 carbon atoms, for example benzene, toluene, xylene, ethylbenzene, diethy! benzene, monochlorobenzene and the like, aliphatic © hydrocarbons, for example hexane, octane, ■ mineral spirits, petroleum naphtha ■: and the same. The phenolic compound, the resinous component and the solvent are mixed together until a uniform homogeneous mixture is obtained will. The solvent is generally used in a proportion from about 20 to about 90 parts by weight, per 100 parts by weight « dividing the total mixed solids of the phenolic compound and the resinous component, preferably in men gen from about 35 to about 80 parts by weight of solvent each 100 parts by weight of the total blended solids of the phenolic compound and the resinous component is used.

Suitable solvents or diluents for the mixtures of the binder components, which the invention phenolic compounds, the furan alcohol-aldehyde condensation product and the organic polyisocyanate are those described above.

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3 03818 / 078S

The solvent is generally used in an amount of about 15 to about 65 parts by weight per 100 parts by weight of the total mixed solids of the binder components, preferably in an amount of from about 35 to about 55 Parts by weight of solvent per 100 parts by weight of the mixed Total solids of the binder components is used.

Various organic polyisocyanates can be used to prepare the compositions according to the invention}. Under these isocyanates are 2,4-toluene diisocyanate and 2,6-toluene diisocyanate and their mixtures, in particular the raw mixtures, as commercial products. Examples for others typical polyisocyanates are methylenebis (4-phenol) isocyanate, n-hexyl diisocyanate, 1,5-naphthalene diisocyanate, 1,3-cyclopentylene diisocyanate, p-phenylene diisocyanate, 2,4,6-toluene triisocyanate, 4,4 '^ "- triphenylmethyltriisocyanate. The commercially available impure or crude polyisocyanates are also used considered herein. For the invention, the polyaryl polyisocyanates are particularly useful with the following general Formula:

HCO

NCO

CX.

preferred, wherein R ^ hydrogen, chlorine, bromine, alkyl with 1 to 5 carbon atoms and / or alkoxy with 1 to 5 carbon atoms and X for hydrogen, alkyl with 1 to 10 carbon atoms and / or phenyl and where m has an average value of at least 1 and in general

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3098 18/0 7 85

BAD ORIGfNAL

of about 1 to 3. A preferred example of this is polymethyliipolyphenyl polyisocyanate. The organic polyisocyanate is preferably used in a solution of the abovementioned solvents, in general in general Ratio of about 15 to about 50 parts by weight of solvent per 100 parts by weight of solids of the organic polyisocyanate. Amounts of about 25 to about 40 parts by weight of solvent per 100 parts by weight of the are preferred organic polyisocyanates.

If desired, a small amount of an auxiliary compound which can react with the isocyanate groups • is to be mixed with the resinous condensation products. Examples of such compounds are hydroxyl-terminated Polyester, e.g. products of a glycol, such as ethylene or propylene glycol, or a polyol, such as glycerine, with an acid such as phthalic acid, adipic acid, succinic acid and the like, polyethers such as polyethylene glycol, Polypropylene glycol and the like, phenol-formaldehyde resins, alkyds, alkanolamines, such as ethanolamine, triethanolamine, n-butylethanolamine, 2-amino-2-methyl-1-propanol and the like. The auxiliary compounds can contain up to about 2% by weight of the Make up the weight of the total mass. Furthermore, if desired, conventional catalysts for the Hydroxyl isocyanate conversion, such as dibutyltin dilaurate, di-, butyltin diacetate, Zinc naphthanate, lead naphthanate and the like in the resin composition in an amount of about 0.1 to about 5% by weight, based on the total weight of the binder mass, preferably in an amount of about 3 to about 5% by weight.

In preparing the moldable materials according to the invention, the foundry aggregate bz \\ ^r. "Put the foundry aggregates in a conventional pan mixer or another

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3 0 9 8 18/0785

brought their appropriate mixer. The aggregate or the The aggregate of the individual inert solid particles usually consists of sand and often contains smaller amounts Amounts of other materials such as iron oxide, grain, and the like. To the aggregate or to the aggregates becomes a binder component consisting of a solution of, (1) the resinous condensation product and (2) a phenolic compound, (3) the furan alcohol resin condensation product, (4) a furan alcohol resinous mass and a phenolic compound, or (5) the phenolic compound, given in a sufficient amount that about 0.4 to 5 wt .-% binder component, based on the weight of the foundry unit or the foundry additives, preferably about 0.6 to 2.5 wt .-? o, are present. It will take 1 to 10 minutes preferably about 1 to about 3 minutes. The aggregate grains or aggregate grains are in this way coated by the sand binder component. This is followed by the mixture of aggregate or aggregate, solvent and the binder component is a polyisocyanate component consisting of a polyisocyanate or its solution, and mixing is continued for about 1 to 5 minutes, preferably about 2 to 3 minutes. the organic polyisocyanate component is used in an amount sufficient that about 0.4 to about 5 wt .-% polyisocyanate component, based on the weight of the foundry aggregate or the foundry additives, preferably around 0.5 to 2.5 wt .- / 3, are present. The amount of total binder components plus polyisocyanate component is in the range from about 0.8 to 10 wt .- / o, based on the weight of the foundry assembly or the foundry additives, and is preferably about 1 to 5 wt .- / o. The ratio of the resinous Condensation product to the phenolic compound in the binder coraponent can be 50 to 100%, wherein in the mixed masses a ratio of about 30% to

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about 60% is preferred. Some of the solvent generally evaporates in the muller mixer. The ratio of the furan alcohol condensation product to the phenolic compound in the binder component can be 0% to 100%, with a ratio of about 30% to about 60% in the mixed compositions being preferred. The binder component and the polyisocyanate are used in a ratio sufficient to be about 0.9. to about 1.1 isocyanate groups per hydroxyl group, preferably about one isocyanate group per hydroxyl group. The. resulting deformable hasse is then removed from the mixer and molded into a suitable mold of the desired shape.

The deformable mass can also be made by using a device known as a slinger is used, which includes two screw conveyors which at a common point into a single screw conveyor converge. It is part of the foundry unit in one of the two screw feeders or the foundry aggregates and the resin introduced. The polyisocyanate and the rest of the foundry aggregate or the foundry aggregates are fed into the second of the screw-in feeders brought in. The two screw conveyors carry the sand, which is mixed with the respective compo- " nenten is coated, in the common screw conveyor, in which all reaction components with. the total batch the foundry aggregate or the foundry additives are intimately mixed.

The deformable mass is introduced into a suitable mold and using a tertiary amine as a catalyst cured at room temperature. Although it is particularly preferred to use gaseous tertiary amine, one can

3098 18/0785 BAD ORIGINAL

also with vaporized tertiary amines in an inertial current, for example from nitrogen, carbon dioxide or the like, work. Examples of suitable tertiary Amines, which generally contain up to 20 carbon atoms, are tr "i methyl amine, triethylamine, tributylamine, Tripropylamine, diraethyl-sec.-butylamine, Ν, Κ-dimethylaniline, N-methyl-Ii-ethy! Aniline, p-nitroso-K, N-diinethylaniline, N-methylmorpholine, N-ethylmorpholine, tetramethylguanidine, N, N> N ', N' -Te tramethyl-1,3-butanediamine, triethylenediamine and the same. The preferred gaseous tertiary amine is triethylamine. The fumigation can be done in the way v / ground that one manifold over the top and bottom of the core forming a tight seal lays and that then the gaseous aniine or vaporized Amine passes through the core in an inert gas stream.

The deformable compositions according to the invention can be hardened at room temperature or, if desired, at higher or lower curing temperatures, for example at temperatures of about 10 to about 10 to about 100%. ^r a 100 ⁰ C or more. In this way, a polyurethane reaction product is formed from the hydroxyl containing components of the binder component and the polyisocyanate. The hardened foundry aggregate masses or foundry aggregate masses generally contain around 0.3 to around 9% by weight total polyurethane binder mass (dry basis), based on the weight of the foundry aggregate or the foundry aggregates, and preferably around 0.4 to approx / a 5 Gew.-Jo. These masses show very good properties, for example faster hardening, better flexural strength, better flowability of the binder aggregate or binder aggregate mass, excellent removal from the mold, retention of strength at elevated temperatures (e.g. 65.6 to 149 ° C) compared to at Room temperature with volatile amines go) Arteten Gießeroizuschlagstoffeii and cores.

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Binders for easy removal for cores and molds contain a fatty acid ester, a tall oil, as a component a polyethylene glycol ester of a fatty acid or a mixture thereof. The use of polyethylene glycol esters of Fatty acids and /. Or of fatty acid esters results in increases in tensile strength and a simultaneous improvement in the ability to remove the shape. Mixtures of tall oil and fatty acid esters or polyethylene glycol esters of fatty acids are due the improved removability and the high tensile strength of the cores and / or molds compared to unmodified ones Particularly to strive for binder system according to the invention.

The tall oil and / or the fatty acid ester can be more advantageous " v / eise either in the mixture of the resinous component and the phenolic compound or in the organic Polyisocyanate component can be incorporated to give a stable mixture. The "polyethylene glycol esters of fatty acids can be incorporated into the mixture of the resinous component and the phenolic compound.

Examples of suitable fatty acids' for the production of low (C ,, to Cp) alcohol and polyethylene glycol derivatives, the are suitable for the invention are stearic acid, isostearic acid, lauric acid, oleic acid, palmitic acid, myristic acid, Pelargonic acid, isodecanoic acid, peanut oleic acid, behinic acid, palmitoleic acid, ricinoleic acid, petroselinic acid, Vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, liqueuric acid, parinaric acid, godeleic acid, Arachidonic acid, getoleic acid (cetoleic acid), erucic acid, Capric acid, caprylic acid, caproic acid, isovaleric acid, butyric acid, dodecylcarboxylic acid, Stillingic acid, decylenic acid and the like as well as their mixtures. Typical suitable lower alcohols are methyl alcohol, butyl alcohol

BAD ORIÄAL 309818/0785

hol and propyl alcohol. Typical esters are methyl and butyl stearic acid esters.

The amount of the shape-taking binder component or the mixture of such components is an effective amount of up to 10% by weight, based either on the resin-phenol compound solution or on the solution of the organic polyisocyanate. This means that a maximum of up to 20 % by weight, based on the total binder solution, can be used up. The amount of the release binder components is preferably about 5 to about 8% by weight, based on either the resin-phenolic compound solution or the organic polyisocyanate solution.

The invention is illustrated in the examples. In the absence of any information to the contrary, "parts" are parts by weight.

example 1

A typical modified phenol-aldehyde condensation product was prepared by placing 3000 parts of phenol, 13 parts of oxalic acid catalyst and 6 parts of a wetting agent in a jacketed reactor and heating ^{to 100 ° C.} An alkylarylsulfonate type anionic wetting agent is preferred. 1110 parts of 37% aqueous formaldehyde solution were introduced into the reactor at such a rate that the heat of reaction caused a vigorous reflux. The reflux was continued two hours after the addition of formalin was complete. The contents of the reactor were dewatered at 180 ° C. and then freed from phenol at 200 ° C. and under a vacuum of 50 mm. Approximately 2030 parts of phenol-aldehyde condensate were produced. 7.2 parts of sodium hydroxide were added to the reactor

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brought in. Ethylene oxide was then introduced into the reactor either as a liquid or as a vapor. The reactor temperature was initially held for two hours at 190 ⁰ C and then to 200 bit 22O ⁰ C allowed to rise, the addition bit of 878 parts of ethylene oxide was terminated. The resulting condensation product had a hydroxyl number of 370 and a Gardner viscosity at 50 ° C. of about 2000 seconds.

Example 2

A typical modified phenol-ketone condensation product was prepared according to Example 1 by adding 3000 parts of phenol, 820 parts of acetone under reflux conditions for four hours were reacted in the presence of 10 parts of sulfuric acid catalyst and 10 parts of alkylbenzenesulfonate wetting agent. After dehydration and removal of phenol as in Example 1, 10 parts of sodium hydroxide were converted into phenol-acetone condensate given. Then 900 parts of ethylene oxide were added to the reaction mixture, which at 180 to 220 C. was held. The resulting condensation product had a hydroxyl number of 310.

The characteristic properties of the compositions according to Example 1 and 2 can be changed drastically by the ratio of ethylene oxide to phenolic hydroxyl groups varies and by also changing the ratio of phenol to Aldehyde or ketone in the base condensate varies. In Examples 3 to 6, the ratio of ethylene oxide was to phenolic hydroxyl groups-varies from 1.50 to 3.00, the ratio of phenol to .formaldehyde in the basic condensate of 3: 2 was maintained. In Examples 7 to 9 the ratio of phenol to aldehyde was from

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Changed 5 to 4 and the ethylene oxide ratio was varied from 1.25 to 1.72. In Table I are the influences on the viscosity and the hydroxyl number of the resulting addition products are compiled. All other conditions in Examples 3 and 9 are the same as in the example

Table I.

Example Ratio of no. Phenol to aldehyde in the base condensate

Ratio of ethylene oxide to hydroxyl groups

Hydroxyl viscosity number

3/2 3/2 3/2 3/2 3/2 5/4 5/4 5/4

1.0 376 2000 1.50 339 335 2.0 301 52 2.5 267 23 3.0 250 13.7 1.25 340 19500 1.50 320 2200 1.72 292 545

The viscosity and hydroxyl numbers of the condensation products can also be varied by varying the type of alkylene used while varying both the chain length of the base condensate and the length of the alkylene oxide side chains keeps constant. In Examples 10, 11 and 12, the preparation procedure of Example 5 is repeated except that part of the ethylene oxide or all of the ethylene oxide was replaced by propylene oxide. The hydroxyl numbers and the viscosities of the resulting addition products are compiled in Table II, in which this fourth is compared with those of Example 5

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the. Also in Table II are the properties of the resins prepared in the preceding examples, but with different properties Proportions of phenol, formaldehyde and alkylene oxides compiled.

The following examples describe the preparation of further modified phenol-aldehyde compositions according to present invention.

Table II 2.5 ethylene oxide Hydroxyl
number Viscose
activity example
No. Ratio of ratio of
Phenol to Al-ethylene oxide too
dehydration in the basic hydroxyl groups
condensate 2.0 ethylene oxide
plus
0.5 propylene oxide 267 23 5 3/2 1.73 ethylene oxide
plus
0.76 propylene oxide 10 3/2 2.5 propylene oxide 256 21 3.5 ethylene oxide
plus
3.5 propylene oxide 257 19th 11 3/2 244 31 12th 3/2 200 0) 13th 4/3

2500 Centipoises at 30 ⁰ C,
Example 14

21 parts of an oxyalkylated novolac with 4 phenyl ceramics per 3 methylene radicals, in which 7.5 alkylene oxide units per phenolic hydroxyl group had been converted, prepared according to Example 13, were mixed with 20 parts of xylene, 20 parts of cellosolve acetate, 5 parts of furfuryl alcohol and 5 parts

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309818/078 5

Parts Ilethylisobutylketon, mixed and placed in a provided with a reflux condenser and heated therein with stirring at 70 to 80 ⁰ C. 29 parts bisphenol-A were slowly added and mixing continued until the bisphenol-A was dissolved. The resin was then cooled to 5O ⁰ C and stripped. Sixty-five parts of an organic polyisocyanate, commercially available under the trademark "Mondur IiR", was dissolved in 35 parts of an ethylbenzene-type solvent, commercially available as "SC-150" from Buffalo Solvents and Chemicals. A core mix was prepared by adding 24 g of the above resin solution, 24 g of the above polyisocyanate solution and 3.18 kg / cm2 of sea sand (AFS-45) to a Hobart mixer. Mixing was continued for four minutes. The mixture was then blown into an aluminum die with air at a pressure of 7.03 kgf / cm to prepare three cores. The shape of these cores can be described as a truncated cone with a diameter of 1.90 cm at the top, a diameter of 3.97 cm at the bottom and a height of 12.06 cm. The template or the template was gassed for 30 seconds with triethylamine gas in an air carrier at an air supply pressure of 3.52 kp / cm. The triethylamine catalyst container was filled with nitrogen at a pressure of 5.62 kgf / cm. The triethylamine catalyst was injected into the carrier air stream at a rate of 10 cnr / min. After gassing, the cores were rinsed with the air carrier stream for 30 seconds. The die was used to assess mold adhesion or retention. The cores made according to the procedure of this example exhibited unsatisfactory mold removal. In order to achieve adequate mold release of the core, it was necessary that a mold release agent be sprayed on the aluminum die.

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Standard test specimens for tensile stress, 2.54 cm by blowing the mixture into a two-cavity die. 15 minutes after after gassing, the tensile strength was 16.5 kp / cm or 16.7 kp / ciTi "". The air and nitrogen pressures were the same as in the production of the truncated cones described above. The test specimens were gassed for 10 seconds and with air Rinsed for 10 seconds.

Example 15

Following the procedure of Example 14, a resin was prepared by adding 25 parts of the oxyalkylated novolac of Example 13, 35 parts of bisphenol-A, 20 parts of a solvent of the ethylbenzene type, commercially available under the trademark "SC-IOO" from Buffalo Solvents & Chemicals Co., and 20 parts of cellosolve acetate were mixed together. Following the procedure of Example 14, a Sand mixture prepared, including 3.18 kg of sea sand, 24 g of the resin solution of this example and 24 g of the organic polyisocyanate solution of Example 14 were used. The components were mixed over a period of 4 minutes. Then, as in Example 14, standard test specimens for tension, but using a blowing pressure of 4.92 kg / cm. The specimens were as in Example 14, gassed for 10 seconds and flushed with air for 10 seconds. The specimens were about 3 minutes produced after mixing is complete. They showed an aging of 15 minutes after gassing a tensile strength of 14.4 and 13.0 kgf / cm, respectively.

Example 16

A resin was prepared by mixing 60 parts of the oxyalkylated novolac of Example 13 with 25 parts of cello

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solveacetat and 15 parts of a solvent of the A'tliylb'eiizoltypß κ it dom trademark "SC-IOO" were mixed. The resin was molded into the standard specimens according to the procedure of Example 15. which 10 seconds gifted and purged with air for 10 seconds. Test specimens, which 6 minutes after the end of the process had a tensile strength of

° 2

7.42 kg / cm "or 8.23 kg / cm. A second set of tensile specimens was gassed for 30 seconds and flushed with air for 30 seconds. 12 minutes after mixing is complete

these bodies showed a tensile strength of 9.63 kgf / cm

2
and 8.93 kgf / cm, respectively.

Example 17

Following the procedure of Example 14, a sand mixture was prepared using a resin solution prepared by mixing 25 parts of the oxyalkylated novolac of Example 13, 35 parts of bisphenol-A, 25 parts of cellosolve acetate and 15 parts of an ethylbenzene-type solvent. urde. Following the procedure of example a sand mixture was prepared, to which _3} 18 kg of sea sand, 24 g of the resin solution of this example and 24 g of an organic polyisocyanate solution were used. the latter solution was prepared by mixing 65 parts of an organic ?! polyisocyanate with the Trademark "Mondur MR" were dissolved in 35 parts of a solvent of the ethylbenzene type with the trademark "SC-100." Following the procedure of Example 14, standard test specimens measuring 2.54 cm were produced, but with a blowing pressure of 7.03 kp / The tensile strength after 15 minutes of aging following the gassing was 10.7 kp / cm and 10.9 kp / cm '"feet set up.

BAD ORIGINAL 3098 1 8/0785

The procedure of Example 17 was repeated using the same ingredients, except that 6 1/4% of a polyethylene glycol ester of a fatty acid with the trademark "Kessco PEG 200 Monoleate" was added to the resin solution. The standard test specimens of 2; 54 cm produced and examined according to Example 17 had a tensile strength of 12.7 kp / cm ² , 13.9 kp / cia ² , 13.4 kp / cn ² and 14.1 kp / cm ² .

Example 19

Following the procedure of Example 17, but with a Addition of 6 i / 4? O methyl stearate to the resin solution the preparation of the sand mixture was also prepared as described in Example 17,

ρ ρ

which have a tensile strength of 14.9 kg / cm and 14.6 kg / cm had.

Example 20

The truncated cone described in Example 14 was used to produce samples of the binder sand masses of the Examples 17, 18 and 19 to deform. Using the above blends, all were made from them three cores found a scratch hardness of 80 to 90. The dispensing capacity was very good to excellent at the cores using the sand binders of Example 18. At the cores of the sand binding medium masses for example 19 it was good to very good and for the sand binder compositions of the example 17 moderate to good. The scratch resistance test was carried out according to the information in Foundry Sand Handbook, 7th Edition, American Foundry

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Society Publication Mr. 12, using a Dietert Test device No. 373 performed. A scratch hardness value of 75 is acceptable in the foundry industry.

21

The procedures described above made 5 / j butyl stearate and. alternatively 5 / ί tall oil to the resin solution of the Example, 17 given and examined according to Example 17. The results obtained show in the case of butyl stearate an improvement in the tensile strength of the molded specimens compared to the tensile strength of the roughest des Example 17. When tall oil is used, a reduction in tensile strength is obtained. The evaluation of butyl stearate and Tall oil additions, as described above, in the production of truncated cones shows that the tall oil is more effective at preventing sticking and sticking than butyl stearate. It also shows that both substances improved results in the manufacture of truncated cones bring as with additive-free truncated cones.

Example 22

Following the procedure of Example 14, a resin solution was prepared with 25 parts of the oxyalkylated novolac of Example 13 and 35 parts of bisphenol-A, 22.5 Parts of cellosolve acetate and 17.5 parts of a solvent of the ethylbenzene type with the trademarks "SC-100" became. To 100 parts of this resin solution were 3 parts of a polyethylene glycol ester of a fatty acid with the Trademark "PEG 200 Honooleate" given. there has been a Solution of an organic polyisocyanate prepared by adding 65 parts of an organic polyisocyanate with the trademark "Mondur MR" in 35 parts of a solvent

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of the ethylbenzene type with the trademark "SC-IOO" became. The technical evaluation in the foundry was carried out using a sand binder formulation of 100 parts of sand mixed with 34-0.2 each g of the liquid of the resin phenol compound solution described above and the organic polyisocyanate solution. The gassing cycle used in the foundry normally consists of a 30-second gassing with triethylamine gas and a 30 second. Rinsing with air if a binder sand mass according to the state of the art is used, which is a benzyl ether-like phenol aldehyde resin combination represents with an organic polyisocyanate. It was found that compared to the molds in which a sand binder composition according to the prior art had been used, a satisfactory one Tensile strength could be maintained by reducing the gassing time with triethylamine to 15 seconds and the purge time with air was limited to 15 seconds. A core weighing 4.54 kg was produced in the foundry, the described sand binding agent was used. The tensile strength measurement with the standard 2.54 cm specimens that were used in the foundry of the sand binder mass and an 8 second gassing cycle resulted in tensile strength of about 13.0 kp / cm and a scratch hardness, as described above, above 90 to 95.

Example 23

Following the procedure of Example 14, a resin solution was prepared using 25 parts of the oxyallrylated novolac of Example 13, 35 parts of bisphenol-A, 22.5 parts of Cellofjolve acetate and 17.5 parts of a solvent dos ÄthyD.benzoltyps with the trademark "SC-IOO"

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309818/0785. ■ bador, q, nal

det were. To 100 parts of this resin solution were added 5 parts of butyl stearate and 5 parts of tall oil. Like in the example 22 a solution of the organic polyisocyanate was prepared. To 100 parts of this solution became 5 parts Given butyl stearate. The technical evaluation in a foundry was carried out using a sand binder formulation ■ of " 100 parts of sand mixture each with 283.5 g of the above-described solution of the resin and the phenolic Compound and the solution of the organic polyisocyanate. The gassing cycle consisted of an 8 second Gassing with triethylamine gas and flushing with air for 8 seconds.

The results show with a test specimen with 2.54 era a tensile strength of about 11.7 kgf / cra and about 10.5 kg / cm

Example 24 - Comparative Example

With a commercially available benzyl ether-phenol-aldehyde-organic Polyisocyanate system, a comparative experiment was carried out according to the procedure of Example 23 by a sand binder formulation with 100 parts each mixed with 340.2 g of benzyl ether resin solution and solution of the organic polyisocyanate was used.

The tensile strength with specimens of 2.54 cm, which according to the procedure of example 23 had been prepared, betx'ug 11.0 kg / cm and 10.7 kg / cm.

Example 25

A resin was prepared by adding 90 parts of furfuryl alcohol and 4.5 parts of 37% formalin in the presence of sulfuric acid were heated to reflux. The reflux was

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3 0 9 8 18/0785 ^B * D ORIGINAL

maintained until the index of refraction of the resin ranged from 1.5340 to 1.5370. Sodium hydroxide was then added to neutralize the acid. The reaction mixture was dehydrated in vacuo until the Karl Fischer moisture content was 3.6%. It was determined that the resin had a density of 1.224, a Brookfield viscosity at 25 ⁰ C of 1700 eps and a refractive index of 1.5390.

Example 26

A portion of the resin of Example 25 was added to 100 parts of Wedron 7020 sand in a Koller mixer, and 2 Mixing minutes »Then a portion of a 75% reactive solids solution of polymethylene polyphenyl polyisocyanate was added to the Koller mixer in xylene was added as a solvent and mixed for a further two minutes. the The resulting deformable mass was deformed into rods with the dimensions 2.54 cm 2.54 cm 22.8 cm and cured, by bubbling trimethylamine gas through the sand mixture at different temperatures. Then were the flexural strength and the flexural modulus are determined. The results obtained are shown in Table III.

Table III

Curing conditions flexural strength flexural modulus

kp / cm

Room temperature 30th , 5 2, 99 X 1Q ⁵ 1 hour at 65.6 ° C.
■ examined at 65.6 C 24 , 2 1, 11 X 10 ⁵ 1 hour at 149 ⁰ C.
examined at 149 C 24 , 6 9, 39 X

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309818/0785

Example 27

80 parts of the resin of Example 25 were mixed with 13 parts of xylene, 5 parts of cellosolve acetate and 2 parts of ethanol R-650-X, an alkanolamine. The mixture had a density of 1.147, a Brookfield viscosity at 25 ⁰ C of 125 cps and a refractive index of 1.5240.

Example 28

Example 26 was repeated except that the resin of Example 25 and the resin of Example 27 were prepared became. The flexural strength and flexural modulus are summarized in Table IV.

Table IV Bending module Curing conditions kp / cm ² 1.38 10 ⁵ Room temperature 31.8 1.67 x 10 ⁵ 1 hour at 65.6 ° C.
examined at 65.6 C. 40.9 1.43 x 10 ⁵ 1 hour at 149 ° C _A
examined at 149 C 38.2 Example 29

A resin was prepared as in Example 25, except that corn starch (Sweetose 4300) was used in place of formalin. The resin had a Karl Fischer water content of 0.37, a Brookfield viscosity at 25 ⁰ C of 535 cps and a refractive index of 1.5331. The resin was mixed with sand and molded according to the procedure of Example 26. Then it became

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cured by bubbling triethylamine in nitrogen through the sand mixture for 10 seconds Purged with nitrogen for 10 seconds.

Example 3.0

The procedures of Examples 25 and 26 were repeated with the exception that 2 parts of ethylene glycol were added to the resin before mixing with the sand. It was treated with triethylamine in nitrogen gas for 10 seconds, followed by purging with nitrogen for 10 seconds. The tensile strength, determined 15 seconds after the gassing, was 7.03 kg / cm ² .

Example 31

The working methods of Examples 25 and 26 are repeated, using trimethylolpropane instead of formalin, triethylamine in nitrogen instead of trimethylamine and a gassing cycle of 10 seconds of gassing and 10 seconds of purging with nitrogen was applied became. After one minute the tensile strength was determined to be 7.03 kgf / cm.

Example 32

A resin was prepared by refluxing 100 parts of furfuryl alcohol, 41.5 parts of 37% formalin, 0.88 part of 10% oxalic acid aqueous solution, and 0.40 part of triethanolamine. The reaction mixture was then neutralized and dehydrated to a Karl Fischer water content of 1.4. The resin had a density of 1.261, a Brookfield viscosity at 25 ⁰ C of 53500 cps and a refractive index of 1.5518. The resin was with

^309818/0785

- suffered -

Sand mixed and shaped as in Example 26. The mixture was cured by passing trimethylinin gas through the deformed register for 10 seconds. Then became
Purged with nitrogen for 10 seconds. The rods formed therefrom developed a tensile strength of 2.25 kgf / cm "15 seconds after gassing.

Example 33

A portion of the resin of Example 25 was added to 100 parts of Wedron 7020 sand in a Koller mixer and 2
Minutes mixed with it. A portion of a 75% solution of toluene diisocyanate in xylene was then added to the Koller mixer and mixing was continued for an additional 2 minutes. The resulting deformable mass was formed into rods measuring 2.54 cm by 2.54 cm by 22.86 cm and cured by passing triraethylamine gas through the sand mixture.

Example 34

80 parts of the resin from Example 25 were mixed with 13 parts of xylene, 5 parts of carbitol acetate and 2 parts of Thanol R-650-X, an alkanolamine. That had mixed resin
a density of 1.138, a Brookfield viscosity at 25 ⁰ C of 148 cps and a refractive index of 1.5250.

Examples 35 to 38

Following the procedure of Example 25, foundry aggregate binders were made produced using the following furan alcohols instead of furfuryl alcohol.

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Example furan alcohol

35 '2 ~ (2 ~ furyl) ethyl alcohol

36 3- (2 ~ furyl) propyl alcohol

37 methyl furfuryl alcohol

38 chlorofurfuryl alcohol

Example 39

30 parts of the resin of Example 25 was added to 30 parts of bisphenol-A, 20 parts of xylene, 15 parts of cellosolve acetate and 5 parts of furfuryl alcohol. The mixture was stirred, Ms both the bisphenol-A and the resin des Example 25 had been resolved. Then 3/4 parts of this solution to 100 parts of sea sand (AFS-45) in one Added Koller mixer and mixed with it for 2 minutes. Then became 3/4 parts of the polymethylene polyphenyl polyisocyanate of Example 26 was added to the Koller mixer and mixed for a further 2 minutes. The resulting deformable The mass was tamped into a tensile strength die with a width of 2.54 cm and triethylamine was passed through (Τ.Ε, Α.) Hardened by the sand mixture at room temperature, then flushed with nitrogen. After a The tensile strength was determined by aging the molding compositions for 15 minutes and 60 minutes. The results obtained are compiled in Table V.

Table V

Cure time tensile strength, kp / cm

(Seconds at room temperature). '- TE, A, -Gas nitrogen purge after 15 min, after 60 min,

5 5 11.6 13.2

10 10 12.5 13.9

15 10 12.9. 12.7

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BATH ORIGINAL

Example 40

A binder component solution was prepared, including 20 parts of the resin of Example 25, 40 parts of bisphenol-A, 15 parts of xylene, 15 parts of cellosolve acetate, 5 parts of acetone and 5 parts of furfuryl alcohol were used. The components were mixed thoroughly to ensure complete dissolution. After that, 3/4 parts of this were made Add binder solution to 100 parts of sea sand (AFS-45) in a Koller mixer and mix for 2 minutes. Then 3/4 parts of polymethylene polyphenylpolyisoeyanat des Example 26 was added to the Koller mixer and mixed for more than 2 minutes. The resulting deformable The mass was tamped into a 2.54 cm tensile strength matrix and hardened by passing various through the sand mixture Times triethylamine gas was passed. This was done at room temperature. The tensile strength was then determined on the samples that were allowed to age for 15 and 60 minutes after curing and purging with nitrogen became. The results obtained are shown in Table VI.

Table VI

Cure time tensile strength, kp / cia

(Seconds at room temperature)

T.E.A. gas nitrogen purge After 15 min. After 60 min.

11.2 12.0 13.9 15.6 13.9 12.7

5 5 10 10 15th 15th Example 41

A binder component solution was prepared by adding 60 parts of bisphenol-A to 20 parts of cellosolve acetate

309818/0785

-47- ORIGINAL BATHROOM

and 20 parts of acetone were added. The components were mixed thoroughly to ensure dissolution of the bisphenol-A to ensure. 3/4 parts of this bisphenol-A solution were then added to 100 parts of sea sand (AFS-45) and mixed in a Koller mixer for 2 minutes. 3/4 parts of the polymethylene polyphenyl polyisocyanate were then added of Example 26 was added to the Koller mixer and mixed for a further 2 minutes. The resulting deformable box was pulped into a 2.54 cm tensile die and cured by blowing triethylamine gas through it the sand mixture was passed for various times. Then the same period of time became nitrogen passed through the sand mixture. All curing was done at room temperature. Thereupon the tensile strength certainly. The results obtained are shown in Table VII.

Table VII

I-Curing Time Tensile Strength, kp / cm

(Seconds at room temperature)

T.E.A. gas nitrogen purge After 15 min. After 60 Hin.

4.6 7.38

: 7.4 13.0

5 5 10 10 Example 42

The procedure of Example 41 was repeated "except that the ratio of bisphenol A solution was to 3/4 part of the polyethylene polyphenyl polyisocyanate solution of Example 26 and 0.6 part of the bisphenol A solution in combination with 0.9 parts of polymethylene polyphenyj.polyisocyanate of Example 26 was varied. The results obtained are shown in Table VIII.

309818/0785 'bad

Table VIII

Curing time

(Seconds at room temperature)

T.E.A. gas nitrogen purge

Tensile strength, kp / cra

After 15 min. After 60 min.

5
10

5 10

10.4 8.44

11.1 11.0

Example 43 (comparison experiment)

Following the procedure of Example 40, a foundry sand mix was made prepared by adding 20 parts of the phenol resin resin A according to column 8 of US Pat. No. 3,409,579, 20 Parts of butyl acetate and 20 parts of polymethylene polyphenyl polyisocyanate of Example 26 with 2000 parts of sea sand in were mixed in a Koller mixer. The mingling was Continued for 2 minutes until the binder had spread evenly over the sand particles. The resulting Deformable mass was tamped into a tensile strength die with 2.54 cm and cured by adding triethylamine gas was passed through the sand mixture at different times. The tensile strength is then determined. The results obtained are shown in Table IX.

Table IX

Curing time

(Seconds at room temperature)

T.E.A. gas nitrogen purge

■ j

Tensile strength, kp / cm After 15 min. After 60 min,

10
15th

10 10

16.7 16.3 17.4

19.0 18.6

309818/0785

-49-BATH ORIGINAL

Claims (3)

Pat e π ta η s ρ r μ c h. e 1. Mass for foundry purposes, thereby g e k eη η drawing η e t that they (1) an organic polyisocyanate and (2) -oine essentially anhydrous, in organic Solvent soluble component that has the following formula: R ₁ has, or a condensation product of an aldehyde and a furan alcohol with the general formula? -O R ₁ , CH ₂ (CH ₂ ) _v OH represents where η has a mean value of 'about "0.2 to 6, x, y and ζ are integers from 1 to 25, ν is from Ö to 4, R _- J independently denotes hydrogen, fluorine, chlorine, bromine and / or a hydrocarbon radical, 1 * 2 and R * independently hydrogen, a hydrocarbon radical or / and mean a halogen-substituted hydrocarbon radical and Ra stands for a hydrocarbon radical, and 309 818/0785 -50-BATH ORIGINAL (3) a phenolic compound of the general formula: ^R 5 R ₆ VM wherein X is oxygen or sulfur, y is an alkylidene radical, an arylbisalkylene radical, an arylene radical, -S-, -SS-, or / and -b-, η is 0 or 1 and where R ^ and R _{2 are} hydrogen, alkyl radicals with 1 to 6 carbon atoms and / or halogen, contains. 2. Composition according to claim 1, characterized in that it is in solution in an inert solvent is present. 3. Composition according to claim 1 or 2, characterized in that the substituents R * _t R «and R, are hydrogen. 4. Composition according to one of the preceding claims, characterized in that the organic polyisocyanate is a polyaryl polyisocyanate. 5. Composition according to claim 2, characterized in that the solvent is ethylbenzene. 6. Binding agent for foundry units or foundries * irritant additives, by which I mark η et, that they use the Ilasse according to claim 1 and tall oil, polyethylene glycol ester of fatty acids and / or low alcohol esters of fatty acids. ORiGlMAL BATHROOM -51- 3098 18 / afäS 7. Foundry aggregate mass or foundry aggregate mass, characterized in that it is a foundry aggregate or foundry aggregate and the Comprises composition according to claim 2, the latter in amounts of about 0.8 to about 10 wt .- ^, based on the weight of the foundry aggregates or the foundry additives. 8. mass, characterized in that 'that it contains the composition of claim 7 which has been cured with a tertiary amine. 9. Composition, characterized in that it is (1) an organic polyisocyanate, (2) an inert one Contains solvents and (3) tall oil and / or lower alcohol esters of fatty acids as a further component. 10. mass for foundry purposes, characterized in that it (1) is a substantially anhydrous, Component of the general formula that is soluble in organic solvents: η has a mean value: from about 0.2 to 6, x, y and ζ are integers from 1 to 25, R ^ independently hydrogen, fluorine, chlorine, bromine or / and means a hydrocarbon radical, 309818/078 6. -52- BATH ORIGINAL Ro and Pw independently hydrogen, a hydrocarbon mean radical or a halogen-substituted carbon radical and R. stands for a hydrocarbon radical, (2) a phenolic compound of the formula: where X is oxygen or sulfur, y is an alkylidene radical, an aryl bisalkylene radical, an arylene radical, -S-, -S-S-, and / or -S-, η is 0 or 1 and Re and Rg Hydrogen, alkyl having 1 to 6 carbon atoms and / or Mean halogen, and (3) contains an inert solvent. 11. Composition according to claim 10, characterized in that the phenolic compound is a bisphenol is. 12. Composition according to claim 10, characterized in that the mass additionally tall oil, polyethyleneglycol ester of fatty acids and / or lower alcohol esters of fatty acids as a further component. 13. Composition according to claim 10, characterized in that the solvent ethylbenzene and / or cellosolve acetate. 14. Binder mass for foundry units or foundry additives, dthrough g e k e η η ζ e 1 c h η e t, 309818/0785 BATH ORIGINAL that it contains the composition according to claim 1, wherein the PoIyisocyanat is present in an amount that will be provided to 1.1 reactive isocyanate groups per reactive hydrogen present available about 0.9 in the components (2} and. _{(3).> If} 15. Wet foundry aggregate or foundry aggregate mass. characterized in that they a foundry aggregate or foundry aggregate, the mass according to claim 1 and tall oil low alcohol ester of Contains fatty acids and / or polyethylene glycol esters of fatty acids as a further component, the mass based on on the weight of the foundry aggregate or the foundry aggregates, in amounts of about 0.8 to about 10 wt .-? o is available. 16. Composition according to claim 15, characterized in that the mass with a tertiary amine has been hardened. 1?. Process for connecting individual inert solid particles, characterized , that one (1) the particles with a solution of a binder coated in an organic solvent; ,, c & e (A) an organic polyisocyanate (B) an essentially anhydrous »in organic Dissolvable components with 4 © · ^ general Forsieii. ., ■ BAD ORi§f; worm η has a mean value of about 0.2 to 6, x, y and ζ are integers from 1 to 25, I-L · independent! / Hydrogen, fluorine, chlorine, bromine or / and means a hydrocarbon radical, Rp and R _{7 are} independently hydrogen, a hydrocarbon radical or a halogen-substituted hydrocarbon radical and R. stands for a hydrocarbon radical, and (C) a phenolic compound of the formula: HX ^ / ^ N- ~ (y) _n ^ 0V-XH where X is oxygen or sulfur, y is an alkylidene radical, an aryl bisalkylene radical, an arylene radicalsl, -S-, -S-S-, or / and -S-, η 0 or 1 and R, - and Rg hydrogen, alkyl rait 1 to 6 carbon atoms and / or halogen contains and that one (2) hardens the Maese obtained. 18. The method according to claim 17, characterized in that the binder further contains tall oil, lower alkyl esters of fatty acids and / or polyethylene glycol esters of fatty acids as mold release agents, the mass in amounts of about 0.8 to about 10 wt the weight of the foundry aggregate or the foundry to.nch] 8gnt.offe is available. -55- BAD OR (GiNAL 309 8 18/0785 19. The method according to claim 18, characterized in that the mass is passed through a "tertiary amine hardens. 20. The method according to claim 17, characterized in that g e k e n.n - draws' that one enters as a phenolic compound Bisphenol used. 21. The method according to claim 20, characterized in that there is a phenolic compound Bisphenol-A used and that the mass is cured by a tertiary amine is passed through. 22. Method.nach claim 21, characterized in that the organic Pblyisocyanat a polyaryl polyisocyanate is used and that a solvent consisting of a mixture of ethylbenzene and cellosolve acetate is used used. 25. The method according to claim 21, characterized in that ge k e η η that triethylamine is used as the tertiary amine. 24. Composition for foundry purposes, characterized in that it (1) · an organic polyisocyanate and (2) a substantially anhydrous, organic solvent soluble condensation product an aldehyde and a furan alcohol of the general Formula: -56- '„· ■; - · -.- BAD ORIGINAL 3 09818/0765 where ν is 0 "to 4 and R ,, individually hydrogen, alkyl or / and means halogen. 25. Composition according to claim 24, characterized in that it contains an inert solvent. 26. Hasse according to claim 25, characterized in that geke η η draws _; that the furan alcohol is furfuryl alcohol and the aldehyde is formaldehyde. 27. Composition according to claim 25, characterized in that the organic polyisocyanate is a Is polyaryl polyisocyanate. 28. Composition according to claim 25, characterized in that the solvent is xylene. 29. Binder mass for foundry units or foundry additives, characterized in that it contains the composition of claim 24, the aldehyde Has 1 to 8 carbon atoms, and in an amount from about 0.01 to about 50 weight percent based on weight of the condensation product. 30. Foundry aggregate mass or foundry aggregate mass, characterized in that they have a foundry aggregate or foundry additives and the The composition of claim 25, wherein the composition is used in amounts of from about 1 to about 10 wt .- ^ based on the weight of the Foundry aggregate or the foundry additives, is available. 31. Composition according to claim 30, characterized in that the composition with a tertiary amine has been hardened. -57- 309818/0785 BATH ORIGINAL 32. Composition for foundry purposes, characterized in that it (1) is an organic polyisocyanate and (2) a phenolic compound of the general formula: \ _y where X is oxygen or sulfur, y is an alkylidene radical, an aryl bisalkylene radical, an arylene radical, -S-, -S-S-, or / and -S-, η is 0 or 1, and FU and Rg hydrogen, alkyl with 1 to 6 carbon atoms or / and mean halogen. 33 · Composition according to claim 32, characterized in that it contains an inert solvent. 34. Composition according to claim 33, characterized in that. the phenolic compound is a bisphenol and the organic polyisocyanate is a polyaryl polyisocyanate. 35. Composition according to claim 33, characterized in that the solvent is a ketone. 36.Binder mass for foundry aggregates or foundry additives, characterized in that it contains the composition of claim 32, wherein the polyisocyanate is present in such amounts that about 0.9 to 1.1 reactive isocyanate groups per reactive present -. ven hydrogen can be provided in the phenolic compound. -58- BAD ORIGINAL 309818/0785 ~~ ^ 37. Foundry aggregate mass or ' Foundry aggregate mass, characterized in that they have a foundry aggregate or foundry additives and the The composition of claim 33, wherein the composition is in amounts of from about 1 to about 10 weight percent based on weight of the foundry aggregate or the foundry aggregates is available. 38. mass, characterized in that it contains the mass according to claim 13, which with a tertiary amine is cured. 39. Composition for foundry purposes, characterized in that it (1) is an organic polyisocyanate nat and (2) a Geraisch of (A) an essentially water-free, The condensation product of an aldehyde and a furan alcohol which is soluble in organic solvents general formula: XJH CH ₂ (CH ₂ ) _v OH v / orin ν is 0 to 4 and FL is individually hydrogen, alkyl or / and denotes halogen, and (B) a phenolic compound the formula: where X is oxygen or sulfur, y is an alkylidene radical, an aryl bisalkylene radical, an arylene radical, 0
-S-, -SS- or / and -S-, η is 0 or 1 and R _r and -59-BATH ORIGINAL 309818/0785 _ 59 - Rg hydrogen, alkyl with 1 to 6 carbon atoms or / and mean halogen. 40. Composition according to claim 39, characterized in that g e k e η η, that it throws a solution in an inert solvent. 41. Composition according to claim 40, characterized in that the phenolic compound is a bisphenol and that the organic polyisocyanate is a polyaryl polyisocyanate is. 42. mass nach'Anspruch 41, characterized in that the solvent is a mixture of a ketone and an aromatic solvent. 43. Binder mass for foundry units or »foundry additives, characterized , that it contains the composition of claim 16, wherein the polyisocyanate is contained in an amount that in the mixtures (A) and (B) about 0.9 to 1.1 reactive isocyanate groups can be made available for each reactive hydrogen present. 44. Foundry aggregate mass or foundry aggregate mass, characterized in that it contains a foundry aggregate or foundry aggregate and the binder mass according to claim 40, the binder in amounts of about 1 to about 10 wt. % _T based on the weight of the foundry aggregate or the foundry aggregates, is available. 45. ' Composition according to Claim 44, characterized in that it is hardened with a tertiary amine is. -60- 3 0 9 8 18/0785 BAD - 60 - 7251888 46. Process for connecting individual inert solid particles, characterized , that (1) the particles are coated with a solution of a binder in an organic solvent ", wherein the binder (A) an organic polyisocyanate and an essentially anhydrous, · soluble in organic solvents condensation product of an aldehyde and of a furan alcohol of the formula: where ν is 0 to 4 and where R ^ is individually hydrogen, Is alkyl or / and halogen, and a solvent is or (B) an organic polyisocyanate and a phenolic compound of the formula: where X is oxygen or sulfur, y is an alkylidene radical, an aryl bisalkylene radical, an arylene radical, -S-, -S-S-, or / and -S-, η 0 or 1 and R, - and Rg are hydrogen, alkyl with 1 to 6 carbon atoms and / or halogen are -61- BAO OR (QINAL 309 8 1 S / 0 78 B is, or (G) 'a mixture of (A) and. (B) is ■ and that (2) the mass obtained is hardened. 47. The method according to claim 46, characterized in that the furan alcohol is furfuryl alcohol
and the aldehyde is formaldehyde. 48. The method according to claim 47, characterized in that the mass is passed through
of a tertiary amine hardens. _: 49. The method according to claim 48, characterized in that the organic polyisocyanate is a
Polyaryl polyisocyanate and the solvent is xylene » 50. The method according to claim 46, characterized in that the phenolic compound is a
Is bisphenol. 51. The method according to claim 50, characterized in that the phenolic compound is bisphenol and that the mass is cured by passing a tertiary amine through it. . 52. -, The method according to claim 51, characterized geke η η ζ eich η et that that organic polyisocyanate
Polyaryl polyisocyanate and that the solvent. Mixture of xylene and gel dissolving acetate is. - 53. The method of claim 51, characterized 'g e k e η η - characterized in that the tertiary amine is triethylamine. 3 0 9 § I $ P % 8 § : ■ '; ■}: - ORIGINAL IHSPECIBD