Calcia catalyzed resins

Claim 3

A method as in claim 1 for making infinitely dilutable substantially phenol free aqueous solutions of thermosettable phenol formaldehyde resins, by selectively catalyzing and controlling the methylolation of phenol with formaldehyde to increase resinification, minimize the content of monomethylol phenols and higher phenyls and maximize the content of .[.o-p-dimethylol phenols.]. .Iadd.2,4,6-trimethylol phenols.Iaddend., thus producing a resin solution component for binder formulations having low air and wash water polluting characteristics when applied to a substrate, comprising the steps of: a. mixing U.S.P. phenol, in the absence of other monomers, with aqueous formaldehyde in an amount of 3.5 to 4.4 mols of formaldehyde per mol of phenol, and correspondingly from 6 to 10 moles of water per mol of the reactants, at a temperature not exceeding about 85° F., and, b. introducing calcium oxide or calcium hydroxide catalyst with cooling up to or near its solubility limit in the aqueous mixture present, catalyst in an amount of 4.9 to 7 percent as calcium (Ca) based upon the weight of phenol, 0.11 mol to 0.16 mol calcium (Ca) per mol of phenol), c. controlling the exothermic rise in temperature of the reactants without heat input so as to increase to not more than about 125° F. during at least the first hour of reaction, d. continuing the methylolation reaction without heat input at a suitable temperature up to 155° F., and e. terminating said reaction by cooling when the condensation reaction product is substantially phenol free, is still water soluble, and contains between 3 to 16% unreacted formaldehyde.

Claim 4

A continuous method as in claim 1 for making infinitely dilutable substantially phenol free aqueous solutions of thermosettable phenol formaldehyde resins, by selectively catalyzing and controlling the methylolation of phenol with formaldehyde to increase resinification, minimize the content of monomethylol phenols and higher phenyls and maximize the content of .[.o-p-dimethylol phenols.]. .Iadd.2,4,6-trimethylol phenols.Iaddend., thus producing a resin solution component for binder formulations having low air and wash water polluting characteristics when applied to a substrate, comprising the steps of: a. continuously mixing U.S.P. phenol, in the absence of other monomers, with aqueous formaldehyde in an amount of 3.5 to 4.4 moles of formaldehyde per mol of phenol, and correspondingly from 6 to 10 moles of water per mol of the reactants, continuously introducing calcium oxide or calcium hydroxide catalyst with cooling up to or near its solubility limit in the aqueous mixture present, in an amount of 4.9 to 7 percent as calcium (Ca) based upon the weight of phenol, (0.11 mol to 0.16 mol calcium (Ca) per mol of phenol, while maintaining a temperature of not exceeding about 85° F., b. controlling the exothermic rise in temperature of the reactants without heat input so as to increase to not more than about 125° F. during at least the first hour of reaction, c. continuing the methylolation reaction without heat input at a suitable temperature up 155° F., and d. terminating said reaction by cooling when the condensation reaction product is substantially phenol free, is still water soluble, and contains between 3 to 16% unreacted formaldehyde.

Claim 5

A method as in claim 1 wherein the formaldehyde is introduced in an amount of 3.5 to 4 mols per mol of phenol and the calcium oxide in an amount of from 0.11 mol to 0.14 mol calcium per mol of phenol.

Claim 6

A method as in claim 1, wherein the formaldehyde is introduced in an amount of 3.6 to 3.8 mols per mol of phenol, and the calcium oxide or hydroxide in an amount of from 0.12 mol to 0.13 mol calcium per mol of phenol.

Claim 7

A method as in claim 1 wherein the reaction is carried out under subatmospheric pressure, and a reflux condenser is employed to maintain the reagent concentrations.

Claim 8

A method as in claim 1 further comprising the step of bringing the reaction product to a pH of 7 to 7.6 by addition of an acid.

Claim 9

A method as in claim 7 wherein the acid is chosen from sulfamic, phosphoric, sulfuric, acetic, maleic and carbonic acids, and their ammonium salts.

Claim 10

An aqueous solution of a thermosettable phenol formaldehyde condensation resin made according to the method of claim 1.

Claim 11

An aqueous solution of a thermosettable phenol formaldehyde condensation resin made according to the method of claim 7.

Claim 12

In aqueous thermosettable compositions suitable for bonding, comprising a mixture of aminoplast resins of nonphenolic monomeric materials capable of co-condensing with formaldehyde, a phenol formaldehyde resin, ammonia or a water soluble amine, an acidic curing catalyst, and water, the improvements comprising: the phenol formaldehyde resin is present in the form of an aqueous solution of a thermosettable phenol formaldehyde condensation resin made according to the method of claim 1, the pH of the composition is in the range of about 7 to 9, the acidic catalyst is present in an amount of 0.1 to 2 percent by weight based on the weight of the resin components, and the water is present to a solids content in the range of 1-80 percent by weight.

Claim 13

In aqueous thermosettable compositions suitable for bonding, comprising a mixture of aminoplast resins or nonphenolic monomeric materials capable of co-condensing with formaldehyde, a phenol formaldehyde resin, ammonia or a water soluble amine, an acidic curing catalyst, and water, the improvements comprising: the phenol formaldehyde resin is present in the form of an aqueous solution of a thermosettable phenol formaldehyde condensation resin made according to the method of claim 6, the pH of the composition is in the range of about 7 to 9, the acidic catalyst is present in an amount of 0.1 to 2 percent by weight based on the weight of the resin components, and the water is present to a solids content of 1-80 percent by weight.

Claim 14

An aqueous bonding composition as in claim 11 where the aminoplast resins are chosen from the group consisting of melamine formaldehyde, urea formaldehyde or alkylated amine formaldehyde copolymer resins, and the co-condensable monomers are chosen from the group consisting of urea, dicyandiamide, melamine, methanol and glycols.

Claim 15

A binder composition as in claim 11 wherein the acidic curing catalyst is an ammonium salt of an acid selected from the group consisting of sulfuric acid, phosphoric acid, sulfamic acid, acetic acid, maleic acid and carbonic acid.

Claim 16

A binder composition as in claim 11 having a pH in the range of 8.3 to 8.6.

Claim 17

A binder composition as in claim 11 wherein the solids content is 2 to 30 percent by weight.

Claim 18

A binder as in claim 11 further comprising one or more binder components chosen from the group consisting of coupling agents, emulsified mineral oil, ammonium ligno sulfonate, tall oil, finely divided mineral fillers, animal glue and dyes.

Claim 19

A binder as in claim 11 wherein the water soluble amine is chosen from the group consisting of benzylamine, diethylamine, diethanolamine, dimethylamine, ethylamine, methylamine, trimethyl-amine, monoethanolamine, triethanolamine.

Claim 20

A binder composition as in claim 13 wherein 50 percent by weight of urea solids are admixed or co-condensed with 50 percent by weight of the phenol formaldehyde resin solids resulting from the selective catalyzation by calcium oxide or hydroxide of 3,5 to 4.0 mols of formaldehyde with mol phenol.

Claim 21

A binder composition as in claim 13 wherein 46 percent by weight of urea solids are admixed or condensed with 54 percent by weight of phenol formaldehyde resin solids resulting from the selective catalyzation by calcium oxide or hydroxide of 3.5 to 3.7 moles of formaldehyde with 1 mole phenol.

Claim 22

A binder composition as in claim 13 wherein 35 percent by weight of urea solids are admixed or co-condensed with 25 percent by weight of an alkylated amine copolymer resin solids and with 40 percent by weight of phenol formaldehyde resin solids resulting from the selective catalyzation by calcium or hydroxide of 3.5 to 3.8 mols of formaldehyde with 1 mol phenol.

Claim 23

A binder composition as in claim 13 wherein 5 percent by weight of urea solids are admixed and/or co-condensed with 70 weight percent of alkylated amine copolymer resin solids and with 25 percent by weight of phenol formaldehyde resin solids resulting from the selective catalyzation by calcium oxide or hydroxide of from 3.5 to 3.8 moles of formaldehyde to 1 mol of phenol.