IE48542B1 - Polymeric isocyanate binder with internal release agent - Google Patents

Abstract

The use of polyisocyanates as binders in the preparation of particle boards is subject to the drawback that the boards exhibit a tendency to adhere to the face of the platens used in their formation. This problem is minimized by incorporating minor amounts of a mixture of certain mono- and di- (saturated or unsaturated aliphatic) acid phosphates or the corresponding pyrophosphates, into the polyisocyanate to be used as binder. The polyisocyanates and the acid phosphates and or pyrophosphates, are applied to the particles separately, or after preblending one with the other. Whether the components are applied separately or in combination one with the other, they can each be applied either neat or in the form of an emulsion or emulsions.

Description

This invention relates to particle board binders and or more particularly concerned with the use of organic polyisocyanates as particle board binders, with compositions for said use, with the particle boards so prepared.

The use is now widely recognized of organic polyisocyanates, particularly toluene diisocyanate, methylenebis(phenyl isocyanate), and polymethylene polyphenyl polyisocyanates, as binders, or as a component or a binder, for the preparation of particle boards; see for example, U.S. Patents 3,428,592; 3,440,189; 3,557,263; 3,636,199; 3,870,665; 3,919,017 and 3,930,110.

In a typical process the binder resins, optionally in the form of a solution or aqueous suspension or emulsion, are applied to or admixed with the particles or cellulosic material, or other types of material capable of forming particle boards, using a tumbler apparatus or blender or other form of agitator. The mixture of particles and binder is then formed into a mat and subjected to heat and pressure using heated platens. The process can be carried out in a batch operation or continuously. To avoid adhesion of the board so formed to the heated platens it has hitherto been necessary to interpose a sheet, impermeable to isocyanate, between the surface of the board and the platen during the forming process, or to coat the surface of the platen, prior to each molding operation, - 3 with an appropriate release agent or to coat the surface of the particles themselves with a material which will not adhere to the platen. Any of these alternatives, particularly where the process is being operated on a continuous basis, is cumbersome and a drawback to what is otherwise a very satisfactory method of making a particle board with highly attractive structural strength properties.

We have now found that the above drawbacks to the use of organic isocyanates as particle board binders can be minimized in a very satisfactory manner by incorporating certain phosphorus-containing compounds as internal release agents in the isocyanate compositions so utilized. We are aware of U.S. Patent 4,024,088 which describes the incorporation of phosphorus-containing compounds as internal release agents in the preparation of polyether polyurethanes, We have found that the phosphorus compounds disclosed in this reference are not suitable for use in the process of the present invention.

This invention comprises an improved process for the preparation of particle board in which particles of organic material capable of being compacted are contacted with a polyisocyanate and the treated particles are subsequently formed into boards by the application of heat and pressure, which process comprises contacting said particles, in addition to the treatment with polyisocyanate, with from 0.1 to 20 parts, per 100 parts by weight of polyisocyanate, of a phosphate selected from: (aj acid phosphates of the formulae o ί t p.o.—P--OH and (RO) - P-Oh I OH (II) (I) and the ammonium, alkali metal and alkaline earth metal salts thereof; (b) pyrophosphates derived from the acid phosphates (I) and (II) and mixtures of (I) and (II) as herein defined; (c) The O-monoacyl derivatives of the acid phosphates (I) and (II) having the formulae 0 t t ro— P — OCOR^ and (RO) 2P-OCOR^^; OH (V) (VI) (d) carbamoyl phosphates having the formula R2NHCO-0-P (OR) (VII) and the ammonium, alkali metal and alkaline earth metal salts of the compounds of formula (VII); (e) branched polyphosphates of the formulae ϊ ί RO— P-0 — P (OR). 0—— P (OR) „ i 2 (vnr) and - 5 0 0 0 ΐ ί ΐ (R0)q Ρ—0—.Ρ—0 — Ρ (OR) 2 Ο ί ο-Ρ (OR) 2 (IX) (f) polyphosphates corresponding to the general formula f .

(RC'P — 0 j Xi (X) including the cyclometaphosphates (n = J) ; and (gi mixtures of two or more of said compounds; wherein, in the various formulae shown above, each R is independently alkyl having up to 35 carbon atoms, inclusive, alkenyl having up to 35 carbon atoms, inclusive or a group of general formula: (0 —CH-CH-CH I I wherein R* is alkyl having up to 35 carbon atoms, inclusive, one of A and B represents hydrogen and the other is hydrogen or methyl, and n .is a number having an average value from 1 to 5; R^ is hydrocarbyl having up to 12 carbon atoms, inclusive; R, is a hydrocarbyl group having up to 12 carbon atoms or a hydrocarbyl group substituted by at least one additional Ο _ NHCOO.—Ρ (OR) 2 group wherein R has the significance defined above; and n is an integer.

In one preferred embodiment, the phosphate is a mixture of oleyl diacid phosphate and dioleyl monoacid phosphate.

The invention also provides in another aspect a storage stable composition suitable for use as a binder in the manufacture of particle board comprising a mixture of (a) a polymethylene polyphenyl polyisocyanate containing from 25 to 90 percent by weight of methylenebis (phenyl isocyanate) the remainder of said mixture being oligomeric polymethylene polyphenyl polyisocyanates having a functionality higher than 2.0; and (b) from 0.1 parts by weight to 20 parts by weight, per 100 parts by weight of said polyisocyanate, of a pyrophosphate derived by removal of water of condensation from at least one acid phosphate having one of the formulae: 0 I wherein each R is independently alkyl having up to 35 carbon atoms, inclusive, alkenyl having up to 35 carbon atoms, inclusive or a group of general formula: R'- (0 —CH—CH ΙΑ B - 7 wherein R' is alkyl having up to 35 carbon atoms, inclusive, one of A and B represents hydrogen and the other is hydrogen or methyl, and n is a number having an average value from 1 to 5, and mixtures of two or more of said acid phosphates.

The term alkyl having up to 35 carbon atoms means a saturated monovalent aliphatic radical, straight chain or branched chain, which has the stated number of carbon atoms in the molecules. Illustrative of such groups are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl, heneicosyl, docosyl, tricosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and pentatriacontyl, including isomeric forms thereof.

The term alkenyl having up to 35 carbon atoms means a monovalent straight or branched chain aliphatic radical containing at least one double bond, and having the stated number of carbon atoms in the molecule. Illustrative of such groups are octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, pentacosenyl, triacontenyl and pentatriacontenyl, including isomeric forms thereof.

The term pyrophosphates----derived from the acid phosphates (I) and (II) and mixtures of (I) and (II) has the following meaning. The acid phosphates (I) and (II) are generally prepared in the form of mixtures of the monoacid phosphate (II) and the diacid phosphate (I) which mixtures are produced by reaction of the corresponding alcohol ROH, wherein R is as above defined, with phosphorus pentoxide in accordance with procedures well-known in the art for the preparation of acid phosphates; see, for example, Kosolapoff, Organophosphorus Compounds, pp 220221, John Wiley and Sons, Inc., New York, 1950. The mixture - 8 of the mono- and di-acid phosphates so obtained can be separated, if desired, for example by fractional crystallization of the barium and like salts as described in the above cited reference. The individual acid phosphates or mixtures of the two can be used in the process of the invention. The pyrophosphates (III) and (IV) are readily obtained from the corresponding acid phosphates (II) and (I) respectively, by reaction of the latter with a dehydrating agent such as carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates and Ν,Ν'-dihydrocarbylcarbodiimides, in accordance with procedures well-known in the art; see, for example, F. Cramer and M. Winter, Chem. Ber. 94, 989 (1961); ibid 92, 2761 (1959); M. Smith, J.G. Moffat and H.G. Khorana, J. Amer. Chem. Soc. 80, 6204 (1958); F. Ramirez, J.F. Marecek and I. Ugi, JACS 97, 3809 (1975). The individual acid phosphates (I) and (II) can be separately converted to the corresponding pyrophosphates or mixtures of the two types of acid phosphate (I) and (II) can be converted to the corresponding mixture of pyrophosphates .

In the case of the acid phosphates having the formula (II) above the corresponding pyrophosphates are those represented by the formula:0 0 (R0)2P—0—P (OR) 2 (III) wherein R has the meaning hereinbefore defined. In the case of the acid phosphates having the formula (I) above the corresponding pyrophosphates are a complex mixture whose average composition is represented by the formula:- 9 - OR (IV) wherein x is a number having an average value of 1 or higher and R has the meaning hereinbefore defined.

The term hydrocarbyl having up to 12 carbon atoms, inclusive means the monovalent radical obtained by removing one hydrogen atom from the parent hydrocarbon having the stated carbon atom content. Illustrative of such groups are alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl including isomeric forms thereof; alkenyl such as vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, decenyl and dodecenyl including isomeric forms thereof; aralkyl such as benzyl, phenylpropyl, phenethyl and naphthylmethyl, aryl such as phenyl, tolyl, xylyl, naphthyl and biphenylyl; eycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, including isomeric forms thereof; and cycloalkenyl such as cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctenyl including isomeric forms thereof.

The term alkali metal has its well recognized meaning as being inclusive of lithium, sodium, potassium, rubidium and caesium. The term alkaline earth metal also has its well recognized meaning as being inclusive of calcium, strontium, magnesium and barium.

The process of the invention may be carried out substantially in accordance with methods previously described in the art in which an organic polyisocyanate is used as the binder resin, or a component thereof, (see, for example, German Offenlegungsschrift 2610552 and U.S. 3,428,592) with the chief exception that a phosphate as hereinbefore defined is employed in combination with the isocyan- 10 ate composition which is used to treat the particles which are to be bonded together to form the particle board.

Thus, particle board may be produced according to the invention by bonding together particles of wood or other cellulosic or organic material capable of being compacted using heat and pressure in the presence of a binder system which comprises a combination of an organic polyisocycnate and a phosphate as hereinbefore defined, hereinafter referred to as the phosphate release agent.

The polyisocyanate and the phosphate release agent can be brought into contact with the particles as separate, individual components or, in a preferred embodiment, the polyisocyanate and phosphate are brought into contact with the particles either simultaneously or after admixture.

Whether the polyisocyanate and phosphate are introduced separately or in admixture, they can be employed neat, i.e. without diluents or solvents or one or other or both can be employed in the form of aqueous dispersions or emulsions.

The particles are preferably contacted with water prior to contact with the polyisocyanate amd phosphate.

The polyisocyanate component of the binder system can be any organic polyisocyanate which contains at least two isocyanate groups per molecule. Illustrative of organic polyisocyanates are diphenylmethane diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, α,α-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and the mixture of these two isomers which are available commercially, triphenylmethane triisocyanates, 4,4'-diisocyanatodiphenyl ether, and polymethylene poly30 phenyl polyisocyanates. The latter polyisocyanates are mixtures containing from 25 to 90 percent by weight of methylenebis(phenyl isocyanate) the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality higher than 2.0. Such polyisocyanates and methods for their preparation are well-known in the art; see, for example, U.S. Patents 2,683,730; 2,950,263; 3,012,008 - 11 and 3,097,191. These polyisocyanates are also available in various modified forms. One such form comprises a polymethylene polyphenyl polyisocyanate as above which has been subjected to heat treatment, generally at temperatures from 150°C to 300°C, until the viscosity (at 25°C) has been increased to a value within the range of 800 to 1500 centipoises. Another modified polymethylene polyphenyl polyisocyanate is one which has been treated with minor amounts of an epoxide to reduce the acidity thereof in accordance with U.S. Patent 3,793,362.

The polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the binder systems of the invention. Particularly preferred polymethylene polyphenyl polyisocyanates are those which contain from 35 io 65 percent by weight of methylenebis(phenyl isocyanate).

When the organic polyisocyanate is to be employed as binder system in the form of an aqueous emulsion or dispersion in accordance with the invention, the aqueous emulsion or dispersion can be prepared using any of the techniques known in the art for the preparation of aqueous emulsions or dispersions, prior to use of the composition as the binder. Illustratively, the polyisocyanate is dispersed in water in the presence of an emulsifying agent. The latter can be any of the emulsifying agents known in the art including anionic and nonionic agents. Illustrative of nonionie emulsifying agents are polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene; alkoxylated alkylphenols such as nonyIphenoxy poly(ethyleneoxy)ethanols; alkoxylated aliphatic alcohols such as ethoxylated and prcpoxylated aliphatic alcohols containing from 4 to 18 carbon atoms; glycerides of saturated and unsaturated fatty acids such as stearic, oleic, and ricinoleic acids and the like; polyoxyalkylene esters of fatty acids such as stearic, « 48542 - 12 lauric and oleic acids; fatty acid amides such as the dialkanolamides of fatty acids such as stearic, lauric and oleic acids. A detailed account of such materials is found in Encyclopedia of Chemical Technology, Second Edition, Vol. 19, pp. 531-554, 1969, Interscience Publishers , New York.

The formation of the emulsion or dispersion can be carried out at any time prior to its use as the binder composition, but, preferably, it is carried out within about 3 hours prior to use. Any of the methods conventional in the art for the preparation of agueous emulsions can be employed in preparing the aqueous polyisocyanate emulsions employed in the process of the invention. Illustratively, the emulsion is formed by bringing the polyisocyanate, emulsifying agent and water together under pressure using a conventional spray gun in which the streams of water and polyisocyanate impinge and are mixed under turbulent conditions in the mixing chamber of the spray gun. The emulsion so formed is discharged in the form of a spray which is applied to the cellulosic particles to be formed into boardstock in the manner discussed below.

As discussed above, the phosphate release agent can be brought into contact with the particles as a separate component in which case it is employed in neat form, i.e. without diluents, or as an aqueous solution of dispersion. Preferably the phosphate either neat or in diluted form when used alone i.e. separately from the polyisocyanate, is presented to the particles in the form of a spray. However, in a preferred embodiment of the invention the phosphate release agent and the polyisocyanate are employed together in a single composition.

This can be accomplished in several ways. Thus, when the polyisocyanate is employed as binder resin without diluents such as water, the phosphate release agent can be incorporated in the polyisocyoanate by simple admixture. Where the polyisocyanate is employed as binder resin in - 13 the form of an aqueous emulsion the phosphate release agent can be added as a separate component during the formation of the emulsion or after its formation or, in a particularly advantageous embodiment, the phosphate is premixed with the organic polyisocyanate prior to emulsification of the latter. Thus, the organic polyisocyanate and the phosphate release agent can be premixed and stored for any desired period prior to formation of the emulsion. Further, when an emulsifying agent is employed in preparation of the emulsion said agent can also be incorporated into the mixture of organic polyisocyanate and phosphate release agent to form a storage stable composition which can be converted, at any desired time, to an aqueous emulsion for use as a binder resin by simple admixture with water.

When the polyisocyanate is employed as binder in the form of an aqueous emulsion, the proportion of organic polyisocyanate present in the said aqueous emulsion is advantageously within the range of 0.1 to 99 percent by weight and preferably within the range of 25 to 75 percent by weight.

Whether the phosphate release is introduced as a separate component or in combination with the polyisocyanate, the portion of phosphate release agent employed is within the range of 0.1 to 20 parts by weight, per 100 parts of polyisocyanate and, preferably, is within the range of 2 to 10 parts by weight, per 100 parts of polyisocyanate. The proportion of emulsifying agent required to prepare the aqueous emulsion is not critical and varies according to the particular emulsifying agent employed but is generally within the range of 0.1 to 20 percent by weight based on polyisocyanate.

The starting material for the particle board comprises particles of e.g. cellulosic and the like material capable of being compacted and bonded into the form of boards. Typical such materials are wood particles derived - 14 from lumber manufacturing waste such as planar shavings, veneer chips, and the like. Particles of other cellulosic material such as shredded paper, pulp or vegetable fibres such as corn stalks, bagasse and the like, and of non-cellulosic materials such as scrap polyurethane, polyisocyanurate and like polymer foams can also be used. The methods for producing suitable particles are well known and conventional. If desired, mixtures of cellulosic particles may be used. Particle board has been success10 fully produced, for example, from wood particle mixtures containing up to 30% bark.

The moisture content of the particles suitably may range from 0 to 24 percent by weight. Typically, particles made from lumber waste materials contain 10 15 20% moisture, and may be used without first being dried.

Particle board is fabricated e.g. by spraying the particles with the components of the binder composition, either separately or in combination, while the particles are tumbled or agitated in a blender or like mixing apparatus. Illustratively, a total of 2 to 8% by weight of the binder system (excluding any water present therein) is added, based on the bone dry weight of the particles, but higher or lower amounts of binder resin may be used in any given application. If desired, other materials, such as wax sizing agents, fire retardants, pigments and the like, may also be added to the particles during the blending stage.

After blending sufficiently to produce a uniform mixture, the coated particles are formed into a loose mat or felt, preferably containing between 4% and 18% moisture by weight. The mat is then placed in a heated press between caul plates and compressed to consolidate the particles into a board. Pressing times, temperatures and pressures vary widely depending on the thickness of the board produced, the desired density of the board, the size of the particles used, and other factors well known in the - 15 art. By way of example, however, for 1/2 (12.7 mm) thick particle board of medium density, pressures of 300 to 700 psi (2.07-4.83 Pa) and temperatures of 325° - 375°F (163-190.5°C) are typical. Pressing times are typically 2-5 minutes. Because a portion of the moisture present in the mat reacts with polyisocyanate to form polyurea, as described earlier, the level of moisture present in the mat is not as critical with isocyanate binders as with other binder systems.

The above-described process can be carried out on a batch basis, i.e. individual sheets of particle board can be molded by treating an appropriate amount of particles with the binder resin combination and heating and pressing the treated material. Alternatively, the process can be carried out in a continuous manner by feeding treated particles in the form of a continuous web or mat through a heating and pressing zone defined by upper and lower continuous steel belts to which, and through which, the necessary heat and pressure are applied.

Whether the process of the invention is carried out in a batchwise or continuous manner, it is found that the particle board produced using the polyisocyanate and phosphate release agent combination of the invention is released readily from the metal plates of the press used in its formation and shows no tendency to stick or adhere to said plates. This is in direct contrast to previous experience with the use of polyisocyanates alone as binder resins as discussed above.

While any of the phosphate release agents defined hereinbefore can be used, either alone or in combination, in the process of the invention, it is preferred to use the pyrophosphates (III) and (V) or mixed pyrophosphates derived from mixtures of the acid phosphates (I) and (II). Thus, the free hydroxyl groups present in the pyrophosphates, or any free hydroxyl groups present in the form of unconverted acid phosphate starting material, are generally sufficiently hindered as to be unreactive at ambient temperatures with the polyisocyanate employed in the process of the invention and the pyrophosphates can be stored in combination with said polyisocyanate for prolonged periods without showing any evidence of deterioration. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and employed in the process of the invention the processing temperature and the steam generated in the formation of the particle board are believed to result in hydrolysis of the pyrophosphate with regeneration of the corresponding acid phosphates which latter then serve to. facilitate subsequent release of the particle board from the plates of the press. It is to be understood that the above theory is presented for purposes of explanation only and is not to be construed as limiting in any way the scope of the present invention.

As set forth above, the monoacid phosphates (II) and the di-acid phosphates (I) and the salts thereof which are employed in the process of the invention are obtained by conventional procedures such as reaction of the corresponding alcohol ROH, wherein R is as hereinabove defined, with phosphorus pentoxide; Kosolapoff, ibid. As will be obvious to one skilled in the art, it is possible by using mixtures of two or more different alcohols in the above reaction to obtain a corresponding mixture of acid phosphates (I) and or (II) wherein the various components of the mixture have different values of the group R. As also set forth above the mixture of mono- and di-acid phosphates obtained in the above reaction can be separated into its individual components by conventional methods, such as fractional crystallization, and the individual compounds so obtained can be employed in the process of the invention. Alternatively, and preferably, the mixture of mono- and di-acid phosphates obtained in the above reaction can be employed as such, without separation, into its components, in the orocess of the invention or can be - 17 converted to the corresponding mixture of pyrophosphates using the procedures discussed hereinbefore, which latter mixture is then employed in the process of the invention.

Illustrative of the acid phosphates of the formula (I) above which can be employed individually or in combination .with other acid phosphates in the process of the invention are: mono-O-octyl, mono-0-nonyl, mono-O-decyl, mono-0undecyl, mono-O-dodecyl, mono-O-tridecyl, mono-O-tetradecyl, mono-O-pentadecyl, mono-O-hexadecyl, mono-O-heptadecyl, mono-O-octadecyl, mono-O-nonadecyl, mono-O-eicosyl, mono-0heneicosyl, mono-O-docosyl, mono-O-tricosyl, mono-0pentacosyl, mono-O-hexacosyl, mono-O-heptacosyl, mono-0octacosyl, mono-O-nonacosyl, mono-O-triacontyl, mono-0pentatriacontyl, mono-O-dodecenyl, mono-O-tridecenyl, monoO-tetradecenyl, mono-O-pentadecenyl, mono-O-hexadecenyl, mono-O-heptadecenyl, mono-O-octadencyl, mono-O-nonadecenyl, mono-O-eicosenyl, mono-O-heneicosenyl, mono-O-docosenyl, mono-O-tricosenyl, mono-O-pentacosenyl, mono-O-triacontenyl and mono-O-pentatriacosenyl di-acid phosphates and the diacid phosphates in which the esterifying radical is that derived from a monohydric alcohol such as lauryl alcohol which have been capped using from 1 to 5 moles of ethylene oxide.

Illustrative of the acid phosphates of the formula (II) above which can be employed individually or in combination with other acid phosphates in the process of the invention are: 0,0-di(octyl), 0,0-di(nonyl), 0,0-di(decyl), 0,0-di(indecyl), 0,0-di(dodecyl), 0,0-di(tridecyl), 0,0di (tetradecyl), 0,0-di(pentadecyl), 0,0-di(hexadecyl), 0,0-di(heptadecyl), 0,0-di(octadecyl), 0,0-di(nonadecyl), 0,0-di (eicosyl), 0,0-di ( heneicosyl) , 0,0-di (docosyl) , 0,0di (tricosyl), 0,0-di(pentacosyl), 0,0-di(hexacosyl), 0,0di (heptacosyl) , 0,0-di(octacosyl), 0,0-di(nonacosyl), 0,0di (triacontyl), 0,0-di(pentatriacontyl), 0,0-di(dodecenyl), 0,0-di(tridecenyl), 0,0-di(tetradecenyl), 0,0-di(pentadecenyl), 0,0-di(hexadecenyl), 0,0-di(heptadecenyl), 0,048542 - 18 di(octadecenyl), 0,0-di(nonadecenyl), 0,0-di(eicosenyl), 0,0-di(heneicosenyl), 0,0-di(docosenyl), 0,0-di(tricosenyl) , 0,0-di(pentacosenyl), 0,0-di(triacontenyl), and 0,0-di(pentatriacosenyl) mono acid phoaphafces, and the di5 esterified mono acid phosphates in which the esterifying radical is that derived from lauryl and like monohydride alcohols which have been capped with 1 to 5 moles of ethylene oxide. Illustrative of the latter types of phosphate which are available, in admixture with the corres10 ponding diacid phosphates, are the materials marketed under the trade name Tryfac by Emery Industries Inc.

Illustrative of the pyrophosphates of the formula (III) above which can be employed individually or in combination with other pyrophosphates in the process of the invention are : tetraoctyl, tetranonyl, tetradecyl, tetraundecyl, tetradodecyl, tetra(tridecyl), tetra(tetradecyl) , tetra(pentadecyl), tetra(hexadecyl), tetra(heptadecyl) , tetra(octadecyl), tetra(nonadecyl), tetra(eicosyl), tetra (heneicosyl), tetra(docosyl), tetra(tricosyl), tetra20 (pentacosyl), tetra(hexacosyl), tetra(heptacosyl), tetra(octacosyl), tetra(nonacosyl), tetra(triacontyl), tetra(pentatriacontyl), tetra(dodecenyl), tetra (tridecenyl), tetra(tetradecenyl), tetra(pentadecenyl), tetra(hexadecenyl), tetra(heptadecenyl), tetra(octadecenyl), tetra25 (nonadecenyl), tetra(eicosenyl), tetra(heneicosenyl), tetra(docosenyl), tetra(tricosenyl), tetra(pentacosenyl), tetra(triacontenyl), and tetra(pentatriacosenyl)pyrophosphates .

Illustrative of the pyrophosphates of formula (IV) above which can be employed individually or in combination with other pyrophosphates in the process of the invention are di(octyl), di(nonyl), di(decyl), di(undecyl), di(dodecyl) , di(tetradecyl), di(pentadecyl), di(hexadecyl), di(heptadecyl), di (octadecyl), di(nonadecyl), di(eicosyl), di(heneicosyl), di(docosyl), di(tricosyl), di(pentacosyl), di(hexacosyl), di(heptacosyl), di(octacosyl), di(nonacosyl), - 19 di(triacontyl), di(pentatriacontyl), di(dodecenyl), di(tridecenyl), di(tetradecenyl), di(nentadecenyl), di(hexadecenyl), di(heptadecenyl), di(octadecenyl), di(nonadecenyl) , di(eicosenyl), di(heneicosenyl), di(docosenyl), di(tricosenyl), di(pentacosenyl), di(triacontenyl), and di(pentatriacosenyl)pyrophosphates.

The 0-monoacyl derivatives of the acid phosphates (I) and (II), which can be employed in the process of the invention and which are shown as formulae (V) and (VI) above, are readily prepared by procedures well-known in the art. Illustratively, the corresponding acid phosphate (I) or (II) in the form of its silver or other metal salt, is reacted with the appropriate acyl halide R^COHal where Hal represents chlorine or bromine and R^ is as hereinbefore defined, using the procedures described by Kosolapoff, ibid, p. 334. Illustrative of the 0-monoacyl derivatives of the acid phosphates (I) and (IX) are the O-acetyl, 0-propionyl, 0-octanoyl, 0-decanoyl, O-dodecanoyl, O-benzoyl, O-toluoyl, O-phenacetyl derivatives of the various acid phosphates (I) and (II) exemplified above.

The carbamoyl phosphates having the formula (VII) which are employed in the process of the invention are readily prepared by reaction of the appropriate acid phosphate (I) or (II) with the appropriate hydrocarbyl monoor polyisocyanate using, for example, the procedure described by F. Cramer and M. Winter, Chem. Ber. 92 2761 (1959). Illustrative of such carbamoyl phosphates are the methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, hexylcarbamoyl, decylcarbamoyl, dodecylcarbamoyl, allylcarbamoyl, hexenylcarbamoyl, octenylcarbamoyl, decenylcarbamoyl, dodecenylcarbamoyl, phenylcarbamoyl, tolylcarbamoyl, diphenylylcarbamoyl, benzylcarbamoyl, phenylpropylcarbamoyl and like hydrocarbamoyl derivatives of the monoacid phosphates (stabilized in the form of their ammonium or alkali metal salts) as exemplified above. The carbamoyl phosphates (VII) may contain free OH groups due - 20 to incomplete conversion of the acid phosphates in the reaction with the appropriate hydrocarbyl isocyanate because of low order of reactivity of the OH groups in question with the isocyanate. Such compounds containing said free OH groups can be used in the process of the invention without producing undesirable side-effects because of the low order of reactivity of the OH groups with isocyanate.

The polyphosphates corresponding to the formula (X), which are employed in the process of the invention, are readily prepared by reaction of the appropriate trialkylphosphate (RO)^PO, wherein R is as hereinbefore defined, with phosphorus pentoxide using the procedures described by Kosolapoff, ibid, p. 341. The polyphosphates'are generally complex mixtures whose composition is represented generically by the formula (X), and include cyclic compounds (n = 3) having a six-membered ring composed of alternate phosphorus and oxygen atoms.

The polyphosphates corresponding to the formula (VIII) and (IX), which are employed in the process of the invention, are readily prepared by the reaction of the appropriate di or trialkylphosphate and the appropriate halophosphate VJ (RO) 2P-Hal where Hal is chlorine or bromine, using, for example, the procedure described by Kosolapoff, ibid, p. 338. The procedure involves elimination of alkyl halide.

In a further embodiment of the invention it is found that the combination of polyisocyanate and phosphate release agent employed as binder in the process of the invention can be used in conjunction with thermosetting resin binders hitherto employed in the art such as phenolformaldehyde, resorcinolformaldehyde, melamine-formaldehyde, - 21 urea-formaldehyde, urea-furfural and condensed furfuryl alcohol series. Not only does the use of such a combination avoid the problems of adhesion of the finished particle boards to the platens of the press, which problems were previously encountered with a blend of isocyanate and the above type of thermosetting resin binder, but the physical properties of the particle boards so obtained are markedly improved by the use of the combination.

The following preparations and examples illustrate preferred embodiments of the invention but are not to be construed as limiting.

PREPARATION 1.

Preparation cf pyrophosphate from lauryl acid phosphate A mixture of 70 g. lauryl acid phosphate (a mixt15 ure of 0,0-dilauryl monoacid phosphate and 0-lauryl diacid phosphate; Hooker Chemical Company) and 60 g. of phenyl isocyanate was charged to a dry flask fitted with stirrer, condenser and drying tube, the flask was immersed in an oil bath preheated to 80°C and the contents of the flask were stirred while the temperature of the oil bath was slowly raised to 115°C. Carbon dioxide was evolved over a period of about 1 hour. When evolution of carbon dioxide had ceased, the reaction mixture was cooled to room temperature and diluted with 100 ml. of chloroform. The resulting mixture was filtered and the solid so collected (24.6 g. of Ν,Ν'-diphenylurea) was washed with chloroform. The combined filtrate and washings were concentrated on a rotary evaporator at a bath temperature of 50°C. When most of the solvent had been evaporated, crystals of Ν, Ν', N30 triphenylbiuret separated and the evaporation was interrupted to filter off this solid material {6.6 g.). The filtrate was evaporated to dryness and subjected finally to reduced pressure at 50°C to remove excess phenyl isocyanate. The residue (70 g.) was the desired pyrophosphate in - 22 48542 the form of a colorless to pale yellow liquid. The infrared spectrum of the product (in CHCl^) did not show any bands characteristic of P-OH bonds but had a strong band at 940cm characteristic of P-O-P bonds.

PREPARATION 2 Preparation of pyrophosphate from lauryl acid phosphate A total of 70 g. of lauryl acid phosphate (same starting material as used in Preparation 1) was charged to a flask fitted with stirrer, reflux condenser and gas inlet and was heated under nitrogen at 65 - 75°C until molten.

The melt was stirred while a slow stream of phosgene was passed in for a total of 2.5 hours. The temperature was maintained in the above range throughout the addition. Evolution of gas from the reaction mixture was vigorous in the first hour of the phosgene addition but gradually subsided and was very slow at the end of the period of addition of phosgene. After addition was complete, the mixture was purged with nitrogen for 15 hours while maintaining the temperature in the above range. At the end of this time the pressure in the reaction flask was gradually reduced to about 1.0 mm. of mercury to remove gaseous hydrogen chloride and carbon dioxide. The viscous residue so obtained solidified completely on allowing to stand overnight. There was thus obtained 66 g. of pyrophosphate as a solid which melts gradually at about 60°C.

PREPARATION 3 Preparation of pyrophosphate from oleyl acid phosphate A mixture of 200 g. of oleyl acid phosphate (.comprised of a mixture of 0,0-dioleyl acid phosphate and 030 monooleyl acid phosphate as supplied by Hooker Chemical Company) was reacted with 160 g. of phenyl isocyanate at a temperature of 85° - 90°C for 5.5 hours using the procedure described in Preparation 1. The Ν, Ν'-diphenylurea (68 g.) - 23 was removed by filtration after the reaction mixture had been diluted with 200 ml. of chloroform. The filtrate was connected on a rotary evaporator and the excess unreacted phenyl isocyanate was removed by distillation at reduced pressure. Ν, Ν', N-triphenylbiuret crystallized from the oily residue on standing at room temperature. Removal of the crystals by filtration yielded 196 g. of a liquid product, the infrared spectrum of which exhibited a band at 940 cm 1 characteristic of P-O-P bands but showed no bands characteristic of the P-OH band.

PREPARATION 4 Preparation of pyrophosphate from lauryl acid phosphate A solution of 30.4 parts by weight of lauryl acid phosphate (same starting material as in Preparation 1) in 21 parts by weight of toluene was charged to a dry reactor previously purged with nitrogen. The solution was heated to 40°C with agitation at which point a solution of 7.6 parts by weight of polymethvlene polyphenyl polyisocyanate /eg. wt. = 133; functionally 2.8; containing circa 50 percent methylenebis)phenyl isocyanate// in 5 parts by weight of toluene was added. The resulting mixture was stirred while a stream of phosgene was introduced (ca. 0.1 parts by weight per minute) and the temperature was slowly raised to 80°C. The temperature was maintained at this level, with continuous introduction of phosgene until a total of 20 parts by weight of the latter had been introduced. The total time of phosgene addition was 5 hr. 50 mins. The reaction mixture was heated at the same temperature for a further 40 minutes after phosgene addition was complete before being heated to 90 to 95°C and purged with nitrogen for 2 hours to remove excess phosgene. The pressure rn the reactor was then reduced until refluxing of toluene commenced and the purging with nitrogen was continued for a further 2 hr. The toluene was then removed by distillation under reduced pressure, the last traces being removed in vacuo. The residue was cooled to room temperature, treated - 24 with diatomaceous earth (Celite 545)(CELITE is a Registered Trade Mark) and filtered after agitating for 30 minutes. There was thus obtained 23.7 parts by weight of a mixture of lauryl pyrophosphate and polymethylene polyphenyl poly5 isocyanate which was found to contain 6.O8S w/w of phosphorus .

PREPARATION 5 Further preparation of pyrophosphate from lauryl acid phosphate Using the procedure described in Preparation 4 but replacing the polymethylene polyphenyl polyisocyanate there used by an equivalent amount (6.8 parts by weight) of phenyl isocyanate there was obtained a further batch of lauryl pyrophosphate.

Example 1 A series of samples of wood particle board was prepared using the following procedure from the components and quantities of components (all parts by weight) shown in Table 1 below.

The wood chips (Turner shavings”) were placed in a rotating blender drum and the drum was rotated while the particles were sprayed with an aqueous emulsion of the polyisocyanate, water, phosphate and emulsifying agent.

The emulsion was prepared by blending the components thereof using a Turrex mixer. The resulting emulsion was sprayed with a paint spray gun on to the wood particles while tumbling for 45 - 120 seconds to achieve homogeneity. The coated particles were formed into a felted mat on a 12 x 12 (34.5 x 34.5 cm) cold-rolled steel plate with the aid of a plywood forming frame. After removal of the forming frame, steel bars having a thickness corresponding to the desired thickness (1/4 6.35 mm) of the final particle board were placed - 25 along two opposing edges of the aforesaid steel plate and a second 12 x 12 cold-rolled steel plate was placed on top of the mat. The complete assembly was then placed on the lower platen of a Dake press having a capacity of 100,000 lbs. of force (c.444.8 kN). Both platens of the press were preheated to a selected temperature shown in Table 1 below. Pressure was then applied and the time of molding shown in Table 1 was calculated from the point at which the pressure exerted on the mat reached 500 psi (3.45 Pa). At the expiry of the molding time shown in Table 1 the pressure was released and the particle board was demolded. In all instances it was found that demolding was accomplished readily with no tendency of the board to stick to the plates with which it was in contact. This is in direct contrast to the behaviour of a board prepared under identical conditions but without the presence of the lauryl acid phosphate in the emulsion used as binder in preparing the board.

The various samples of particle board so prepared were then subjected to a series of physical tests and the properties so determined are recorded in Table 1. These properties demonstrate the excellent structural strength properties of the boards. - 26 sr ST ω Ό σ\ «Η ο ro rd Ο ο rd Ο [“*· • • sr • rd ό CO rd Ο ο η rd ro SO Ο ro rd o o rd tn r* • • sr r- • ro rd O o CO rd oj ffl O ro so rd o o rd O sr • ό ro rd OJ TABLE so o ro rd o o H in 0» • • sr r- » co rd O o ro rd rd TJ p nJ ffl Ό Φ ω 0) Φ Φ (X -P P •id nJ nJ 42 42 ro β ϋ β & •P nJ P o 0} {2 >1 Φ Φ C rd •id 0 Φ 0 P fd a • 42 tn 0 β Md 0 X J rd P4 nJ n 42 fd μ nJ 3 •id Jd a to • φ β E TJ tn >1 Φ to rd & 03 .u nJ Φ •H β I—J 44 0 3 ε Qj ¢0 ΐ >1 □ •id 0 3 42 S φ fd 5 □ fi nJ ϊ>» A £ a Φ Eh £ □ 0 id Md (0 rd Md fd 5 £ & β o d k >1 to \ \ > Φ TJ >i Φ Jd rd 5 5 & •P o . rd +J 3 3 dt> dP dP dP nJ 0 +J 0 nJ flf ε rd 5 J3 ffl JS H * 4( 4c 4( a Mold time, minutes - 27 Γ* o o CM O CO r» · O •cf ro Μ* Γ* in m O (J's CN KO d KO (rt in CM r~i ίο 7··} in cf ID in O O frt OK Ν' CM frt O CM *y r> in co > CM Cι-1 · irt O in in M· KO CM rt TABLE 1 (continued) CQ rt in N* KO KO rrt CN CM cn m Γ- CN N* frt rt* O CM r> d m in rt* KO CN rrt rd O rt· rt* co ο m rt · r-- in *rt cm rrt CM Φ O rt* in ro CN O r-> o KO frt in CM rt ZJ k ffl o 0) fl ZJ Φ CO to r—i fl -r-l k Φ rt fl S rt O a rt -rt CO G Φ a rrt £ ί’ Ai rt •rt Φ k V -rl O o ZJ 3 rt to rt G 0 C C CL fl X Λ Λ 3 r*d k Φ trt rt rt rt fl •rt fl •rt rt CO rt fl G co G fl 0 CL 0 n k Φ CL k Φ Qi W fl rt rt □ 3 G C rrt rt -rt •rt 3 *0 3 ZJ >1 rt fl o to Ο- fl k to £ fl s fl Χ fl Q fl & Ai r Cl n· CL %r CL in AJ - 28 TABLE 1 (continued) Footnotes to Table 1 1: Polymethylene polyphenyl polyisocyanate: eg. wt. = 133; functionality 2.8; containing circa 50 percent methyl5 enebis(phenyl isocyanate).

: Mixture of lauryl diacid phosphate and dilauryl mono acid phosphate: Hooker Chemical Company. •3 : Ethoxylated propoxylated butanol: Witconol APEB: Witco Chemical Company.

S Tests carried out in accordance with ASTM-1037-72.

: Tests carried out in accordance with German V-100 specifications.

* Calculated on dry weight of wood particles.

Example 2 A series of samples of wood particle board was prepared using the procedure described in Example 1 using the various components and quantities (all parts by weight) shown in Table 2 below. The mold time shown in the Table for Samples E and F is the time for which the mat was maintained under pressure (500 psi 3.45 kPas) after the internal temperature of the mat (as determined by a thermocouple inserted therein) had reached 130°F (54.5°C). Sample G was a control sample molded as described in Example 1. The physical properties determined for each of the finished particle boards are also shown in Table 2 and demonstrate the excellent structural strength of the various samples. All of the samples demolded readily and showed no sign of adhering to the steel plates used in - 29 their preparation.

TABLE 2 Board E F G Materials used Wood chips 644 644 644 Wt. of water in chips 56 56 56 Polyisocyanate (same as Ex.1) 21 42 21 Water in emulsion 56 56 56 Lauryl pyrophosphate'' 2.1 4.2 2.1 Emulsifying agent (same as Ex. 1) 0.1 0.1 0.1 A %w/w polyisocyanate 3.3 6.6 3.3 A %w/w water 17.4 17.4 17.4 A %w/w pyrophosphate 0.33 0.65 0.33 A %w/w emulsifer 0.016 0.016 0.016 Platen temp. °F 355 355 355 °C 179 179 179 Mold time, minutes 2 2 2 Physical Properties Density: pcf 41 41 42 , ,- 3 kci/in 656.8 656.8 672.8 2 Modulus of rupturej psi 5130 5090 5320 Pus 35.37 35.05 36,68 TABLE 2 (continued) Board E F G Materials used 2 Modulus of elasticity: psi (x 10^) 505 513 521 Pas 3482 3537 3592 2 Dry internal bond: psi 128 141 132 Pas 0.88 0.97 0.91 ^Wet internal bond: psi 32 38 31 kPas 220.6 262.0 213.7 Footnotes to Table 2 I; Prepared as described in Preparation 1.

: Test carried out in accordance with ASTM 1037-72. o : Tests carried out in accordance with German V-100 specifications.

* Calculated on dry weight of wood particles.

Example 3 A series of samples of wood particles board was prepared using exactly the same reactants and proportions shown in Example 1 and using exactly the procedure described in that Example, save that the platens of the press were preheated to 400°C (204.5°C) and maintained thereat for the various molding times shown in Table 3 below. The physical properties of the samples so prepared are also recorded in Table 3 and show that these samples all possessed excellent structural strength. None of the samples showed any tendency to adhere to the molding plates during demolding. 48549 rn CG < EH Lf! O Om C £ rH Ό P fl CG ω Φ -P G fi •P e Mold time -ΒίγΟ o -a* ΧΡ Ο oj Ο* » m m fO 04 Ο -a· m tn η 5f m Μ* Γ- Ο» Ο rH Ο in m «ν ID 04 rH LO rd in «5* LO ΓΟ O «tf -tf lc m O rH rp « 04 m rs O 04 m O «a* m γΟ ΓΟ «sr in r04 H o in r> cr oh XT *r *a* O rn co oo \D O LC CO m in 04 H n m <0 -tf m -tf r-i o Γ6 m n -tf i£> OJ rH O LO r* n O OS 0>. o -tf O OJ *r σ» m iD C LD CO m m r-j *P to a cn Φ 0> P Ή 3 P •P p ft Φ 3 cu P 0 Uh P a UH cu cu 0 i-H ,, Ui fl >1 3 o •P rH •P •P 3 a to £ Ό is c X 0 X2 Φ cn X ft Q r-4 (Λ fl CU >1 P •P ϋ •i-i •P (/} fl rH 0) O rH ω x iH Ό -w w •P *P ft a Ό ^3 C 3 0 C Λ Λ i-H i-H fl fl c 3 P P Ci +4 -P G £ *P •P > (0 «Ρ P fl fl) Q cu - 32 Footnotes to Table 3 Test carried out in accordance with ASTM 1037-72, : Tests carried out in accordance with German V-100 specifications, Example 4 A series of samples of wood particle board was prepared using the procedure described in example 1 but varying the nature of the polyisocyanate and employing, in place of the lauryl acid phosphate, the pyrophosphate derived from oleyl acid phosphate prepared as described in Preparation 3. The various components and the proportions thereof (all parts by weight) are shown in Table 4 below together with the physical properties determined on the finished samples. The thickness of the board samples in all cases was 3/8 inch (9.5 mm)(spacer bars of appropriate thickness were used). None of the samples showed any tendency to stick to the molding plates during demolding. The physical properties of the various samples show that they all have excellent structural strength. - 33 Tf Tf VO o <0 Φ h r- · · CM Tf CM O Tf Tf VO E-ι vo in r-4 r—I Μ C- · · CM Tf CM O Tf Tf VO OQ vo in r-t C* · · CM Tf CM O Tf Tf VO ccj VO L/Ί i-4 CM rTf CM Tf Tf VO O vo in r-i ΓΜ l—t r—i C* · · Tf CM O tf Tf Tf Tf vO vo in »-4 CM «—J Γ- · Tf CM TABLE Tf Tf vO O vd m r—i Γ* · Tf CM Tf Tf vo vo m Η H > . .

Tf CM O Ό L4 nJ CQ S Tf Tf VD vp m 0) to tf •ri ti ϋ β •Η μ φ Ρ φ +J rt β rt ω tf rt Cn r—i •r4 2 ϋ rt Λ 0 •r4 ϋ ιμ 10 0 Η Φ TJ >. 4J 0 • r—i rt 0 4J 0 2 & tf τ Tf in vd O Q W tf oo tn O W ► r-4 H Γ-. · · Tf CM O β 0 •Η 4-> β Φ tn ι—4 r-4 Φ rt β 4J • ε rt tn X φ χ: β W β tf η *Η (0 Ή 0 ιμ rt μ XJ tf •Η Κ φ φ 0 r—i ε μ β rt rt ΪΝ ε ω £ tf W —* co ro O kD pH O o kD r—I o o - 34 PrM Ο H *3· t*· co κ O co o •3· o *3· kO kO H tn vo O kD σ> CM O kD rM kD o σ» tn O CM ΓCM O *3« CM O T3 Φ β •H 4-> c ϋ co co co CO co O O O k£> rM o kO co H co O O O kD rM o o •31 rM O’ o o CD · CO Pin co o <3* co Ο «Η p* CO l-l ΟΟ rM Ο -34 kO rM • ιη •3* Ο kO <3* CO 00 rM Ο O' CM Ο* » Ρ* •31 Ρ” kD ιη CO O w •3* P* CO rM o *3* O •3* kO O O rM in μ rt m kD rM o o o -3< CO ι—I PrM ko in kO O co O 3* fi fd to φ Χ2 μ φ -Ρ CU φ «μ fd to -Μ fa α β β 0 0 0 β fd Λ •Η •«Μ >1 μ cu CO ♦ ε ϋ φ 0 rM s* 0 -μ μ β ε * (0 fd s £ φ φ •Η 5 cu Φ -μ ε •Η MM □ CU \ dP & \ dP β Φ μ nJ rM CU Ό rM S fd o •H » cu >1 +» •H W β Φ Q Φ M β «μ §· μ ΨΙ ο ω β rM *§ Ό Ο Ο & >ι Μ Ό β Φ > Ο β Ο co Ό φ to _ β \ ·Η W ώ ί Ο w (U **4 Η PrCM μ< - 35 o UO fN σι □ ro CN ro > · O O M· un ω TABLE 4 (continued) ro «ί* O (N CO *0 «3 CQ £ o CN u •ri P β τ> G X03 d /—i G T3 o £ G P Φ 4-» G •P >1 ·Η p 01 Q & β A in > , ro ro CN CN I Ή >1 XJ •Ρ CN Φ ε ω 00 i—i -Ρ ro CN CO Γ—! G Φ Ο il Ρ r*· Φ CU r-i P CN un 2P un P ν© σ β ω υ co ρ «· •ι-ί X-. υ f-H φ tr r-i Ρ <0 G G Ρ β G cc >1 •Ρ υ β Ο Ρ —i ω <2 ρ 0 o > Φ ro SO G Ρ Μ Φ β ϊ-ί ο XJ G CN CN α Φ Ί ro CN > 03 Φ • Ρ Ο Ρ Λ 03 ΓΝ Φ •Ρ G >1 • νθ Φ r—i σ1 r- οΟ ·—i Ο φ <Ν γΗ >1 a >* Ρ, s Ρ t-i φ Φ >< Ρ ι-1 Ε G β Φ G Ρ χ; β CO CN Ο {X >4 <Ρ γ—1 >1 Ο ρ r-i 0 Φ Ο 03 Ε a •Ρ >1 fP φ rp Ο G >, CU Φ G *r Φ γΡ Φ Ό Ρ £“ι Χ3 £2 0) & χ: α Ο r-i Ρ *·- Λ ja Τ3 φ 01 β •Η ε Ρ r-i £* 3 >t Ρ β σ r—l φ G Ο -Η Ο C, Ρ Ρ a Φ Φ -μ 03 G Φ ·» »· »« •Η Ρ r-i <Ν *< 03 Ο Ρ -Η β G Φ 01 X Ρ 3 α X Ο π -ί V IX - 36 : Polymethylene polyphenyl polyisocyanate containing : circa 45 percent methylenebis(phenyl isocyanate) : eg. wt. = 133.5 4: Liquid methylenebis(phenyl isocyanate) prepared in 5 : accordance with U.S. 3,384,653: eq. wt. = 143 5: Polymethylene polyphenyl polyisocyanate containing circa 35 percent methylenebis(phenyl isocyanate): : eq. wt. 140 6: Polymethylene polyphenyl polyisocyanate containing 10 : circa 35 percent methylenebis(phenyl isocyanate): : eq. wt. 140 : Polymethylene polyphenyl polyisocyanate containing : circa 70 percent methylenebis(phenyl isocyanate): : eq. wt. = 133 Σ 5 8 : Same as Example 1 : Toluene dnsocyanate 'θ: Tests carried out in accordance with ASTM 1037-72 Tests carried out in accordance with German V-100 : specifications Example 5 This example illustrates the preparation of particle board in accordance with the invention using a binder . composition in which no extraneous emulsifying agent is - 37 present and the polyisocyanate was applied neat, i.e. not in the form of an aqueous emulsion.

A series of samples of wood particle board was prepared using the various components and quantities (all parts by weight) shown in Table 5 below and using the procedure described in Example 1 with the exception that the wood particles were first sprayed with the stated amount of water and thereafter were sprayed with a mixture of the polyisocyanate and the phosphate release agent. The physi10 cal properties determined for each of the finished particle boards are also shown in Table 5 and demonstrate the excellent structural strength of the various samples. All of the samples demolded readily and showed no sign of adhering to the steel plates used in their preparation. - 38 σ» ω ρ* r-1 SO in OJ ΟΙ rd σ\ so o OJ \ rd o co \ CO M ffl ffl < sr o* so o in oi oo co in σν sr γιο O co \ co TJ P iO ffl Φ ffl Φ ffl 3 ffl w nJ β rd β tn a 32 nJ nJ Λ Φ ffl a Sm ffl a «Ρ 43 rd tn OI 0 0 tn 3 □ Φ 0 0 P 0 β ffl , 32 • tn 32 ffl β d X a ffl P a ε ffl β w 0 W >1 Φ 0 ω nJ P ffl ffl P a p >1 ω >1 tn 0 nJ φ id Φ 0 β a nJ a a ε XJ ϋ ffl nJ 0 (0 Φ rd Φ s £ £ •η •P •η g P >1 ε \ TJ >1 nJ Φ P nJ 5 TJ 0 . rd tn ffl 3 tn dP dP dP ffl o -p 0 ·— nJ nJ *—* 0 5 5 a £ ffl * * * s ω Φ □ β ffl ϋ •«d ffl TJ P nJ o ffl - 39 48542 vo h in tq «τ vo tq vo O «-» rH « ro *3« ro rq ro m ro co cm vo ro r* · ro r-l ι-i H oo r* Os ro •$j* ro Γ6 O ’'T cq vo ι—I * O ** in ro TABLE 5 (continued) co rq rq r* VO O σν co · r* σ> m co rM* CO vo co in ro rr-i cn «Φ · rH O VO H CO k CO CQ vo rH m X M VO vO vo r* co · «η in m co C «Η m IN co •O’ CO O vo CN · ro vo m co *r r-i in o *r n co ro in cn co · l-H O m vo ro cn rr cq ω Φ Φ k 3 4J -Ρ p α Φ 3 P, k 0 Μη k 4Η a υ 0 α Ή ω rt >1 3 u -Ρ rH Ή Ή ro 3 ω ϋ) C Ό 5η C X 0 £ Φ Ζ 04 Q ^4 γΗ >1 -P Ή υ •Η -Ρ tn rt r-H Φ ω rt A U-i w rH Ό o rH X w a •Η (Λ α •ri ω CU *Ό T3 C c 0 0 Λ Λ rH rH rt rt a c k k a> 0) P +j 3 •ri •iH w ω >1 w •P rt rt k rt Φ (Xi CL a Ox S & rH - 40 Footnotes to Table 5 Calculated on dry weight of wood particles Tests carried out in accordance with ASTM 1037—72 n Tests carried out in accordance with German V-100 5 specifications.

Example 6 This example illustrates the preparation of three particle boards in accordance with the process of the invention from wafer chips having varying dimensions as large as 2 x 2 x 1/32 (50 x 50 x 0.8 mm) and supplied by Weldwood of Canada, Ltd. No extraneous water or emulsifying agent was used and the polyisocyanate and phosphate release agent were applied neat.

A series of samples of particle board from the wafer chips was prepared using the various components and quantities (all parts by weight) shown in Table 6 below and using the procedure described in Example 1 with the exception that the wood wafers were sprayed with a mixture of the polyisocyanate and the phosphate release agent and not with an aqueous emulsion as in Example 1 and that aluminum molding plates were used. All of the samples demolded readily and showed no sign of adhering to the aluminum plates used in their preparation. The excellent structural strength properties of the resulting particle boards, as evidenced by the high modules of rupture shown in Table 6, compare very favourably with the low value of this parameter (2500 psi 17.2 Pas) determined in a board available commercially and prepared from the same type of wafer chips using a phenol-formaldehyde resin binder. - 41 TABLE 6 Board AA BB CC Wafer chips 955 955 955 Wt. water in chips 45 45 45 Polyisocyanate^ 19.1 50 50 Lauryl pyrophosphate (same as Ex. 2) 2.5 6.5 6.5 at %w/w polyisocyanate 2 5.2 5.2 * %w/w total water 4.7 4.7 4.7 * Sw/w pyrophosphate 0.26 0.68 0.68 Mold time (mins.) 4.5 4 4.5 Board thickness (in.) 1/2 1/2 1/2 (mm) 12.7 12.7 12.7 Density, pcf 46 43 45 kg/m 3 736.9 688.8 720.8 Modulus of rupture: psi 7317 7946 10,860 Pas 50.45 54.79 74.88 Calcd. on dry weight of wood wafers 1 Polymethylene polyphenyl polyisocyanate: eq. wt, = 139: functionality 3.0. Viscosity at 25°C = 700 cps: containing circa 35 percent methylenebis(phenyl isocyanate) . 8 542 - 42 Example 7 This example illustrates the preparation of a series of particle boards using polyisocyanate binders in combination with various commercially available phosphates in amounts corresponding to approximately 0.7 percent w/w phosphorus in the binder resin combination.

The various samples were prepared using the. various components and quantities (all parts by weight) shown in Table 7 and using the procedure described in Example 1 with the exception that no emulsifying agent was employed, and the water was sprayed onto the chips first, followed by the isocyanate mixed with the release agent. All of the samples demolded readily and showed no sign of adhering to . the steel plates used in their preparation. In contrast, a control board, prepared in exactly the same manner but omitting the use of a phosphate release agent, adhered to the steel plates used in the preparation and could not be demolded without damage to the surface of the board. rTABLE 8 512 Ο *tf -tf ο lo r-H LO 00 Ο *Ρ Η5 *tf * Ι-) -tf 0 Ό Η LO 00 Ο -tf -tf rp Ο LD r-H LO CO O -tf -tf · ffi rtf O LD X r-4 LD CO O -tf · -tf O ’ LD rH LD CO -tf O LD rH LO CO ft O *r X r-ί to co i-i O fQ -tf · Q -TOO CQ Q r-t LO CO Ο ΓΗ νο co Ο ΓΗ o CH rH tn in o ΓΗ O CM o CH rH -ΤΟ O CH rH O O rH rH -tf lO o rn CH · rH CO fl) , 44 X fl ω 43 ft ω ω W a ft 0 •ri 43 fl) 43 rH ft ro £ υ fl) XJ ΓΗ fl •P . m «3 4j . xj tn W β fl X -Η CH — -ri C fl ft iH fl) O fl ω >. in •P fl) ft fl) ϋ fl fl l-i σ» •H HJ 0 £ >1 Sh 43 fl tn 0) ϋ fl) O £ •H £ XJ 0) •P Ό > fl fl) XJ tn 0 • rH m XJ •ri 0 o -P 0 XJ J4 ft 5 3 ft < rH OL CH CO CH Γ m < < r* tn o ft tn CH rH m m lO fl) tn o O ϋ iH fl fl fl fl) UH UH UH -P St Sr >, tn iH μ iH 0 e* £h H ft ch ro -tf n Φ < P fl 43 ft W O 43 ft 0 in in ch Sr in ft 7\ Γ-Η fl Sr '44 in Sr 3 iH fl PJ Γ48542 - 44 rOJ OJ X OJ SO rd sr r-d rd OJ SD rd roj · X oj OJ sr rd ΓOl ffi ΓΟ] TABLE 7 (continued) Γ— O1 · OJ X CN SO rd sT rd ffl Γ— OJ · fe IN k so ffl sr ffl ffl oOI Η οι X oj W so ffl sr rd ffl TJ P ti « Ol SO rd sT Ol X rd ΓO1 rd Φ 32 ffl β β P ϋ β fd ni >1 Φ ffl . u nJ Ul 0 £ β tn Ul fd Φ id ffl 3 β >1 nJ ffl ffl ffl ϋ 0 0 φ •Ρ a ffl ε 32 5 5 ffl ffl ffl X X TJ 3 £ TJ P <#> <#> ffl nJ * 0 £ 0 a Ul β 0 0 β rd fd H . 0 ffl ffl P Ul 0 0 Φ 0 a fd rd 0 nJ P β P ffl ffl a β -Ul 0 P 3 •id P 0 TJ ffl nJ Md • β β ffl id β H ffl 0 rd β a ε β •rl >1 *r| u rd P rd fO 0 Φ β «. P ε Λ Φ β a Ul ffl β Q - Φ •id P ffl S 0 ffl «·. □ ffl ffl rd β tJ ffl 3 0 β Φ O ffl Ρ ffl β CO 0 Λ 0 ffi 0 nJ rd β Φ K c β •Η P fd β φ o TJ rd ffl P β rd >1 ϋ a Η 3 p I β 3 TJ rd rd £ β •Ρ 0 Φ rd ε 32 ffl * 0 β • TJ TJ O Φ 0 Φ φ rd ffi β ffl ffl nJ Η β β Md rd . rd rd 0 Ul X >1 >1 Φ X X P β -rl 0 0 3 0 Ρ ffl ffl β •id ffl ffl ffl ffl Ul Ul Φ φ Ή 3 ε > TJ ε ' ε 0 •rl β 0 0 P Q H P Ρ Md Md Md β >1 TJ β P • TJ TJ Φ β Φ Φ Φ > rd ε > > •rl fd a •id •Η P ffl P Ρ Φ X Φ Φ T3 Φ ·«. TJ TJ ·- H φ 0 Φ •p Φ Φ β ffl β ffl •Ρ H r- nj • K ffl β β xj Φ a ffl ffl Φ a TJ Ul a a OT rd Ul ffl 0 Ul OT Φ: ffl 0 X ffl 0 0 fd nJ ffl 0 a ffl ffl P a a a ffl Φ TJ Ul 0 TJ β fd TJ TJ 3 ffl •id Φ ϋ •id , •P TJ ϋ rd β ϋ 0 β Ul nJ >1 • β β H Φ ffl rd ffl rd ffl >1 rd rd >1 0 >1 Φ P P β ffl 3 ffl ffl Φ ffl rd Md β rd rd ε 0 0 Pl < a 0 a rd Ol ro si* - 45 Footnotes to Table 7 b Alkyl acid phosphate derived from n-octyl alcohol; Textilana, ibid. θ Alkyl acid phosphate derived from ethoxylated lauryl 5 alcohol; Emery Industries Inc. τ Prepared as described in Preparation 5.

* Calcd. on dry weight of wood wafers.

Example 8 A further series of particle board samples was prepared using the same phosphate release agents and procedure employed in Example 7 but at lower levels of concentration in the binder resin combination. The various components and the proportions thereof (all parts by weight) are shown in Table 8 below together with the physical pro15 perties determined on certain of the samples. All the samples could be demolded without damage to the board or significant adhesion to the mold plates. The samples prepared using the higher concentrations of phosphate release agent slid out from between the mold plates when demolded whereas some of those prepared using the lower concentrat- · ions of phosphate release agent (00, QQ, and UU) required assistance, e.e. tapping of the mold plates, in order to effect release. All the samples has a thickness of 1/2 (12.7 mm) in the final board. co W XI Oi τι μ (0 ο CQ - 46 tf tf tf tf XI XI Ό Φ β μ φ -μ rt Ο ο to cm co ττ σι α> m Ο Ο to co cm co τρ tn σι Ο O tO 03 cm co Tf in σ Ο O to co cm co tt in σ Ο O to co cm co tt in σ Ο O to co cm co Tf tn σ co Ο O to co · CM CO Tf in CM σ co co Ο O to co · CM oo Tf in Tf σ Ο O to co CM CO Tf m σ Ο O to co CM CO Tf in σ Ο O to co cm co *ί· in σ Ο O to co cm co Tf in σ CM CM rd rd in I to CD H cn cn CM Γ* rd Γto m co rO to rd CM to rd to m cn 01 tf •ri id rd 0 • □ Φ m rt X 4J , CM o tf £ rt in c ♦td β tf μ rij CM 0 0} rt Φ in tf O ε Φ in tf μ >1 01 •μ CM rd +1 CM •rd Φ ϋ rt rt tn Φ Φ to ··—·. rd rt 4J 0 2 Γ tn r- tn Γ* r- Χί 0 rt 05 Φ ϋ μ μ ϋ o tf 0 £ •id ε 'd rt , φ • Φ • rt • Φ 05 rt Ό >1 rt φ Md •μ X •μ X Ud X Ό 0 Md o , rd 05 τ? >1 W 05 H 05 tf >1 H •H Χί 0 4J 0 Ό μ ο *—* Ο *—* μ *-* μ tf μ £ 2 tf tf tf Ed £h TABLE 8 (continued) Ό k fl CQ CM O Ν' Ν* fl υ •rt fl >1 fi ft Eh z Eh Z rt ϋ Qi rt •rt CO fl G Φ O CP fi a o ιΛ KO N co N· O co •rt fl rt ft fl Φ 3 k rt 3 3 rt Ό ft fl ft rrt fl rt «* CO G 0 O k •rt rt rrt Φ fl *0 •rt rt ft 3 ϋ G frt •rt *-*· •rl ·» 3 rt Ό *0 fl •rt fl G fl 0 fl fl fl k 0 fl X irt ft ft O Λ ft CM Φ CM - 48 Footnotes to Table 8 1 Percent P in combination of polyisocyanate and phosphate. n Tests carried out in accordance with ASTM 1037-72.

N.T. = material not tested.

Example 9 This example illustrates the use of a binder resin combination in accordance with the invention in association with a phenol-formaldehyde resin binder of the prior art.

All of the samples (1/2, 12.7 mm thickness) were prepared using the procedure described in Example 1, with the exceptions detailed below, and using the reactants and proportions (all parts by weight) set forth in Table 9. Xn the case of Boards YY and ZZ the phenol-formaldehyde resin was incorporated in the emulsion of the isocyanate whereas, in the case of Board AAA, the chips were sprayed firstly with the indicated amount of added water, then with the phenol-formaldehyde resin and finally with the polyisocyanate. In the case of control Board BBB the chips were sprayed with water and then with phenol-formaldehyde resin. The Boards XX and ZZ showed no significant adhesion to the mold plates after molding whereas serious adhesion problems where encountered in the case of Boards YY, AAA, and. BBB. The physical properties of the various boards are also shown in Table 9, from which it will be seen that the properties of Boards XX and ZZ, both within the scope of this invention, are clearly superior to those of Boards YY, AAA and BBB all of which are outside the scope of the invention. - 49 1920 1920 1920 1920 1920 CM CM O OQ rM I rM O o ID co kD oo σ\ h O oo oo σ) *3· Ο co «χ» . · r-ί CJ Ο O w id co (Τ'- rM CM o co kD σι ’«f kD O CJ CM O') in in κ m in r-1 tn rM in in rM m iTi rM c -H Ul 0 Φ +j TJ ε fd if] >1 fd -P XJ CU XJ w c cu •ri Φ Φ UJ X TJ tn 0 ϋ rM Φ fd XJ fd -μ cu q ε fd tn 0 •ri μ C μ C μ ω 0 fd φ •H >1 Ul cu μ UM >, P >4 cu rM Ή φ 1 o fd UM fl fi -μ i-M 0 x~. ί Ή rM •r) ϋ nJ 0 « rM UJ > μ £ c •μ TJ rM μ 0) TJ Φ >5 • β □ P 0 * ♦C rM X TJ ε 0 fi Λ 0 a TJ w £ s r-M iU CM m O > m m r- · CO r-M in O r* m m r* · co rM in in CM O Op- in m r* · m r-i m O t*· m in P* · M rM in in O • in r* in c CO PrM in - 50 ft ft Ο ΓΓΓΗ Ο ΓΟ ΓΟ ΓΗ CTL Ο LO Ο · Η Ο Ό φ C Ή 4J ο ϋ co ΓΗ ι—I ΓΟ ιη ΓΗ rH ΓΗ ι-Η ι—3 Ο ιη w ft co < Eh Ο ΓΗ ΓΟ ιη ιη ΓΟ co Μ1 ιη ΓΗ Ο ιη · j—ί Η γΗ ιη οο ιο ω ιο Ο ΓΗ οο Ο ιη · rH rH ω xJ Μ (0 ο « ο ο ιη Γ* Ο «-Η Γ* · rH rd 537.8 441.3 420.6 344.7 151 ω φ Ή +J Μ Φ ft μ ft γΗ Φ ϋ τΗ ϋϊ >ι ft m ϋ ft >1 •Ρ Ή Φ Q Φ μ +> ft ft ΜΗ >ι -μ •Η ϋ τΗ fl Γ0 •Η (0 ft ι—I φ ΜΗ X Ο Τ5 •rH to (0 ♦rH 3 to fl 3 CO γΗ ft ft t-H ft Γ0 3 3 S Ό Ό \ 0 0 tP 2 2 44 -3* -tf fl ft Ό to 3 fl 3 0 ft O ft ft rH rH fl fl 3 3 μ μ Φ 0) -μ P 3 3 ‘«Η τΗ >1 ft μ Φ Ω £ -tf in ♦Η (0 ft - 51 *· PB-65: Borden; aqueous suspension, 50% solids. 2 Aqueous solution: sodium salt of styrene-maleic anhydride copolymer; 30% solids: Monsanto. o Prepared as described in Preparation 4. 4 Tests carried out in accordance with ASTM-1037-72. c Test carried out in accordance with German V-100 specifications.

Calcd. on dry weight of wood particles.

Claims (17)

1. CLAIM S:1. A process for the preparation of particle board wherein particles of organic material capable of being compacted are contacted with a polyisocyanate and the treated 5 particles are subsequently formed into boards by the application of heat and pressure, which process comprises contacting said particles, in addition to the treatment with said polyisocyanate, with from 0.1 to 20 parts, per 100 parts by weight of said polyisocyanate, of a phosphate selected from:. 10 (a) acid phosphates of the formulae Ϊ i RO-P—OH and (RO) „P-OH I OH (I) (II) and the ammonium, alkali metal and alkaline earth metal salts thereof; (b) pyrophosphates derived from the acid phosphates (I) and (II) and mixtures of (I) and (II) and, as herein defined; (c) The 0-monoacyl derivatives of the acid phosphates (I) and (II) having the formulae KO P —QC OR 3nd (RO) 2 P-OCOR 1 OH (V) (VI) - 53 (d) carbamoyl phosphates having the formula t R-NHCO— O-P (OR) I OH (VII) and the ammonium, alkali metal and alkaline earth metal salts of the compounds of formula (VII); 5 (e) branched polyphosphates of the formulae t f RO— P— 0-P (OR) _ I O—P (OR) 2 i (VIII) and 0 0 0 t f ί (R0) 2 Ρ—0 — Ρ— 0 —P (OR) 2 ί o-P (OR) 2 (IX) (f) polyphosphates corresponding to the general formula - 54 /rop— Ο? η (X) including the cyclometaphosphates ( η = 3) ; and (g) mixtures of two or more of said compounds; wherein, in the various formulae shown above, each R is independently 5 alkyl having up to 35 carbon atoms, inclusive, alkenyl having up to 35 carbon atoms, inclusive or a group of general formula: R' — (0 — CH — CH -p I I A B wherein R' is alkyl having up to 35 carbon atoms, inclusive, 10 one of A and B represents hydrogen and the other is hydrogen or methyl, and n is a number having an average value from 1 to 5; R^ is hydrocarbyl having up to 12 carbon atoms, inclusive; R 2 is a hydrocarbyl group having up to 12 carbon atoms or a hydrocarbyl substituted by at least one 15 additional t —NHCOO—P (OR) 2 group wherein R has the significance defined above; and n is an integer.

2. The process of Claim 1 wherein said polyisocyanate is a polymethylene polyphenyl polyisocyanate con20 taining from 25 to 90 percent by weight of methylenebis(phenyl isocyanate), the remainder of said mixture being - 55 oligomeric polymethylene polyphenyl polyisocyanates of functionality greater than 2.

3. The process of Claim 2 wherein the polymethylene polyphenyl polyisocyanate contains from 35 to 65 per5 cent by weight of methylenebis(phenyl isocyanate).

4. The process of Claim 1 or Claim 2 wherein said phosphate is a mixture of lauryl diacid phosphate and dilauryl monoacid phosphate.

5. The process of Claim 1 or Claim 2 wherein said 10 phosphate is a pyrophosphate derived by removal of water of condensation from a mixture of lauryl, diacid phosphate and dilauryl monoacid phosphate.

6. The process of Claim 1 or Claim 2 wherein said phosphate is a mixture of oleyl diacid phosphate and 15 dioleyl monoacid phosphate.

7. The process of Claim 1 or Claim 2 wherein said phosphate is a pyrophosphate derived by removal of water of condensation from a mixture of oleyl diacid phosphate and dioleyl monoacid phosphate. 20

8. The process of any preceding claim wherein the particles employed in the preparation of said particle board are wood chips.

9. The process of any preceding claim wherein said polyisocyanate and said phosphate are applied simultaneously 25 to said particles in the form of an aqueous emulsion.

10. The process of Claim 9 wherein said aqueous emulsion of polyisocyanate also comprises an emulsifying agent.

11. The process of any Claims 1 to 8 wherein said particles are contacted separately with said polyisocyan48542 ate and said phosphate. 11 wherein said poly- » each employed in the 11 or Claim 12 wherein water prior to being

12. The process of Claim isocyanate and said phosphate are form of an aqueous dispersion. 5

13. The process of Claim said particles are contacted with contacted with said polyisocyanate and said phosphate.

14. A storage stable composition suitable for use as a binder in the manufacture of particles board comprising a mixture of 10 (a) a polymethylene polyphenyl polyisocyanate containing from 25 to 90 percent by weight of methylenebis(phenyl isocyanate) the remainder of said mixture being oligomeric polymethylene polyphenyl polyisocyanates having a functionality higher than 2.0; and 15. (b) from 0.1 parts by weight to 20 parts by weight, per . 100 parts by weight of saidpolyisocyanate, of a pyrophosphate derived by removal of water of condensation from at least one acid phosphate having one of the formulae: 0 0 t t RO— P— OH and (RO)-P—OH I OH 20 wherein each R is independently alkyl having up to 35 carbon atoms, inclusive, alkenyl having up to 35 carbon atoms, inclusive or a group of general formula: - 57 R'- (Ο — CH— CH -H I I A B wherein R' is alkyl having up to 35 carbon atoms, inclusive, one of A and B represents hydrogen and the other is hydrogen or and methyl, and n is a number having an average 5 value from 1 to 5, and mixtures of two or more of said acid phosphates.

15. A composition according to Claim 14 wherein the pyrophosphate is derived from a mixture of lauryl diacid phosphate and dilauryl monoacid phosphate. 10

16. A composition according to Claim 14 wherein the pyrophosphate is derived from a mixture of oleyl diacid phosphate and dioleyl monoacid phosphate.

17. A composition according to Claim 14 which also comprises an emulsifying agent. 15 tS. A process according to Claim 1 substantially as described with reference to any one of the Examples.