FI68648C - FOER FARING FOER FRAMSTAELLNING AV SPAONSKIVOR SAMT BINDEMEDELSKOMPOSITION FOER UTOEVANDE AV FOERFARANDET - Google Patents

Description

Ιΰήτ · Ί ΓΒ1 Μ \ ANNOUNCEMENT * a * λ n lBJ (11) UTLÄGGNINGSSKRIFT 0 0 040 C (45) Γλtentti issued 10 10 1925 (51) Kv.lk.7lnt.CI.4 C 09 J 3/16, C 08 L 75/0 **, B 27 N 1/02 FINLAND —FINLAND (21) Patent application - Patentansökning 792872 (22) Date of application - Ansökningsdag 1 A. 09.79 (* = 1) (23) Starting date - Giltighetsdag 1 A. 09-79 (41) Made public - Blivit offentlig 30.03.80

National Board of Patents and Registration / 44) Date of publication and publication. - 28.06.85

Patent and registration authorities Ansökan utlagd och utl.skriften publicerad (32) (33) (31) Claim claimed privilege — Begärd priority 29-09.78 Ο3.Ο5.79 USA (US) 9 ** 7209, 356A7 (71) The Upjohn Company , 301 Henrietta Street, Kalamazoo, Michigan, USA (72) Alexander McLaughlin, Meriden, Connecticut, Reinhard Hans Richter,

North Haven, Connecticut, Harold Eugene Reymore, Richmond, Virginia, USA (US) (7 **) Berggren Oy Ab (5 **) Method for the production of particle board and the binder mixture for the implementation of the method - Förfarande för framstä11 Ning sp spansskivor samt bindemede1skomposition för utövande av förfarand

The present invention relates to a method for manufacturing particle boards and to a binder mixture for carrying out the method.

Organic polyisocyanates, in particular toluene diisocyanates, methylene bis (phenyl isocyanates) and polymethylene polyphenyl polyisocyanates, are currently used on a large scale in the manufacture of particle board as one of their constituents or binders, see e.g. U.S. Pat. 557,263, 3,636,199, 3,870,665, 3,919,017 and 3,930,110.

In the conventional method, the binder resins are optionally added in the form of a solution or aqueous suspension or emulsion to particles of cellulosic material or other types of material capable of forming sheets of particles, such as particle boards, or mixed with them using various mixing equipment or other mixing methods. The mixture of particles and binder is then formed into a web and is heated and pressed using heated press plates. The method can be carried out intermittently or continuously. In order to prevent the thus formed sheet from adhering to the heated sheets, it has previously been necessary to fit a sheet 68648 impermeable to isocyanate between the chipboard surface and the pressboard during the manufacturing process, or to coat the pressboard surface with a suitable release agent before each treatment, or grab the disc. Each of these alternatives, especially if the production is carried out continuously, is laborious and this is a disadvantage in other respects to the very satisfactory method of producing particle boards with good strength properties.

We have now found that the above-mentioned disadvantages of using organic isocyanates as binders for particle board can be reduced in a very satisfactory manner by adding certain phosphorus-containing compounds as internal release agents in the isocyanate mixtures then used. U.S. Patent 4,024,088 discloses the addition of phosphorus-containing compounds as internal release agents in the preparation of polyether polyurethanes. We have found that the phosphorus-containing compounds disclosed in this publication are not suitable for use in the process of the present invention.

The present invention relates to an improved method of making particle boards by contacting particles of organic material which can be compressed with a polyisocyanate and then forming the treated particles into sheets using heat and pressure, which method is characterized by contacting said particles with about 0.1 in addition to polyisocyanate treatment. -20 parts by weight, per 100 parts by weight of polyisocyanate, a phosphate consisting of an acid phosphate of the formula

0 O

t t

RO -P -OH or (RO) ~ P-OH

OH

(I) (II) or a mixture thereof or a pyrophosphate derived from an acid phosphate (I) or (II) or a mixture thereof, wherein R is alkyl having 8 to 35 carbon atoms, alkyl having 8 to 35 carbon atoms or a group R * - (OCH 2 (^ 2 + - ^ -, where R 'is alkyl of 8 to 35 carbon atoms and n is a number having an average of 1-5.

3,68648

The invention also encompasses novel storage-resistant binder compositions comprising a composition comprising (a) polymethylene polyphenyl polyisocyanate containing about 25-90% by weight methylene bis (phenyl isocyanate), the remainder of the mixture being oligomeric polymethylene polyphenyl -polyisocyanates having a functionality greater than 2.0 and (b) about 0.1 to 20 parts by weight, per 100 parts by weight of polyisocyanate, pyrophosphate obtained by removing condensation water from at least one acidic phosphate having formula

0 O

t ΐ

RO-P-OH or (R0)., P-OH

1 2

OH

or a mixture of two or more such acidic phosphates, wherein R is alkyl having 8 to 35 carbon atoms, alkenyl having 8 to 35 carbon atoms or a group R '- (O-CH 2 -CH 2 O-) -, wherein R' is a group having 8 to 35 carbon atoms. alkyl and n is a number averaging 1-5.

The term "alkyl having 8 to 35 carbon atoms" means a saturated *, polyvalent, aliphatic straight-chain or branched radical having a specified number of carbon atoms in the molecule. Such groups include, for example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, docosyl, tricosyl, pentacosyl, hexacosyl, heptacosyl, heptacyl. and the like, including isomeric forms thereof.

The term "alkenyl having from 8 to 35 carbon atoms" means a monovalent straight or branched aliphatic radical having at least one double bond and having a specified number of carbon atoms in the mold. Typical of such groups are octenyl, nonenyl, desenyl, undesenyl, dodecenyl, tridenesyl, tetradesenyl, pentadesenyl, hexadesenyl, hepta-desenyl, octadenyl, nonadesenyl, icosenyl, henico-senyl, docosenyl, tricosenyl, pentacenyl, pentacenyl, pentatriacontin and the like, including their isomeric forms.

4,68648

The term "pyrophosphate derived from acid phosphate (I) or (II) or a mixture thereof" means the following. Acidic phosphates (I) and (II) are generally prepared as mixtures of monohydrogen phosphate (II) and dihydrogen phosphate (I), which mixtures are prepared by a reaction using the corresponding alcohol RÖH, where R is as defined above, and phosphorus pentoxide per se from this field. using well known methods, see e.g. Kosolapoff: Organophosphorus Compounds, pp. 220-221,

John Wiley and Sons, Inc., New York, 1950. A mixture of the monohydrogen phosphates thus obtained can be separated, if desired, e.g., by fractional crystallization of barium and the like salts, as described in the above-mentioned publication. Separate acid phosphates or mixtures of the two phosphates can be used in the process of the invention. Pyrophosphates (III) and (IV) are readily obtained from the corresponding acid phosphates (II) and (I) by the latter reaction with a dehydrating agent such as carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates, N, N'-dihydrocarbylcarbodiimides and the like. using methods well known in the art, see, e.g., 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. 8j0, 6204 (1958); F. Ramirez, J.F. Marecek and I. Ugi; JACS 9_7, 3809 (1975). The individual acid phosphates (I) and (II) may be converted separately to the corresponding pyrophosphates, or mixtures of both types of acid phosphates (I) and (II) may be converted to the corresponding pyrophosphate mixtures.

In the case of acid phosphates of the above formula (II), the corresponding pyrophosphates are those of the formula

O O

T t (RO) 2P - o — P (OR) 2 (III) wherein R is as defined above. In the case of acid phosphates of the formula (I), the corresponding pyrophosphates are complex mixtures whose average composition can be given by the formula 5 68648 ο Γ o ΐ Ί 'HO-P - O-P - OH (IV)

I I

OR OR

L Jx wherein x is a number with an average value of 1 or greater and R is as defined above.

The process according to the invention is carried out mainly using methods previously described in the art in which an organic polyisocyanate is used as a binder resin or a component of this resin (see e.g. German Patent Application 2610552 and U.S. Patent 3,428,592), with the notable difference that said phosphate is used in combination with an isocyanate mixture used to treat the particles that are joined together to form a particle board.

Thus, a particle board is made according to the invention by joining together particles of wood or other cellulosic or organic material which can be compressed by heat and pressure in the presence of a binder system comprising a combination of an organic polyisocyanate and a phosphate as defined below.

The polyisocyanate and phosphate release agent may be contacted with the particles as separate, individual components, or in a more preferred embodiment, the polyisocyanate and phosphate are contacted with the particles either simultaneously or after mixing. If the polyisocyanate and phosphate are added separately or as a mixture, they can be used as such, 68648 6 i.e. without diluents and solvents, or one or both of them may be used in the form of aqueous dispersions or emulsions.

The polyisocyanate component of the binder system may be any organic polyisocyanate containing at least two isocyanate groups in the molecule. Typical organic polyisocyanates include diphenylmethane diisocyanate, m- and p-phenylenediisocyanates, chlorophenylene diisocyanate, α, α-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, and mixtures of the two isomers, marketed, triphenylmethane triisocyanates, 4,41-diisocyanatodiphenyl ether and polymethylene polyphenyl polyisocyanates. The latter polyisocyanates are mixtures containing about 25 to 90% by weight of methylene bis (phenyl isocyanate), the remainder being poly-methylene-polyphenyl polyisocyanates having a functionality greater than 2.0. Such polyisocyanates and methods for their preparation are well known in the art, see, e.g., U.S. Patents 2,683,730, 2,950,263, 3,012,008, and 3,097,191. Such polyisocyanates are also available in a variety of modified forms.

One such form comprises polymethylene polyphenyl polyisocyanate, which is generally heat treated at a temperature of about 150-300 ° C until the viscosity (at 25 ° C) has risen to about 800-1500 cP. Another modified polymethylene polyphenyl polyisocyanate is one that has been treated with minor amounts of epoxide to reduce its acidity in accordance with U.S. Patent 3,793,362.

Polymethylene polyphenyl polyisocyanates are the most preferred polyisocyanates that can be used in the binder systems of the invention. Highly preferred polymethylene polyphenyl polyisocyanates are those containing about 35-65% by weight of methylene bis (phenyl isocyanate).

When an organic polyisocyanate is used in a binder system in the form of an aqueous emulsion or dispersion in accordance with the invention, the aqueous emulsion or dispersion may be prepared using any technique known in the art for preparing aqueous emulsions or dispersions prior to use of the binder composition. For example, the polyisocyanate can be dispersed in water in the presence of an emulsifier. The latter may be any emulsifier known in the art, including anionic and nonionic agents. Typical nonionic emulsifiers include polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more of the monomers ethylene oxide, propylene oxide, butylene oxide and styrene, alkoxylated alkyloxyalkylene phenols, such as nonylphenoxy) (nonylphenoxy) such as ethoxylated and propoxylated aliphatic alcohols having from about 4 to about 18 carbon atoms, glycerides of saturated and unsaturated fatty acids, such as glycerides of stearic acid, oleic acid and castor oil acid polyamide acids, and the like, fatty acids such as stearic, lauric, lauric, lauric, lauric, lauric. such as dialkanolamides derived from, for example, fatty acids such as stearic, lauric, oleic and the like. A detailed list of such products is given in the 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 before its use as a binder mixture, but is preferably carried out within about 3 hours before use. Any method known in the art for preparing aqueous emulsions can be used to prepare the aqueous polyisocyanate emulsions used in the method of the invention. Usually, the emulsion is formed by bringing the polyisocyanate, emulsifier and water together under pressure using a conventional spray device in which streams of water and polyisocyanate collide and mix under turbulent conditions in the mixing chamber of the spray device. The emulsion thus formed is removed in the form of a spray applied to the cellulosic particles to be treated which are present in the raw material of the sheet, as described below.

As mentioned above, the phosphate release agent can be contacted with the particles as a separate component, in which case it is used as such, i. without diluents, or in the form of an aqueous solution or dispersion. The phosphate is preferably added either as such or in diluted form when used alone, i. separately from the polyisocyanate, in the form of a spray. However, according to a preferred embodiment of the invention, 8,63648 phosphate release agent and polyisocyanate are used together as a simple mixture. This can be done in several ways. Thus, when the polyisocyanate is used as a binder resin without diluents such as water, the phosphate release agent can be combined with the polyisocyanate by simple mixing. When the polyisocyanate is used as a binder resin in the form of an aqueous emulsion, the phosphate release agent may be added as a separate ingredient during or after the formation of the emulsion, or according to a highly functional embodiment, the phosphate is premixed with the organic polyisocyanate before emulsifying the latter. Thus, the organic polyisocyanate and phosphate release agent can be premixed and stored for any desired period prior to emulsion formation. When a further emulsifier is used to prepare the emulsion, this substance can also be combined with a mixture of an organic polyisocyanate and a phosphate release agent to form a storage-stable mixture that can be converted at any time to an aqueous emulsion for use as a binder resin simply by adding water.

When a polyisocyanate is used as a binder in the form of an aqueous emulsion, the amount of organic polyisocyanate in said aqueous emulsion is preferably in the range of about 0.1 to 99% by weight and even more preferably in the range of about 25 to 75% by weight.

When the phosphate release agent is added as a separate ingredient or in combination with a polyisocyanate, the amount of phosphate release agent used is in the range of about 0.1 to 20 parts by weight per 100 parts of polyisocyanate, and preferably in the range of about 2 to 10 parts by weight per 100 parts by weight of polyisocyanate. The amount of emulsifier required to make the aqueous emulsion is not critical and will vary depending on the emulsifier used, but will generally be in the range of about 0.1 to 20% by weight based on the polyisocyanate.

The raw material for particle board comprises particles of a cellulosic material or similar material that can be compressed and bonded together to form boards. Typical of such materials are wood particles derived from wood processing wastes such as sawdust, plywood chips, etc. Particles of other cellulosic material such as torn paper, pulp and vegetable fibers such as corn straw, grass, bagasse, etc. and non-cellulose 9 containing materials such as polyurethane waste, polyisocyanurate waste and the like polymer foams can also be used. Methods for making suitable particles are well known and conventional. If desired, mixtures of particles of cellulosic substances can be used. Particleboard can be advantageously made, for example, from wood component mixtures which always contain about 30% bark.

The moisture content of the particles may preferably be in the range of about 0-24% by weight. Typically, particles made from wood processing waste contain about 10-20% moisture and can be used without pre-drying.

The particle or particle board is made by spraying the particles with the ingredients of the binder mixture, either individually or in combination, while mixing these particles in a mixing device or any mixing equipment. The binder system is usually added in an amount of about 2-8% by weight (excluding the water contained therein) based on the dry weight of the particles, but either higher or lower amounts of binder resin may be used if desired. If desired, other substances such as waxy adhesives, flame retardants, pigments, etc. can also be added to the particles during the mixing step.

After sufficient mixing to provide a homogeneous mixture, the coated particles are formed into a loose mat or web, preferably containing moisture at about 4-18% by weight. Such a mat is then fitted between the heated press plates and pressed to secure the particles to the shape of the plate. Compression times, compression temperatures, and pressures vary widely depending on the thickness of the sheet produced, the desired density of the sheet, the size of the particles used, and other well-known factors. By way of example, however, it can be mentioned that in the production of a medium-thickness 12.7 mm sheet, conventional pressures are 2.5-5.0 MPa and temperatures are 163-191 ° C. The pressing time is usually 2-5 minutes. A portion of the moisture in the sludge mat or web reacts with the polyisocyanate to form a polyurea, as previously discussed, the moisture content of the mat or web is not important with isocyanate binders unlike some other binder systems.

The method described above can be carried out periodically, i. the individual particleboards can be formed by treating a suitable amount of particles with a binder resin and heating and compressing the thus treated material. The treatment can also be carried out continuously by passing the treated particles in the form of a continuous web or mat through a heating and pressing zone formed by an upper and a lower continuous steel pressing belt, through which the required heat and pressing are provided.

Whether the process according to the invention is carried out intermittently or continuously, it has been found that the chipboard produced using the combination of polyisocyanate and phosphate release agent according to the invention is easily released from the metal surfaces of used press plates and has no tendency to adhere to these plates. This is not the case in previous methods when polyisocyanate alone is used as the binder resin, as described above.

Although any of the phosphate release agents defined above may be used either alone or in combination in the process of the invention, it is preferable to use pyrophosphates (III) and (IV) or mixed pyrophosphates derived from mixtures of acid phosphates (I) and (II). Thus, the free hydroxyl groups present in pyrophosphates, or any free hydroxyl groups present in the form of a constant acid phosphate starting material, are generally sufficiently prevented from reacting at ambient temperatures with the polyisocyanate used in the process of the invention without the polyisocyanate. that the mixture deteriorates or is damaged in any way. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and used in the process of the invention, it is assumed that the processing temperature and the steam generated by the chipboard cause hydrolysis of the pyrophosphate, regenerating the corresponding acid phosphates, which then contribute to the chipboard detachment.

It is to be understood that the latter theory is presented in a descriptive sense only and does not limit the invention in any way.

As mentioned above, the monohydrogen phosphates (II) and dihydrogen phosphates (I) and their salts used in the process of the invention are obtained by conventional methods, such as by reacting the corresponding alcohol RÖH, where R is as defined above, with phosphorus pentoxide, See Kosolapoff , ibid. Like the industry

II

It will be apparent to those skilled in the art that when mixtures of two or more different alcohols are used in the above reaction, it is possible to obtain a corresponding mixture of phosphates (I) and / or (II) in which the various components of the mixture have different R-values. As indicated above, the mixture of mono- and di-hydrogen phosphates obtained in the above reaction can be separated into its separate components by conventional methods such as fractional crystallization and the like, and the separate components thus obtained can be used in the process of the invention. Alternatively and preferably, the mono mixture of dihydrogen phosphates obtained in the above reaction can be used as such without separation into its components in the process of the invention, or can be converted to the corresponding mixture of pyrophosphates using the above methods, the latter mixture then used in the process.

Typical acid phosphates of formula (I) above which may be used alone or in combination with other acid phosphates in the process of the invention include: mono-O-octyl, mono-O-nonyl, mono-O-Decyl, mono-O- undecyl, mono-O-dodecyl, mono-O-tridecyl, mono-O-tetradecyl, mono-O-pentadecyl, mono-O-hexadecyl, mono-O-heptadecyl, mono-O-octa-Decyl, mono-O- nonadecyl, mono-O-icosyl, mono-O-henicosyl, mono-O-docosyl, mono-O-tricosyl, mono-O-pentacosyl, mono-O-hexacosyl, mono-O-heptacosyl, mono-O-octacosyl, mono-O-nona-cosyl, mono-O-triacontyl, mono-O-pentatriacontyl, mono-O-dodecenyl, mono-O-tridecenyl, mono-O-tetradecenyl, mono-O-pentadecenyl, mono- O-hexadecenyl, mono-O-heptadecenyl, mono-O-octadecenyl, mono-O-nonadecenyl, mono-O-icosenyl, mono-O-henicosenyl, mono-O-docosenyl, mono-O-tricosenenyl, mono-O-pentacosenyl, mono-O-triacontenyl and mono-O-pentatriacosenyl-di- hydrogen phosphates, and di-hydrogen phosphates in which the esterification radical is derived from lauryl and the like monohydric alcohols having about 1-5 moles of ethylene oxide at the terminal position.

Typical acid phosphates of the above formula (II) which may be used alone or in combination with other acid phosphates in the process of the invention are the following: Ο, Ο-di (octyl), Ο, Ο-di (nonyl), Ο, Ο- di (decyl), Ο, Ο-di (undecyl), Ο, ο-di (dodecyl), Ο, Ο-di (tridecyl), Ο, Ο-di (tetradecyl), 0,0-di (pentadecyl), Ο, Ο-di (hexadecyl), Ο, Ο-di (heptadecyl), 0.0-1268648 di (octadecyl), O, O-di (nonadecyl), O, O-di (icosyl), 0.0 -di (hexosyl), 0,0-di (docosyl), O, O-di (tricosyl), 0,0-di (pentacosyl), O, O-di (hexacosyl), 0,0- di (heptacosyl), 0,0-di (octacosyl), 0,0-di (nonacosyl), 0,0-di (triacontyl), 0,0-di (pentatriaconyl), 0,0-di (dodecenyl), O, O-di (tridecenyl), 0,0-di (tetradecenyl), 0,0-di (pentadecenyl), O, O-di (hexadecenyl), 0,0-di- (heptadecenyl) ), 0.0-di (octadecenyl), 0,0-di (nonadecenyl), 0,0-di (icosenenyl), 0,0-di (henocenyl), 0,0-di (docosenyl), 0,0 -di (tricosenyl), 0,0-di (pentacosenyl), 0,0- di (triacontenyl and 0,0-di (pentatriacosenyl) monohydrogen phosphates and diesterified monohydrogen phosphates in which the esterification radical is derived from lauryl and the like monohydric alcohols having about 1-5 moles of ethylene oxide at the terminal position. Typical phosphates on the market of the latter type, sold in admixture with the corresponding dihydrogen phosphates, are those marketed under the trademark "Tryfac" by Emery Industries Inc.

Typical pyrophosphates of formula (III) which may be used alone or in combination with other pyrophosphates in the process of the invention are: tetraoctyl, tetranonyl, tetradecyl, tetraundecyl, tetradodecyl, tetra (tridecyl), tetra (tetradecyl), tetra ), tetra- (hexadecyl), tetra (heptadecyl), tetra (octadecyl), tetraononadecyl), tetra (icosyl), tetra (henicosyl), tetra (docosyl), tetra (tricosyl), tetra (pentacosyl), tetra ( hexacosyl), tetra- (heptacosyl), tetra (octacosyl), tetra (nonacosyl), tetra (triacontyl, tetra (pentatriacontyl), tetra (dodecenyl), tetra (tri-decenyl), tetra (tetradecenyl), tetra (pentadecenyl), tetrahexadecenyl), tetra (heptadecenyl), tetra (octadecenyl), tetra- (nonadecenyl), tetra (icosenyl), tetra (henicenyl), tetra- (docosenocyl), tetra (tricenenyl), tetra (pentacosenyl), tetra- ( triancontenyl) and tetra (pentatriacosenyl) pyrophosphates.

Typical pyrophosphates of the above formula (IV) which may be used alone or in combination with other pyrophosphates in the process of the invention are: di (octyl), di (nonyl), di (decyl), di (undecyl), di (dodecyl), di (tridecyl), di (tetradecyl), di (pentadecyl), di (hexadecyl), di (heptadecyl), di (octadecyl), di (nonadecyl), di (icosyl), di- (henicosyl), di (docosyl) , di (tricosyl), di (pentacosyl),

II

68648 di (hexacosyl), di (heptacosyl), di (octacosyl), di (nonacosyl), di (triacontyl), di (pentatriacontyl), di (dodecenyl), di (tridecenyl), di (tetradecenyl), di ( pentadecenyl), di- (hexadecenyl), di (heptadecenyl), di (octadecenyl), di- (nonadecenyl), di (icosenyl), di (henocenyl), di (docosenoyl), di (tricenenyl), di (pentacosenyl) ), di (triacontonyl) and di (pentatriacosenyl) pyrophosphates.

According to another embodiment of the invention, it has been found that the combination of polyisocyanate and phosphate release agent used as a binder in the process of the invention can be used in combination with thermosetting resin curing agents previously used in the art, e.g. phenol-formaldehyde, resorcinol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, urea-furfural and condensed furfuryl alcohol series. The use of such a combination not only eliminates the adhesion problems of the finished particleboards to the presses previously encountered when using a mixture of isocyanate and the above-mentioned type of curable resin binder, but also the physical properties of the particleboards thus obtained are considerably better.

The following manufacturing methods and examples illustrate the invention and its method of implementation and the best embodiment of the invention identified by the inventors.

Method of manufacture 1

Preparation of pyrophosphate from lauric acid phosphate

A mixture of 70 g of lauryl hydrogen phosphate (a mixture of 0,0-dilauryl monohydrogen phosphate and O-lauryl dihydrogen phosphate, Hooker Chemical 68648

Company) and 60 g of phenyl isocyanate were passed into a dry flask equipped with a stirrer, condenser and drying tube, and the flask was immersed in an oil bath preheated to 80 ° C and the contents of the flask were stirred while the oil bath temperature was slowly raised to 115 ° C. Carbon dioxide evolved within about 1 hour. When the 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 thus recovered (24.8 g of N, N'-diphenylurea) was washed with chloroform. The combined filtrate and washings were concentrated on a rotary evaporator at a bath temperature of 50 ° C. After most of the solvent had evaporated, crystals of N, N ', N "-triphenylburea separated and the evaporation was stopped to separate this solid (6.6 g) by filtration. The filtrate was evaporated to dryness and finally treated under reduced pressure at 50 ° C with excess phenyl isocyanate. The residue (70 g) was the desired colorless pyrophosphate in the form of a pale yellow liquid.The infrared spectrum of the product (in CHCl3) did not have streaks characteristic of P-OH bonds, but had a strong band at 940 cm which was characteristic of POP bonds. .

Manufacturing method 2

Preparation of pyrophosphate from lauryl hydrogen phosphate

A total of 70 g of lauryl hydrogen phosphate (the same starting material used in Production Method 1) was introduced into a flask equipped with a stirrer, a reflux condenser and a gas supply line, and heated under nitrogen at 65-75 ° C until melting. The melt was stirred while phosgene was slowly passed for a total of 2.5 hours. The temperature was maintained in the above range during the addition. Gas evolution from the reaction mixture was strong during the first hour of phosgene addition, but gradually subsided and was very slow at the end of the phosgene addition period. After the addition was complete, the mixture was purged with nitrogen for 15 hours while maintaining the temperature in the above range. After this time, the pressure in the reaction flask was gradually reduced to about 1.0 mm Hg to remove gaseous hydrogen chloride and carbon dioxide. The viscous residue thus obtained completely solidified when allowed to stand overnight. This gave 66 g of pyrophosphate as a solid which gradually melted at about 60 ° C.

I! 15 68648

Manufacturing method 3

Preparation of pyrophosphate from oleyl hydrogen phosphate

A mixture of 200 g of oleyl hydrogen phosphate (consisting of a mixture of O, O-dioleyl hydrogen phosphate and O-mono-oleyl hydrogen phosphate, marketed by Hooker Chemical Company) was reacted with 160 g of phenyl isocyanate at 85-90 ° C. 5.5 hours using Preparation Method 1. N, N'-Diphenylurea (68 g) was removed by filtration after diluting the reaction mixture with 200 ml of chloroform. The filtrate was concentrated on a rotary evaporator and excess unreacted phenyl isocyanate was removed by distillation under reduced pressure. The N, N ', N "triphenyl biuret crystallized from an oily residue while standing at room temperature. Removal of the crystals by filtration gave 196 g of a liquid product having a line in the infrared spectrum at a wavelength of 940 cm-1, which is characteristic of the POP lines but of the P-OH line. the line did not occur.

Manufacturing method 4

Manufacture of pyrophosphate from lauryl hydrogen phosphate

A solution of 30.4 parts by weight of lauryl hydrogen phosphate (same starting material as in Production Method 1) in 21 parts by weight of toluene was introduced into a dry reactor previously purged with nitrogen. The solution was heated to 40 ° C with stirring, at which point a solution of 7.6 parts by weight of polymethylene polyphenyl polyisocyanate / equivalent weight = 133, functionality 2.8, containing about 50% methylene bis (phenyl isocyanate) was added. The resulting mixture was stirred while the phosgene stream was added (about 0.1 parts by weight per minute) and the temperature was gradually raised to 80 ° C. The temperature was maintained at this level while continuously introducing phosgene until a total of 20 parts by weight of toluene was added. The total time of phosgene addition was 5 h 50 min The reaction mixture was heated at the same temperature for a further 40 min after the addition of phosgene before heating to 90-95 ° C and purged with nitrogen for 2 hours to remove excess phosgene The reaction vessel was then depressurized until toluene was refluxed. and purging with nitrogen was continued for an additional 2 hours.The toluene was removed in then by distillation under reduced pressure and its last residues were removed in vacuo. The residue was cooled to room temperature, treated with diatomaceous earth ("Celite 545") and filtered after stirring for 16,68648 for 30 minutes. This gave 23.7 parts by weight of a mixture of lauryl phosphate and polymethylene polyphenyl polyisocyanate, which was found to contain 6.08% w / w phosphorus.

Manufacturing method 5

Second Preparation of Pyrophosphate from Lauryl Hydrogen Phosphate Using the method described in Preparation 4, but replacing polymethylene polyphenyl polyisocyanate with an equimolar amount (6.8 parts by weight) of phenyl isocyanate, a second portion of lauryl pyrophosphate was obtained.

Example 1

A series of particleboard samples were prepared, using the following method, from the ingredients and amounts of ingredients (by weight) shown in Table 1 below.

The wood chips (Turner chips) were fed to a rotary mixing drum and this was rotated while spraying these particles with an aqueous emulsion containing polyisocyanate, water, phosphate and emulsifier. The emulsion was prepared by mixing its ingredients together in a "Turrex" mixer. The resulting emulsion was sprayed with a paint sprayer onto the wood particles while the drum was rotated for 45-120 sec to achieve homogeneity. The coated particles were formed into a mat measuring 30 x 30 cm using cold rolled steel sheets and a plywood making machine. After removal of the fabrication frame, steel bars with a thickness corresponding to the desired thickness of the final chipboard (6.4 mm) were fitted along opposite edges of the aforementioned steel sheet, and another 30 x 30 cm cold rolled steel sheet was fitted above the mat.

This whole arrangement was then fitted to the lower plate of the "Dake" press with a compressive force of 45,400 kg. Both plates of the press were preheated to the specified temperature shown in Table 1 below. The pressure was then increased and the shaping time shown in Table 1 was calculated from the time when the pressure applied to the mat reached 3.5 MPa. At the end of the shaping time shown in Table 1, the pressure was released and the chipboards were removed from the mold. In all cases, it was found that removal was easy and the disc did not tend to adhere to the discs with which it was in contact. This is in stark contrast to the behavior of particleboards made under the same conditions but without the use of lauryl hydrogen phosphate in the binder emulsion used to make the board.

The various samples of the chipboard thus prepared were then subjected to a series of physical experiments, and the properties thus determined are shown in Table 1. These properties show the excellent structural durability properties of the boards obtained.

TABLE 1

Plate A_B__C__p Materials used

Wood chippers 644 644 644 644

Weight of water in chips

Polyisocyanate1 19.2 19.2 19.2 19.2

Aqueous emulsion 51 51 51 51 2

Lauryl hydrogen phosphate 1.9 1.9 1.9 1.9 3

Emulsifier 0.1 0.1 0.1 0.1 x% w / w polyisocyanate 3 '° 3' ° 3 '° 3.0 x% w / w water 17 17 17 17 x% w / w phosphate 0 .3 0.3 0.3 0.3% w / w emulsified. .>, Mis „misaine 0.016 0.016 0.016 0.016

Press plate temperature, ° C 171 171 171 171

Design time, min 1.5 2.0 2.5 3.0

Physical properties

Density, g / cm 3 0.67 0.68 0.68 0.67 4

Refractive index: MPa 25.6 24.9 29.7 30.9 4 3

Modulus of elasticity: MPa x 10 3.47 3.26 3.73 3.75 4Dry strength: MPa 0.705 0.718 0.773 0.622 5Wet strength: MPa 0.16 0.165 0.165 0.16

Notes to Table 1

Polymethylene polyphenyl polyisocyanate: equivalent weight = 133; functionality 2.8; contained about 50% methylene bis (phenyl isocyanate).

2: Mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate:

Hooker Chemical Company.

Ethoxylated propoxylated butanol: "Witconol APEB": Witco Chemical Company.

3: 16 68648 4: Experiments were performed using the method ASTM-1037-72.

5: Experiments were performed using German V-100 conditions.

χ: Calculated on the dry weight of the wood particles.

Example 2

A series of particleboard samples were prepared using the method described in Example 1 and using the various ingredients and their amounts (all parts calculated by weight) shown in Table 2 below. The shaping time of samples E and F in the table is the time the mat was held under pressure (3, 5 MPa) after the internal temperature of the mat (determined by a thermometer fitted to it) had reached 54 ° C. Sample G was a control sample formulated as described in Example 1.

The physical properties determined for each final particle board are also shown in Table 2 and show the excellent structural strength of the different samples. All samples could be easily removed from the mold and did not adhere at all to the steel plates used in their manufacture.

TABLE 2

Levy_ E_F_G

Materials used

Wood chippers 644 644 644

Weight of water in chips

Polyisocyanate (such as e.g. 1) 21 42 21

Aqueous emulsion 56 56 56

Lauryl pyrophosphate "'

Emulsifier (as e.g. 1) 0.1 0.1 0.1 x% w / w polyisocyanate 3.3 6.6 3.3 x% w / w water 17.4 17.4 17.4 x% w / w weight pyrophosphate 0.33 0.65 0.33 x% w / w emulsifier 0.016 0.016 0.016

Press plate temperature, ° C 180 180 180

Design time, min 2 22

Physical properties

Density, g / cm -1 0.68 0.68 0.70 °

Fracture modulus: MPa 35.4 35.1 36.7 li 19 68648 TABLE 2 (cont'd)

Levy_E_____F _G

Physical characteristics (continued) 2 3

Modulus of elasticity: MPa x 10 3.49 3.53 3.60 2Dry strength: MPa 0.882 0.972 0.910 3Wet strength: MPa 0.22 0.26 0.21

Notes to Table 2

Prepared as described in Production Method 1.

2: The experiments were performed using the method ASTM 1037-72.

3: The experiments were performed using the conditions of the method German V-100.

χ: Calculated on the dry weight of the wood particles.

Example 3

A series of particleboard samples were prepared using exactly the same reagents and amounts as in Example 1 and using the method described in this example except that the press plates were preheated to 204 ° C and maintained at this temperature for various lengths of compression times shown in Table 3 below. the physical properties of the samples are also shown in Table 3 and it appears that all of these samples had excellent structural strength properties. None of the samples tended to adhere to the press plates during separation.

TABLE 3

Record H_I_J_K_L

Compression time, min 1.0 1.5 2.0 2.5 3.0

Physical properties

Density, g / cm2 0.67 0.67 0.68 0.67 0.67 1Fractive index: MPa 19.1 24.4 21.7 22.1 23.3 ^ Modulus of elasticity: MPa x 102 2.82 3.26 3.05 3.03 3.13 ^ Dry strength: MPa 0.65 0.705 0.61 0.74 0.74 2Wet strength: MPa 0.16 0.165 0.16 0.175 0.165

Notes to Table 3 * ": The experiments were performed using the method ASTM 1037-72.

2: The experiments were performed using the conditions of the method German V-100.

20 6 8 6 4 8

Example 4

A series of particle board samples were prepared using the method of Example 1, but varying the quality of the polyisocyanate and using pyrophosphate derived from oleyl acid phosphate prepared as described in Production Method 3 instead of lauric acid phosphate. The various components and their amounts (all calculated by weight) are shown in Table 4 below, together with the physical properties determined from the final samples. The thickness of the chipboards was 9 mm in all cases (bars of similar thickness, spaced apart) were used. No sample adhered to the molding plates during compression. The physical properties of the various samples indicate that they have excellent structural strength.

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Notes to Table 4

Methylene bis (phenyl isocyanate) prepolymer: equivalent weight = 181 2: Polymethylene polyphenyl polyisocyanate containing about 65% methylene bis (phenyl isocyanate): equivalent weight = 133 3: Polymethylene polyphenyl polyocyanate containing about 45% n-polyisocyanate isocyanate): equivalent weight = 133.5 4: Liquid methylene bis (phenyl isocyanate) prepared using the method of U.S. Patent 3,384,653: equivalent weight = 143

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Polymethylene polyphenyl polyisocyanate containing about 35% methylene bis (phenyl isocyanate): equivalent weight = 140 7: Polymethylene polyphenyl polyisocyanate containing about 70% methylene bis (phenyl isocyanate): equivalent weight as in Example 1: Same: 9: Toluene Diisocyanate 'The experiments were performed using the method ASTM 1037-72: The experiments were performed using the conditions of the method German V-100.

Example 5 This example illustrates the preparation of particle board according to the invention using a binder mixture without additional emulsifier and the polyisocyanate was added as such, i. not in the form of an aqueous emulsion.

A series of particleboard samples were prepared using different ingredients and amounts (all by weight) as shown in Table 5 and using the method of Example 1, except that the wood parts were first sprayed with a predetermined amount of water and then a mixture of polyisocyanate and phosphate release agent. The physical properties determined for each finished chipboard are shown in Table 5 and show the excellent structural strength of the different samples. All samples were easily removed from the mold and were non-stick to the steel plates used in their manufacture.

24 68648 TABLE 5

Levy_W_X_Y__Z__ZZ

materials

Wood chips 644 644 644 644 644

Weight of water in chips 56 56 56 56 56

Polyisocyanate (same 38.6 as in Example 1) ',

Water 56 56 56 56 56

Lauryl pyrophosphate 39 3g (same as in Example 2) J, y J'y '' 'x% w / w polyisocyanate 666 6 6 * S w / w water all 17 „17 4 17 4 17.4 17.4 K183Γ1 x% w / w pyrophosphate 0,6 0,6 0,6 0,6 0,6 fate

Compression time (min) 2 2.5 3.0 2 2.5

Plate thickness (mm) 9.5 9.5 9.5 12.7 12.7

Physical properties

Density, g / cm ^ 0.70 0.68 0.70 0.67 0.68 ^ Refractive index: MPa 36.8 35.9 40.0 29.9 33.3 ^ Modulus of elasticity: MPa x 10 ^ 3.46 3.52 3.90 2.61 2.53 1 Dry strength: MPa 0.93 0.92 0.97 1.26 1.23 ^ Wet strength: MPa 0.295 0.29 0.32 0.345 0.34

Notes to Table 5

Calculated on the dry weight of wood particles 1 The experiments were performed using the method ASTM 1037-72 2

The experiments were performed using the provisions of the method German V-100. Example 6 This example illustrates the production of three particle boards by the process of the invention from plywood chips of various sizes, as large as 50 x 50 x 1 mm, supplied by Weldwood Canada Ltd. No additional water or emulsifier was used and the polyisocyanate and phosphate release agent were added as is.

A series of chipboard samples were prepared using these chips

II

68648 different ingredients and their amounts (all calculated by weight) as shown in Table 6 and using the method described in Example 1, except that the wood chips were sprayed with a mixture of polyisocyanate and phosphate remover and not an aqueous emulsion as in Example 1 and an aluminum molding board was used. All samples easily left the mold and were non-stick to the aluminum sheets used in their manufacture. The excellent structural strength properties of the resulting particleboards, as evidenced by the fracture toughness of Table 6, successfully compete with the low value (17.5 MPa) of this parameter determined from a commercial board made from the same type of chips using a phenol-formaldehyde resin binder.

TABLE 6

Levy_AA_BB_CC

Plywood chips 955 955 955

Weight of water in chips

Polyisocyanate1 19.1 50 50

Lauryl pyrophosphate (same as in Example 2) '' 5 x% w / w polyisocyanate 2 5.2 5.2 x% w / w total water 4.7 4.7 4.7 x% w / w pyrophosphate 0.26 0, 68 0.68

Formatting time (min) 4.5 4 4.5

Plate thickness (mm)

Density, g / cm 3 0.76 0.71 0.75

Fracture modulus: MPa 50.5 54.8 75.0 x Calculated on the dry weight of the chips ^ Polymethylene-polyphenyl-polyisocyanate: equivalent weight = 139: fm. Viscosity at 25 ° C = 700 cP: contains about 35% methylene bis (phenyl isocyanate).

Example 7 This example illustrates the preparation of a series of particle board using polyisocyanate binders in combination with commercial phosphates in amounts corresponding to about 0.7% w / w phosphorus in the binder resin combination.

Different samples were prepared using the different ingredients and their amounts (all parts by weight) shown in Table 7 and using the method of Example 1 with the difference that no emulsifier was used and water was sprayed first into the chips and then isocyanate mixed with a release agent. All samples easily removed from the molds and did not adhere at all to the steel plates used in their manufacture. On the contrary, a reference plate made in exactly the same manner but without the use of a phosphate release agent adhered to the steel plates used in its manufacture and could not be removed from the mold without damaging the surfaces of the plate.

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Notes to Table 7 ^ Alkyl hydrogen phosphate derived from lauryl alcohol pretreated with 3 molar ratios of ethylene oxide, Textilana Division Henkel Inc., Hawthorne, CA.

2

Lauryl hydrogen phosphate, Emery Industries Inc., Mauldin, South Carolina.

3

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4

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Inc.

^ Alkyl hydrogen phosphate derived from n-octyl alcohol, Textilana, ibid.

^ Alkyl hydrogen phosphate derived from ethoxylated lauryl alcohol, Emery Industries Inc.

7

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χ

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Example 8

An additional set of particle board samples was prepared using the same phosphate release agents and methods as in Example 7, but with lower concentration values in the binder resin combination. The various ingredients and their amounts (by weight) are shown in Table 8 along with the physical properties determined from the specified samples. All samples could be removed from the mold without damaging the plate or substantially adhering to the press plates. Those samples prepared using higher amounts of phosphate remover slipped off between the press plates as they were removed from the mold, while some of the sheets prepared using lower amounts of phosphate remover (00, QQ and UU) required assistance, i. pushing away from the pressure plates to cause detachment. The thickness of all samples was 12.7 mm as the final plate.

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Example 9 This example illustrates the use of a binder resin combination in accordance with the invention in conjunction with a previously known phenol-formaldehyde resin binder.

All samples (thickness 12.7 mm) were prepared using the method of Example 1 with the difference shown below and using the reactants and their amounts (by weight) shown in Table 9. In the case of plates YY and ZZ, the phenol formaldehyde resin was combined with the isocyanate emulsion, while in the case of plate AA, the chips were first sprayed with the indicated amount of added water and then the phenol-formaldehyde resin and finally the polyisocyanate. In the case of the BBB of the control plate, water and then phenol formaldehyde resin were sprayed onto the plates. Plates XX and ZZ did not adhere substantially to the press plates after pressing, whereas severe adhesion problems occurred with the issue of plates YY, AAA and BBB. The physical properties of the various sheets are also shown in Table 9, from which it can be seen that the properties of sheets XX and ZZ, both of which are within the scope of the invention, are clearly superior to sheets YY, AAA and BBB, which are not within the scope of the invention.

TABLE 9

Records XX YY ZZ AAA BBB

Mateiraalit

Wood chips 1920 1920 1920 1920 1920

Weight of water in chips 80 80 80 80 80 ^ Phenol-formaldehyde-^ 1 resin - 96 96 96 192

Polyisocyanate (same as in Example 1) 96 48 48 48

Added water 208 160 160 160 112 2

Emulsifier 2.4 2.4 2.4 3

Lauryl pyrophosphate 9.6 to 4.8 χ% w / w resin 555 5 5 X% w / w water 15 15 15 15 15 £% w / w phosphorus 0.5 to 0.25 phate

Plate temperature, ° C 177 177 177 177 177

Formatting time (min) 5.5 5.5 5.5 5.5 5.5 32 68648 TABLE 9 (continued)

Records XX YY ZZ AAA BBB

Physical properties_

Density, g / cm ^ 0.692 0.711 0.740 0.738 0.687 ^ Refractive index: MPa 25.2 20.7 22.9 22.5 19.1 ^ Modulus of elasticity: 2.14 2.07 2.45 2.20 2.08 MPa x Dry strength: MPa 1.17 1.09 1.05 1.16 0.69 Wet strength: MPa 0.54 0.44 0.42 0.345 0.15 ^ PB-65: Borden aqueous suspension with a solids content of 50%.

2

Aqueous solution, sodium salt of styrene-maleic anhydride copolymer, solids 30%, Monsanto.

^ Prepared by the production method 4.

4

The experiments were performed using the method ASTM-1037-72.

The experiments were performed using the method German V-100. x Calculated on the dry weight of the wood particles.

Example 10

A series of particle board samples were prepared using a combination of polymethyl polyphenyl polyisocyanate and acid phosphate as a binder. The polyisocyanate used was in all cases poly-methylene-polyphenyl-polyisocyanate containing about 48% by weight of methylene bis (phenylisocyanate) and having an equivalent weight of 134.5 isocyanate and a viscosity at 25 ° C of 1.21 MPa. In each case, a different acid phosphate was used, but all the acid phosphates were mixtures of dihydrogen phosphates O and mono- O RO-P- (OH) 2 r hydrogen phosphates (RO 2 PfOH), in which formulas R had the values shown in Table 10.

The manufacturing method for particle board was as follows for all samples:

A bath of 2500 g of Douglas spruce chips was sprayed with a mixture of 112 g of the above polyisocyanate, acid

II

68648 phosphate in the proportions and amounts given in Table 10 and 40-50 g of "Freon R 11" (trichlorofluoromethane) using the method and apparatus described in Example 1. When isocyanate injection and rotational homogenization were complete, a sample of treated chips (2156 g) was used to make a 9 mm thick chipboard using the method described in Example 1, but using cold rolled steel sheets measuring 60 x 90 cm and forming a frame with internal dimensions. were 46 x 75 cm. An aluminum foil sheet was placed between each steel plate and the adjacent chipboard mat surface. The plate temperature was 176 ° C and the compression time was 2.5 minutes with a compression force of at least 3.5 MPa. When the chipboard was removed from the press plates with aluminum foils, the relative ease of removing the aluminum foil separated from the particle board was determined to be either excellent (no removal resistance), good (no film peeling resistance) or moderate (some resistance but could peel off without tearing or otherwise damaging the film).

TABLE 10 R acidic% w / w P 1% w / w ^ Ρ3 * 1 * 1 * Exit phosphate in binder phosphate ease in binder1 2 C12H25 ^ 0 <"H2 ('H2 ^ -3 0/6 9.7 Excellent 3 C12H25 (° CH2 ('H2 ^ 3 0.6 10.6 Excellent 4 C12H25 (OCH2CH2 ^ ~ 5 0.6 13.6 Excellent C8H17— 0.5 4.6 Excellent 52-ethylhexyl 1.2 10 Good ^ tridecyl 0, 8 10 Excellent

Notes: 1: binder = polyisocyanate + acid phosphate 2: "Fosterge A2523"; Textile 3: "Tryfac 325A"; Emery Industries 4: Tryfac 525A; Emery Industries 5: Mobil Corporation 6: Mobil Corporation 68643

Example 11 Using the procedure described in Example 10, with the exception that the polyisocyanate was sprayed onto the wood chips in the first spraying and rotation step and the treated chips were then sprayed as a separate operation with 15.27 g of bis-2-ethylhexylpyrophosphoric acid 00 in 50 g T ΐ [R0-P -0-P-0R; R = 2-ethylhexyl] OH Ah "Freon R 11". The ease of removal of the aluminum foil was rated "excellent" on the resulting chipboard.

Claims (17)

35 6 8 6 4 8 A method of making particle boards by contacting particles of organic material which can be compressed with polyisocyanate and then forming the treated particles into sheets using heat and pressure, characterized in that said particles are contacted in addition to the polyisocyanate treatment with about 0.1 to 20 weight with 100 parts by weight of polyisocyanate, a phosphate consisting of an acid phosphate of the formula 0 OT t RO -P -OH or (RO) 0P -OH 1 2 OH (I) (II) or a mixture thereof or a pyrophosphate derived from an acid phosphate (I) or (II) or a mixture thereof in which R is Alkyl of 8 to 35 carbon atoms, alkenyl of 8 to 35 carbon atoms or a group R '- (OCH.CH 0 -) -2. N wherein R' is alkyl of 8 to 35 carbon atoms and n is a number having an average of 1-5. Process according to Claim 1, characterized in that the polyisocyanate is polymethylene polyphenyl polyisocyanate containing about 25 to 90% by weight of methylene bis (phenyl isocyanate), the remainder being oligomeric polymethylene polyphenyl polyisocyanates, having a functionality greater than 2. Process according to Claim 2, characterized in that the polymethylene polyphenyl polyisocyanate contains about 35 to 65% by weight of methylene bis (phenyl isocyanate). 36 68648 Process according to Claim 1, characterized in that the phosphate is a mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate. Process according to Claim 1, characterized in that the phosphate is a pyrophosphate obtained by removing condensation water from a mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate. Process according to Claim 1, characterized in that the phosphate is a mixture of oleyl dihydrogen phosphate and dioleyl monohydrogen phosphate. Process according to Claim 1, characterized in that the phosphate is a pyrophosphate obtained by removing condensation water from a mixture of oleyl dihydrogen phosphate and dioleyl monohydrogen phosphate. A method according to claim 1, characterized in that the particles used in the manufacture of said particle boards are wood chips. A method according to claim 1, characterized in that the polyisocyanate and the phosphate are added simultaneously to said particles in the form of an aqueous emulsion. Process according to Claim 9, characterized in that the aqueous emulsion of polyisocyanate also contains an emulsifier. Process according to Claim 1, characterized in that the particles are contacted separately with the polyisocyanate and the phosphate. Process according to Claim 11, characterized in that the polyisocyanate and the phosphate are each used in the form of an aqueous dispersion. Process according to Claim 11, characterized in that the particles are brought into contact with water before they are brought into contact with the polyisocyanate and phosphate. 68648 A storage-resistant binder composition, characterized in that it comprises a mixture of (a) polymethylene polyphenyl polyisocyanate containing about 25 to 90% by weight of methylene bis (phenyl isocyanate), the remainder of the mixture being oligomeric polymethylene poly - phenyl polyisocyanates having a functionality of more than 2.0 and (b) about 0.1 to 20 parts by weight, per 100 parts by weight of polyisocyanate, pyrophosphate obtained by removing condensation water from at least one acidic phosphate having formula 0 OT t RO-P-OH or (RO) ,, Ρ-OH 1 1 OH or a mixture of two or more such acidic phosphates, in which formulas R is alkyl having 8 to 35 carbon atoms, alkenyl having 8 to 35 carbon atoms or a group R ' - (O-CH, -CH, * -— λ 2 n wherein R 'is alkyl of 8 to 35 carbon atoms and n is a number having an average of 1-5. Mixture according to Claim 14, characterized in that the pyrophosphate is obtained from a mixture of lauryl dihydrogen phosphate and dilauryl hydrogen phosphate. Mixture according to Claim 14, characterized in that the pyrophosphate is obtained from a mixture of oleyl dihydrogen phosphate and dioleyl monohydrogen phosphate. Mixture according to Claim 14, characterized in that it also contains an emulsifier. 38 68648