DK150195B - PROCEDURE FOR MANUFACTURING PARTICLE PLATES AND USEFUL, STORAGE STABLE BINDING AGENT - Google Patents

Description

i 150195 o

The present invention relates to a process for producing particle plates, such as particle boards or other compressible particles, in which process organic particles which can be compressed are added polyisocyanate (as a binder) and the particles in question are then formed into sheets by applying heat and pressure.

It has recently become widely used to use organic polyisocyanates, especially toluene diisocyanate, methylene bis (phenyl isocyanate) and polymethylene polyphenate. nyl polyisocyanates, as binders or as a component in binders for the manufacture of particle boards, see e.g.

U.S. Patent Nos. 3,428,592, 3,440,189, 3,557,263, 2,636,199, 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 mixed with the particles of a cellulose material or other types of material capable of forming particle plates using a revolutionary apparatus or a mixer or other form of mixer, and the mixture of particles and binder is then formed into a mat and subjected to heat and pressure using heated plates. Such a process can be performed batchwise or continuously. In order to avoid the plate thus formed adhering to the heated plates, it has hitherto been necessary to insert a foil impervious to isocyanate between the surface of the particle plate and the heating plate during the formation process or to coat the surface of the heating plate, casting operation, with an appropriate release agent, or coating the surface of the particles themselves with a material which will not adhere to the hot plate, and any of these options, especially when the process is performed on a continuous basis, is cumbersome and constitutes a minus 35 for what otherwise there is a very satisfactory way

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2 150195 for the manufacture of particle boards with very attractive structural strength properties.

It has now surprisingly been found that the above-mentioned disadvantages of the use of organic isocyanates 5 as particle plate binders can be greatly reduced in a very satisfactory manner by incorporating in the isocyanate mixtures certain phosphorus-containing compounds as internal release agents. Although United States Patent No. 4,024,088 discloses the incorporation of phosphorus-containing compounds as internal release agents in the preparation of polyether polyurethanes, it has been found that the phosphorus compounds mentioned therein are not suitable for use in the process of the present invention.

Further, U.S. Patent No. 3,151,016 discloses the use of acidic phosphates as release agents in the production of fibrous sheets using a polyvinyl acetate emulsion alone or in admixture with the hexamethyl ether of hexamethylol melamine or an emulsion 20 of a copolymer of styrene, acrylonitrile and methacrylic acid. .

Such a binder does not react with the fibers formed to the fibrous sheet, nor does it adhere to the pressing plates in the same way as a polyisocyanate binder does. Therefore, it could not be foreseen that acidic phosphates of a similar nature to those described in U.S. Patent No. 3,151,016 would be useful as release agents using polyisocyanates as a binder. This is all the more true as according to the aforementioned US patent, fibers with a very high water content (40-60%) are used, whereas in the process of the present invention a much lower water content is used, namely up to 24%. as discussed in more detail below.

The present invention relates to an improved process for the production of particle plates in which particles of an organic material which can be compressed produce

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Polyisocyanate is added and the treated particles are then combined into plates by applying heat and pressure, and the process of this invention is characterized in that said particles are additionally added phosphate in an amount of between 0.1 and 20 parts by weight for each. 100 parts by weight of the polyisocyanate, which phosphate is selected from the following groups: (a) acidic phosphates of formulas "1?

RO-R-OH or (RO) 0P-OH

I 2

OH

(I) (II) and the ammonium, alkali metal and alkaline earth metal salts thereof, (b) pyrophosphates corresponding to those derived from the acidic phosphates I and II and mixtures of I and II,

(c) the 0-monoacyl derivatives of the acidic phosphates I and II

20 with the formulas 0 RO-P-OCR1 or (RO) -P-OCR1

OH

(V) (VI) (d) Carbamoyl Phosphates of Formula 30 ^ R2NHCOO-P (OR)

OH

(VII) 35 and the ammonium, alkali metal and alkaline earth metal salts of these compounds, (e) branched polyphosphates of the formulas

Q 0 O O O

f t f t r 5 RO-P -: - O - P (OR) 2 or (RO) 2P-O-P-0-P (OR) 2? (° R> 2x OP (OR) ~ / U δ (VIII) (IX) two (f) polyphosphates corresponding to the formula of [ROP-0] n (X) including the cyclometaphosphates (n = 3), and ( g) mixtures of two or more of the above-mentioned compounds, wherein in the indicated formulas each R is selected from alkyl groups of 8-35 carbon atoms, alkenyl groups of 8-35 carbon atoms, and groups of formula R'- ( 0-CH - <^ · ^ H -

A B

Wherein R 'is alkyl of 8-35 carbon atoms, one of the groups A and B is hydrogen while the other is hydrogen or methyl, and n is a number having an average value of

1 2 1-5, while R is hydrocarbyl of 1-12 carbon atoms, R

is. hydrocarbyl having 1-12 carbon atoms or hydrocarbyl 30 substituted by at least one additional group of formula -NHC00 -— (ii) OR, where R is as indicated above and n is an integer.

The invention also relates to a novel storage stable binder for the manufacture of particle sheets, which binder is characterized in that it comprises a mixture of (a) a polymethylene polyphenyl polyisocyanate containing from 25 to 90% by weight methylene bis (phenylisocyanate), while the remainder of the mixture is oligomeric polyethylene polyphenyl polyisocyanates having a functionality greater than 2.0, and (b) from 0.1 to 20 parts by weight, for every 100 parts by weight of po -lyisocyanate, of a pyrophosphate formed by the removal of condensation water from at least one acid phosphate selected from acidic phosphates of the formulas

0 Q

Ϊ

RO-P-OH or (RO) 0P-OH

1 2

OH

wherein each R is independently selected from alkyl groups of 8-35 carbon atoms, alkenyl groups of 8-35 carbon atoms, and groups of formula 20 R'-10-CH-

A B

wherein R 'is alkyl of 8-35 carbon atoms, one of the groups A and B is hydrogen while the other is hydrogen or methyl, and n is a number having an average value of 1-5, and mixtures of two or more of such acidic phosphates.

By "alkyl of 8-35 carbon atoms" is meant a saturated straight or branched chain monovalent aliphatic group having the indicated number of carbon atoms in the molecule.

Examples of such groups are octyl, nonyl, decyl, un-decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, pentacosyl, hexacosyl, hexacosyl, 6 o 150195 sil, octacosyl, nonacosyl, triacontyl and pentatriacontyl, as well as their isomeric forms.

By "alkenyl of 8-35 carbon atoms" is meant a monovalent straight or branched aliphatic group having at least one double bond and the indicated number of carbon atoms in the molecule. Examples of such groups are octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetra-decenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecyl,. nonadecyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, pentacosenyl, triacontenyl and pentatriacontenyl, and the isomeric forms thereof.

With the indication "pyrophosphates ------ derived from the

acidic phosphates I and II and mixtures of I and II are meant as follows: The acidic phosphates I and II are generally prepared in the form of mixtures of the mono acid phosphate II

and the diacid phosphate I, which mixtures are obtained by reacting the corresponding alcohol ROH, where R is as indicated above, with phosphorus pentoxide according to the known methods for preparing acidic phosphates, see e.g. Kosolapoff, 20 Organophosphorus Compounds, pages 220-221, John Wiley and Sons, Inc., New York, 1950. The mixture of mono- and di-phosphate thus obtained can be separated, if desired. by fractional crystallization of the barium salts and similar salts as described in said article. In the process according to the invention, both the acidic phosphates and mixtures of both can be used. The pyrophosphates III and IV are readily obtained from the corresponding acidic phosphates II and I, respectively, by reacting these with a dehydrating agent such as e.g. carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates and Ν, Ν'-dihydrocarbylcarbodiimides according to known methods, 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. 80, 6204 (1958) and 35 F, Ramirex, J.F. Marecek and I. Ugi, JACS 97, 3809 (1975).

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7 150195

The individual acid phosphates I and II can be separately converted to the corresponding pyrophosphates, or mixtures of the two acid phosphates I and II can be converted to the corresponding mixture of pyrophosphates.

In the case of the acidic phosphates of formula II, the corresponding pyrophosphates are those which can be represented by the formula

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10 (RO) 2i-OP (OR) 2 (III) where R is as indicated above, and in the case of the acidic phosphates of formula I, the corresponding pyrophosphates are a complex mixture whose average composition can be reproduced by the formula f Π Π HO -P - OP - OH (IV) (Ir Ir 20 i- Jx where x is a number with an average value of 1 or more and R is as given above.

By "hydrocarbyl of 1-12 carbon atoms" is meant the monovalent radical obtained by removing one hydrogen atom from the hydrocarbon with the indicated number of carbon atoms. Examples of such groups are alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and the isomeric forms thereof, alkenyl such as vinyl, acetyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl and the isomeric forms thereof, aralkyl such as benzyl, phenylpropyl, phenethyl and naphthylmethyl, aryl such as phenyl, tolyl, xylyl, naphthyl and biphenylyl, cycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the isomeric forms thereof , cyclohexenyl, cycloheptenyl, cyclooctenyl and the isomeric forms thereof.

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8 150195

By "alkali metals" is meant lithium, sodium, potassium, rubidium and cesium, while the term "alkaline earth metals" has the usual meaning including calcium, strontium, magnesium and barium.

The process of the invention is carried out in the main proceedings in accordance with the methods previously described and in which an organic polyisocyanate is used as a binder or a component thereof (see, for example, German Patent Specification No. 2,610,552 and U.S. Pat. No. 3,428,592), with the primary exception that a phosphate of the types listed above is used in conjunction with the isocyanate mixture used to treat the particles to be bonded together to form the particle plate.

Thus, according to the invention, particle sheets are prepared by bonding together particles of wood or other cellulose-like or organic material which can be compressed using heat and pressure in the presence of a binder system comprising a combination 20 of an organic polyisocyanate. and a phosphate of the above types, hereinafter referred to as the "phosphate releasing agent".

The polyisocyanate and phosphate release agent may be brought into contact with the particles as separate single components, or preferably, and preferably; the polyisocyanate and phosphate can be contacted with the particles either simultaneously or after mixing. Whether the polyisocyanate and the phosphate are introduced separately or mixed, they can both be used pure, ie. without diluents or solvents or one or the other or both can 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 per molecule. Examples of such organic polyisocyanates are diphenyl methane diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, α, α-xylylene diisocyanate and 2,4- and 2,6-toluene diisocyanate, as well as mixtures of these two isoforms. 5 more commercially available, and further triphenylmethane triisocyanates, 4,4'-diisocyanatodiphenyl ether and polyethylene polyphenyl polyisocyanates. The latter polyisocyanates are mixtures containing between 25 and 90% by weight of methylene bis (phenyl isocyanate), while the remainder 10 of the mixture are polymethylene polyphenyl polyisocyanates having a functionality greater than 2.0. Such polyisocyanates and methods for their preparation are known, see e.g. U.S. Patent Nos. 2,683,730, 2,950,263, 3,012,008 and 3,097,191. These polyisocyanates are also commercially available in various modified forms, one of which comprises a polymethylene polyphenyl polyisocyanate, as mentioned above, which has been subjected to a heat treatment, usually at temperatures of from ca.

150 to approx. 300 ° C until the viscosity (at 25 ° C) has been increased to a value in the range of approx. 800 to 1500 centipoise, while another modified form is one which is treated with minor amounts of an epoxide to reduce the acidity as disclosed in U.S. Patent No. 3,793,362. The polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the binder systems of the invention, and particularly preferred are those which contain from ca. 35 to approx. 65 weight methylene bis (phenyl isocyanate).

When the organic polyisocyanate is to be used as a binder in the form of an aqueous emulsion or dispersion according to the invention, the aqueous emulsion or dispersion can be prepared by any method of preparing aqueous emulsions or dispersions before the mixture is used as a binder. The polyisocyanate 150195 or e.g. dispersed in water in the presence of an emulsifier, and this may be any known emulsifier, both anionic and nonionic.

Examples of nonionic emulsifiers are polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more of the compounds ethylene oxide, propylene oxide, butylene oxide and styrene, as well as alkoxylated alkyl phenols such as nonylphenoxy poly (ethyleneoxy) ethanols, alkoxylated aliphatic alcohols such as ethoxylated and two propoxylated aliphatic alcohols having 4-18 carbon atoms, glycerides of saturated and unsaturated fatty acids such as stearic acid, oleic acid and castoric acid, and polyoxyalkylene esters of fatty acids such as stearic acid, lauric acid and oleic acid, and fatty acids 15 such fatty acids as e.g. stearic acid, lauric acid and oleic acid. A detailed account of such materials can be found 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 occur at any time before its use as a binder mixture, but preferably it occurs within about 30 minutes. 3 hours prior to use and any aqueous suitable polyisocyanate emulsions used in the process of the invention may be used. The emulsion may e.g. is formed by compressing the polyisocyanate, emulsifier and water in a conventional spray gun, where the streams of water and polyisocyanate strike and, under turbulent conditions, are mixed together in the spray chamber mixing chamber. The emulsion thus formed is discharged in the form of a spray jet directed at the cellulose particles to be converted into a sheet material as described below.

As mentioned above, the phosphate release agent 11 can be contacted with the particles as a separate component, in which case it is used in pure form, ie. without diluents, or as an aqueous solution or dispersion. When the phosphate is used alone, i.e. separated from the polyisocyanate, in undiluted or diluted form, it is advanced 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 used together in a single mixture, and this can be accomplished in various ways. Thus, when the polyisocyanate is used as a binder resin without diluents such as water, the phosphate release agent can be incorporated into the polyisocyanate by simple mixing, and when the polyisocyanate is used as a binder resin in the form of an aqueous emulsion, the phosphate release agent can be added as a separate component during or after formation. of the emulsion, or the phosphate, in a particularly advantageous embodiment, can be incorporated into the organic polyisocyanate prior to emulsification thereof. In this last embodiment, the organic polyisocyanate and phosphate release agent may be pre-mixed and stored for any desired period of time before forming the emulsion. Furthermore, when an emulsifier is used to form the emulsion, this can also be incorporated into the mixture of organic polyisocyanate and phosphate release agent to form a storage stable mixture which can then be converted into an aqueous emulsion for use as a binder resin at any desired time. by simple mixing with water.

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

Whether the phosphate release agent is introduced as a separate component or in combination with the polyisocyanate, the amount of phosphate release agent used ranges from 0.1 to 20 parts per weight. 100 parts by weight of polyisocyanate and preferably in the range of 2 to 10 parts by weight per unit weight 100 parts by weight of polyisocyanate. The amount of emulsifier required to form the aqueous emulsion is not critical and varies according to the particular emulsifier used, but it is generally in the range of 0.1 to 20% by weight based on the polyisocyanate.

The starting material for particle plates can be pairs of particles of cellulose and similar material which can be compressed and bonded to form plates. Typical examples of such materials are wood particles derived from waste from timber production, e.g. planer shavings and veneer shavings. However, particles of other cellulose materials such as paper strips and pulp or vegetable fibers, e.g. corn stalks, straw and bagasse, and of non-cellulose materials such as residues of polyurethane, polyisocyanurate and similar polymeric foam. Methods for forming suitable particles are recognized and conventional and need not be further described herein. If desired, mixtures of cellulose particles may be used, and e.g. with good results, particle plates have been prepared from mixtures of 25 wood particles containing up to approx. 30% bark.

The moisture content of the particles may conveniently be between 0 and 24% by weight, and as an example, particles made from timber waste contain between 10 and 20% moisture and can be used without first drying.

Particle plates are prepared by spraying the particles with the components of the binder mixture, either individually or in admixture, while the particles are turned upside down or stirred in a mixer or similar mixer. For example, A total of between 2 and 8% by weight of the binder (excluding water present therein) is calculated, based on the weight of the crustal particles, but higher or lower amounts of binder resin may also be used for any given application.

If desired, other materials such as e.g. wax finishing agents, fire retardants and pigments.

After mixing sufficiently to form a uniform mixture, the coated 10 particles are laid to a loose mat or loose felt, preferably containing between 4 and 18% by weight of moisture, and the mat is then placed in a heated press between supplementary sheets and compressed to consolidate the particles into a plate. Pressure times, temperatures and pressures 15 may vary within wide limits, depending on it

the thickness of the sheet formed, the desired density of the sheet, the size of the particles used and other well-known factors, but as an example, it can be stated that for particle sheets having a thickness of 12.7 mm and medium density pressures of between 20 and 35 kg / cin and temperatures between 160 and 190 ° C

be typical. The press times are usually between 2 and 5 minutes. Since part of the moisture present in the mat reacts with polyisocyanate to form polyurea, as described previously, the moisture content of the mat is not as critical with isocyanate binders as with other binders.

The process described above can be carried out in portions, that is, separate sheets of particle plate can be formed by treating an appropriate amount of 30 particles with the binder resin combination and heating and pressing the treated material, but the process can also be carried out continuously by treating particles in in the form of a continuous web or had to be passed through a heating and pressing zone bounded by an upper 35 and a lower continuous steel band to which, and

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14 150195 which are supplied with the required heat and exerted the necessary pressure.

Whilst the process of the invention is carried out portionwise or continuously, it has been found that the particle plates obtained by using the combination of the invention of the polyisocyanate and the phosphate release agent are very readily released from the metal plates in the press used for their manufacture. shows some propensity to adhere or adhere to the metal sheets, and this is in direct contrast to previous experiences of using polyisocyanates alone as binder resins as described above.

Although any of the above-mentioned phosphate release agents, either alone or in combination, can be used for the process of the invention, it is preferable to use pyrophosphates III and IV or mixed pyrophosphates derived from mixtures of the acidic phosphates I and II. Thus, the free hydroxyl groups in the pyrophosphates or any free hydroxyl group present in the form of unchanged acid phosphate are generally sufficiently hindered to be non-reactive with the polyisocyanate used in the process of the invention, and the pyrophosphates can be stored with the polyisocyanate for extended periods of time without showing any signs of degradation. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and used for the process according to the invention, the process temperature and the water vapor formed by the formation of the particle plates 30 are believed to result in a hydrolysis of the pyrophosphate to recover the corresponding acidic phosphates which then again serves to facilitate the subsequent release of the particle plate from the plates in the press.

As mentioned above, the monosuric phos.

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Phosphate II and the diacid phosphates I and the salts thereof used in the process of the invention, according to conventional methods such as reacting the corresponding alcohol ROH, wherein R is as indicated above, with 5 phosphorus pentoxide (Kosolapoff, see above). As will be apparent to one skilled in the art, by using mixtures of two or more different alcohols in such a reaction it is possible to obtain a corresponding mixture of the acidic phosphates I and II, wherein the different components contain different R groups. As also mentioned above, the mixture of mono- and di-acidic phosphates obtained by said reaction can be divided into its individual components in the usual manner, e.g. by fractional crystallization, and the single compounds thus obtained can be used for the process of the invention. Alternatively and preferably, the mixture of "mono- and di-acidic phosphates obtained by said reaction can be used as such without subdivision into its components for the process of the invention, or it can be converted into the corresponding mixture of pyrophosphates according to the invention. previously described methods, which mixture is then used for the method according to the invention.

Examples of the acidic phosphates of formula I which can be used alone or in combination with other acidic phosphates for the process of the invention are mono-O-octyl, mono-O-nonyl, mono-O-decyl, mono-O-undecyl, mono-O-dodecyl, mono-O-tridecyl, mono-O-te-tradecyl, mono-O-pentadecyl, mono-O-hexadecyl, mono-30-O heptadecyl, mono-O-octadecyl, mono-O-nonadecyl, mono-O-eicosyl, mono-O-heneicosyl, mono-O-docosyl ·, mo-no-O-tricosyl, mono -O-pentacosyl, mono-O-hexacosyl, mono-O-heptacosyl, mono-O-octacosyl, mono-O-nonacosyl, mono-O-tricontyl, mono-O-pentatriacontyl, mono-O O-dead-cenyl, mono-O-tridecenyl, mono-O-tetradecenyl, mono-O

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16-O-pentadecenyl, mono-O-hexadecenyl, mono-O-heptadecenyl, mono-O-octadecenyl, 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-diacid phosphates, and the diacid phosphates in which esterification radicals The moiety is derived from lauryl alcohol and similar monovalent alcohols, masked using between 1 and 5 moles of ethylene oxide.

two Examples of acidic phosphates of formula II which can be used alone or in combination with other acidic phosphates in the process of the invention are O, O-di (octyl) -, O, O-di (nonyl) -, O, O-di (decyl) -, O, O-di- (undecyl) -, O, O-di (dodecyl) -, O, O-di (tridecyl) -, 0,0-15-di (tetradecyl) - , 0,0-di (pentadecyl) -, 0,0-di (hexadecyl) -, 0,0-di (heptadecyl) -, Ο, Ο-di (octadecyl) -, 0,0-di (nonadeyl) ) -, 0.0-di (eicosyl) -, 0.0-di (heneicosyl) -, 0.0-di (do-cosyl) -, 0.0-di (tricosyl) -, 0.0-di (pentacosyl) -, 0.0 - di (hexacosyl) -, 0.0 - di (heptacosyl) -, 0.0 - di (octacosyl) -, 0.0 - di (nonacosyl) -, 0.0 -di (triacontyl), 0.0-di (pentatrontontyl) -, 0.0-di (dodecenyl) -, 0.0-di (tridecenyl) -, 0.0 - di (tetradecenyl) -, , 0-di (pentadecenyl) -, 0.0-di (hexadecenyl) -, 0.0-di (heptadecenyl) -, 0.0-di (octadecenyl) -, 0.0-di (nonadecenyl) - , 0.0-di (eicosenyl) -, 0.0-di (heneicozenyl) -, 0.0-di (docosenyl) -, 0.0-di (tricosenyl) -, 0.0-di (pentacosenyl) -, 0.0-di (triacontenyl) and 0.0-di (pentatri-cosenyl) -monosuric phosphates, and the same rified monoacid phosphates wherein the esterification radical is derived from lauryl alcohol and similar monovalent alcohols, masked with between 1 and 5 moles of ethylene oxide. Examples of the latter types of commercially available phosphate, mixed with the corresponding disure phosphates, are the products marketed under the designation "Tryfac" by Emery Industries Inc.

Examples of the pyrophosphates of formula III which can 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 (pentadecyl) tetra (hexadecyl) tetra (heptadecyl) tetra (octadecyl) tetra (nonadecyl) tetra (eicosyl) tetra (heneicosyl) tetra (docosyl) -, tetra (tricoyl) -, tetra (pentacosyl) tetra (hexacosyl) tetra (heptacosyl) -, tetra (octacosyl) tetra (nonacosyl) tetra (trisol acontyl) -, tetra (pentatriacontyl) - , tetra (dodecenyl) -, tetra (tridecenyl) tetra (tetradecenyl) tetra (penta-decenyl) -, tetra (hexadecenyl) tetra (heptadecenyl) tetra (octadecenyl) -, tetra (nonadecenyl) -, tetra (eicose-nyl) - , tetra (heneicosenyl), tetra (docosenyl), tetra (tricosenyl) tetra (pentacosenyl) tetra (triacontenyl) - and tetra (pentatriacosenyl) pyrophosphates.

Examples of pyrophosphates of formula IV which can be used alone or in combination with other pyrophosphates for the process of the invention are 20 di (octyl) -, di (nonyl) -, di (decyl) -, di (undecyl) -, di (do-decyl) -, di (tridecyl) -, 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 (hepatacosyl) -, 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 (eicosenyl) -, di (heneicosenyl) -, di (docose-phenyl) -, di (tricosenyl) -, di (pentacosenyl) - , di (triacontenyl) - and di (pentatriacosenyl) pyrophosphates.

The O-monoacyl derivatives of the acidic phosphates I and II which can be used for the process of the invention and represented by formulas V and VI are readily prepared by known methods. By way of example, it is

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180101 corresponding to acid phosphate I or II in the form of the silver salt or other metal salt is reacted with an appropriate acyl halide R 2 COHal, where Hal represents cblor or bromine and R 2 is as indicated above, according to the methods set forth by Kosolapoff (see above, page 334). Examples of the O-monoacyl derivatives of the acidic phosphates I and II are O-acetyl, O-propionyl, O-octanoyl, O-deconeyl-1-, O-dodecanoyl, O-benzoyl, O-toluoyl - and the O-phen-acetyl derivatives of the various acid phosphates I and II mentioned above.

The carbamoyl phosphates of formula VII used for the process of the invention are readily prepared by reacting a suitable acid phosphate I or II with a suitable hydrocarbyl mono- or polyisocyanate, e.g. the method described by F. Cramer and M. Winter in Chem. Ber., 92, 2761, 1959. Examples of such carbamoyl phosphates are methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, hexylcarbamoyl, decylcarbamoyl, dodecylcarbamoyl, allylcarbamoyl, hexenylcarbanoylcarbyl, octenylcarbyl , dodecenylcarbamoyl, phenylcarbamoyl, tolylcarbamoyl, diphenyl-ylcarbamoyl, benzylcarbamoyl, phenylpropylcarbamoyl and the like hydrocarbamoyl derivatives of the mono acid phosphates (stabilized in the form of their ammonium or alkali metal salts), . The carbamoyl phosphates VII may contain free OH groups due to incomplete conversion of the acidic phosphates by reaction with the hydrocarbyl isocyanate, due to the low degree of reactivity of the OH groups in question with the isocyanate. Such compounds containing free OH groups can be used for the process of the invention without causing undesirable side effects due to the low degree of reactivity of the OH groups with Isocyanate.

The polyphosphates of formula X used for

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The process of the invention is readily prepared by reacting an appropriate trialkyl phosphate (ROJ + PO, wherein R is as above) with phosphorus pentoxide according to the methods described by Kosalapoff (see above, page 341). generally complex mixtures whose composition is generically represented by formula X and comprises cyclic compounds (n = 3) having a six-membered ring composed of alternating phosphorus and oxygen atoms.

The polyphosphates of formulas VIII and IX used for the process of the invention are readily prepared by reaction of an appropriate di- or trialkylphosphate. Phat with an appropriate halogen phosphate (RO 2 - Hal, where Hal 15 is chlorine or bromine, for example, by the method described by Kosolapoff (see above, page 338), which comprises removing alkyl halide.

In a further 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 conjunction with heretofore used thermosetting resin binders of phenol-formaldehyde, resorcinol, formaldehyde, melamine - formaldehyde, urea-formaldehyde, urea-furfural, and condensed furfuryl alcohol types. Using such a combination not only avoids the problems of adhering the finished particle plates to the press plates, which also previously appeared with mixtures of isocyanates and thermosetting resin binders of the above-mentioned type, but the physical properties of the particle plates thus obtained also become noticeably improved through the use of the combination.

The following manufacturing descriptions and examples are intended to further illustrate the invention.

35 0 20 150195

Preparation 1

Preparation of pyrophosphate from lauryl acid phosphate A mixture of 70 g lauryl acid phosphate (a mixture of O, O-dilauryl monosuric phosphate and O-lauryl di-5 acid acid phosphate, Hooker Chemical Company) and 60 g of phenyl isocyanate a dry flask equipped with a stirrer, condenser and drying tube, the flask was immersed in an oil bath that had already been heated to 80 ° C and the contents of the flask was stirred while the oil bath temperature was slowly raised to 115 ° C. Carbon dioxide was developed for approx. For 1 hour, and after this development had ceased, the reaction mixture was cooled to room temperature and diluted with 100 ml of chloroform. The resulting mixture was filtered and the combined solid (24.8 g of Ν, Ν'-diphenylurea) was washed with chloroform, and the filtrate and washings were combined and evaporated on a rotary evaporator at a bath temperature of 50 ° C. When most of the solvent was evaporated, crystals were separated by N, N *, N "triphenyl bib and the evaporation was quenched to filter this solid (6.6 g). The filtrate was then evaporated to dryness. dryness and finally subjected to reduced pressure at 50 ° C to remove excess phenyl isocyanate. The residue (70 g) was the desired pyrophosphate in the form of colorless to pale yellow liquid. The infrared spectrum of the product (in CHC13) showed no bands characteristic of P-0H bonds, but a strong band at 940 cm *, there characteristic of P-0-P bonds.

Preparation 2 30 Preparation of pyrophosphate from lauryl acid phosphate In a flask equipped with the stirrer, reflux condenser and gas supply, 70 g of lauryl acid phosphate (the same as in Preparation 1) was placed and heated under nitrogen to 65-75 ° C. melted. The melt was stirred while introducing a slow stream of phosgene into

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A total of 2 1/2 hours, keeping the temperature in the above range during the addition. The gas evolution from the reaction mixture was strong during the first hour of the phosgene addition but gradually decreased and was very slow at the end of the phosgene addition. After completion of the addition, the mixture was rinsed with nitrogen for 15 hours while maintaining the temperature in said range. At the end of this time, the pressure in the reaction vessel was gradually reduced to approx. 1.0 mm Hg to remove gaseous hydrogen chloride and carbon dioxide. The viscous residue thus obtained completely solidified on standing overnight, and 66 g of pyrophosphate was obtained as a solid which gradually melted at ca. 60 ° C.

15

Preparation 3

Preparation of pyrophosphate from oleyl acid phosphate A mixture of 200 g oleyl acid phosphate (containing 0.0-dioleyl acid phosphate and O-monooleyl acid phosphate, from Hooker Chemical Company) was reacted with 160 g phenyl isocyanate at 85-90 ° C in 5 L / 2 hours in the same manner as described in Preparation 1. After diluting the reaction mixture with 200 ml of chloroform, N, N '- diphenylurea (68 g) was removed by filtration, the filtrate was concentrated on a rotary evaporator and excess unreacted phenyl isocyanate was removed by distillation at reduced pressure. On standing at room temperature, the N, N ', N "triphenylbiuric crystallized from the oily residue, and removal of the crystals by filtration gave 196 g of a liquid product whose infrared spectrum showed a band at 940 cm -1, which is characteristic for P-O-P bonds, but no bands characteristic of the P-OH bond.

35

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22 150195

Preparation 4

Preparation of pyrophosphate from lauryl acid phosphate A solution of 30.4 parts by weight of lauryl acid phosphate (the same as in Preparation 1) in 21 parts by weight of toluene g was placed in a dry reaction vessel which had already been rinsed with. nitrogen, and heated to 40 ° C with stirring, during which time a solution of 7.6 parts by weight of polymethylene-polyphenyl-polyisocyanate (eq. weight 133, functionality 2.8) containing about 50% methylene bis (phenylisocyanate) was added. )) in 5 parts by weight of toluene. The resulting mixture was stirred while introducing a stream of phosgene (about 0.1 part by weight per minute) and slowly raising the temperature to 80 ° C, keeping it under continuous introduction of phosgene until a total of 15 parts by weight of phosgene. The total time of the phosgene addition. was 5 hours and 50 minutes. After completion of the phosgene addition, the reaction mixture was heated to the same temperature for a further 40 minutes before being heated to 90-95 ° C and rinsed with nitrogen for 2 hours to remove excess phosgene. The pressure in the reaction vessel was then reduced until reflux of toluene began and the flushing with nitrogen was continued for an additional 2 hours, after which the toluene was removed by distillation under reduced pressure and the last traces in vacuo. The residue was cooled to room temperature, treated with diatomaceous earth ("Celite 545") and filtered after stirring for 30 minutes. There were thus obtained 23.7 parts by weight of a mixture of lauryl pyrophosphate and polymethylene-polyphenyl-polyisocyanate, which was found to contain 6.08% (w / w) phosphorus.

Preparation 5

Further preparation of pyrophosphate from lauryl acid phosphate 35 In the manner described in Preparation 4, but by

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To replace the polymethylene polyphenyl polyisocyanate with an equivalent amount (6.8 parts by weight) of phenyl isocyanate, an additional portion of lauryl pyrophosphate was obtained.

Example 1

A number of samples of wood particle boards were prepared in the manner described below from the components and amounts thereof (parts by weight) listed in Table I.

The wood chips (pivots) were placed in a rotary mixing drum and rotated while the particles were sprayed with an aqueous emulsion of the polyisocyanate, water, phosphate and emulsifier. The emulsion was prepared by mixing the components in a Turrex mixer. The resulting emulsion was sprayed with a paint spray gun on the wood particles, which was swirled for 45-120 seconds to achieve homogeneity. The coated particles were laid out on a felt mat on a cold rolled steel plate of 30 x 30 cm by means of a veneer molding frame.

After removing the mold frame, steel rods 20 were applied to a thickness corresponding to the desired thickness (6.2 mm) for the final particle plate along the two opposite sides of the steel plate, and a second cold-rolled steel plate of 30 x 30 cm was placed on top of the mat. The assembled assembly is then placed on the bottom plate of a baking press 25 having a capacity of 4,4482 Newton (100,000 lbs. Of force).

Both plates in the press were preheated to a selected temperature listed in Table I. Thereafter, pressure was applied and the forming time given in Table I was calculated from the point at which the pressure exerted on the mat reached 35 kg / cm. At the end of the molding time set out in Table I, the pressure was lifted and the particle plate was withdrawn. In all cases, it was found that the removal took place easily without any inclination for the plate to adhere to the plates with which it was in contact, which is in direct opposition to the behavior of a plate produced. under identical conditions, but without the presence of the lauryl acid phosphate in the emulsion used as a binder in the preparation of the plate.

The various samples of such prepared particle plates were then subjected to a series of physical samples and the properties thus determined are listed in Table I. These properties clearly show the excellent structural strength properties of these plates.

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25 150195

Table I

Plade___A_B_C_D

Materials used 5 wood shavings 644 644 644 644 weight of water in chips 56 56 56 56 polyisocyanate1 19.2 19.2 19.2 19.2 water in emulsion 51 51 51 51 2 lauryl acid phosphate 1.9 1.9 1.9 1 , 9 3 10 emulsifier 0.1 0.1 0.1 0.1 0.1

X

% polyisocyanate (w / w). 3.0 3.0 3.0 3.0 51% water (w / w) 17 17 17 17

X

% phosphate (w / w) 0.3 0.3 0.3 0.3 χ% emulsifier (w / w) 0.016 0.016 0.016 0.016 Plate temp., ° C 171 171 171 171 molding time, min. __1 ^ 5_2.0 2.5 3.0

Physical Properties 2 Density, g / cm 0.640 0.656 0.656 0.640 4 2 Breakage Module, kg / cm 259.7 252.0 301.0 312.9 4 2 3 20 Elasticity Module, kg / cm x 10 35.14 33.04 37, 80 38.01 4 2 dry internal bond, kg / cm 7.14 7.28 7.84 6.30 5 »2 in terms of internal bond, kg / cm_1,61 1.68 1.68 1.61

Footnotes to Table I

1: polymethylene-polyphenyl-polyisocyanate, eq. Weight 133, functionality 2.8, containing approx. 50% methylene bis (phenyl isocyanate).

2: mixture of lauryl diacid phosphate and dilauryl monosacid phosphate.

Hooker Chemical Company.

3: ethoxylated propoxylated butanol, "Witconol APEB", Witco Chemical Company.

The 30 tests performed according to ASTM-1037-72.

the tests performed according to German V-100 specifications.

£ calculated on the dry weight of the wood particles.

35

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150195 26

Example 2

A number of samples of wood particle boards were prepared in the manner described in Example 1 using the components and amounts listed in Table II (all in weight by 5 parts). The molding time shown in the table for samples E and F is the time during which the mat under pressure 2 (35 kg / cm) after the internal temperature of the mat (determined with a thermocouple inserted therein) had reached 55 ° C.

Sample G was a control sample shaped as described in Example 1. Table II also lists the physical properties determined for each of the finished particle plates and shows the excellent structural strength of the various samples. All the samples were easy to take and showed no signs of sticking to the steel sheets used for their manufacture.

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27 150195

Table II

Plade_E_F_G

5 Materials used wood chips 644 644 644 weight of water in chips 56 56 56 polyisocyanate (as in Example 1) 21 42 21 water in emulsion 56 56 56 two lauryl pyrophosphate 1 '2.1 4.2 2.1 emulsifier (as in Example 1) Example 1) 0.1 0.1 0.1% polyisocyanate (w / w) 3.3 6.6 3.3 *% water (w / w). 17.4 17.4 17.4

X

% pyrophosphate (w / w) 0.33 0.65 0.33 a 15% emulsifier (w / w) 0.016 0.016 0.016 plate temp, ° C 180 180 180 molding time, min_2_2_2

Physical properties, 2 density, g / cm 0.656 0.656 0.672 2 2 20 modulus of fracture, kg / cm 359.1 356.3 372.4 2 2 3 modulus of elasticity, kg / cm x 10 35.35 35.91 36.47 2 2 dry internal bond, kg / cm 8.96 9.87 9.24 3 2 wet internal bond, kg / cm 2.24 2.66 2.17

Footnotes for Table II

25 S prepared as described in Preparation 1 2: the tests carried out according to ASTM 1037-72 3: the tests carried out according to German V-10Q specifications x, calculated on the dry weight of the wood particles.

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150195 28

Example 3

A number of samples of wood particle plates were prepared using the same reactants and amounts as in Example 1 and exactly the same procedure except that the plates in the press were preheated to 204 ° C and kept at temperature in the molding times listed in Table III. The physical properties of the thus prepared specimens are also listed in Table III, showing that these specimens all had structural strength and none of the specimens showed a tendency to adhere to the plates upon removal.

Table III

Plate H_I_J_K L

Forming time, minutes 1.0 1.5 2.0 2.5 3.0

Physical Properties 2 Density, g / cm 0.640 0.640 0.656 0.640 0.640 In 2 breaking module, kg / cm 195.2 247.1 220.5 224.7 235.9 1 23 modulus of elasticity, kg / cm x 10 28.63 33.04 30.87 30.66 31.78 1, 2 dry internal bond, kg / cm 6.58 7.14 6.16 7.49 7.49 2 2 wet internal bond, kg / cm_1.61 1.68 1 , 61 1.75 1.68

Footnotes for Table III

the tests performed according to ASTM 1037-72 2: the tests performed according to German V-100 specifications.

25

Example 4 ·

A number of samples of wood particle plates are prepared in the manner described in Example 1, but under varying the nature of the polyisocyanate and using the pyrophosphate derived from oleyl acid phosphate prepared as described in Preparation 3, instead of the lau -rylic acid phosphate. The various components and amounts thereof (all in parts by weight) are listed in Table IV together with the physical properties determined on the finished samples.

0 29 150195

The thickness of the plate samples was in all cases 5.9 mm (spacers of appropriate thickness were used).

None of the specimens produced showed any tendency to adhere to the forming plates during removal, and the physical properties of the various specimens show that all had excellent structural strength.

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150195

Footnotes to Table IV

1: liquid prepolymer of methylene bis (phenyl isocyanate), equiv 181.

2 in polymethylene-polyphenyl-polyisocyanate containing 5 65% methylene bis (phenyl isocyanate), equiv 133.

3: polymethylene polyphenyl polyisocyanate containing ca. 45% methylene bis (phenyl isocyanate), equiv 133.5.

4: liquid methylene bis (phenyl isocyanate) prepared according to United States Patent No. 3,384,653, eq. 143.

10 ^: polymethylene-polyphenyl-polyisocyanate containing ca. 35% methylenebis (phenylisocyanant1, equiv. 140).

^: polymethylene-polyphenyl-polyisocyanate containing ca. 35% methylene bis (phenyl isocyanate), equiv. 140.

7: polymethylene polyphenyl polyisocyanate containing approx. 70% methylene bis (phenyl isocyate), equiv 133.

®: as in Example 1.

9: toluene diisocyanate.

the tests performed according to ASTM 1037-72.

11: the tests-performed according to German V-100 specifications.

20

Example 5

This example illustrates the preparation of particle boards according to the invention using a binder mixture in which there is no emulsifier and the polyisocyanate in undiluted form, i.e. not in the form of an aqueous emulsion.

A number of samples of wood particle plates were prepared using the components and amounts listed in Table V (all by weight) and the procedure described in Example 1 except that the wood particles were first sprayed with the specified amount of water and then with a mixture of the polyisocyanate and the phosphate release agent.

Table V also lists the physical properties determined for each of the finished particle plates and shows the excellent structural strength of the various samples. All the samples were easy to take and showed no signs of sticking to steel sheets used in their manufacture.

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33 150195

Table V

Plate W_X_Y_Z ZZ

Materials used 5 wood shavings 644 644 644 644 644 weight of water in shavings 56 56 56 56 56 polyisocyanate (as in Example 1) 38.6 38.6 38.6 38.6 38.6 water 56 56 56 56 56 lauryl pyrophosphate 3 9 3.9 3.9 3.9 3.9 10 (as in Ex. 2)

K

% polyisocyanate (w / w) 6 6 66 6 M% water (w / w) 17.4 17.4 17.4 17.4 17.4% pyrophosphate (w / w) 0.6 0.6 0.6 0.6 0.6 molding time (min) 2 2.5 3, 2.5 2.5 plate thickness (mm) 9.5 9.5 9.5 12.7 12.7

Physical Properties 3 Density, g / cm 0.672 0.656 0.672 0.640 0.656 1 2 Breakage Module, kg / cm 372.40 363.02 405.09 302.75 336.70 1 2 3 Elasticity Module, kg / cm x 10 35.07 35, 70 39.48 26.39 25.55 1 2 20 dry internal bond, kg / cm 9.45 9.31 9.87 12.81 12.46 2 2 wet internal bond, kg / cm_ 3.01 2.94 3 , 22 3.50 3.43

Footnotes to Table V

χ calculated on the dry weight of the wood particles ^ the tests carried out according to ASTM 1037-72 2 25 the tests carried out according to German V-100 specifications.

Example 6

This example illustrates the preparation of three particle plates by the process of the invention from 30 wafer chips of varying dimensions up to 51 x 51 x 0.79 mm 'from Weldwood of Canada, Ltd.

No water or emulsifier from the outside was used and the polyisocyanate and phosphate release agent were used undiluted.

35 A number of samples of particle plate were prepared.

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Using the components and amounts (all in parts by weight) of the planer shavings and the method described in Example 1, except that the planer shavings were sprayed with a mixture of the polyisocyanate and phosphate release agent and not with a aqueous emulsion as in Example 1, and that aluminum forming plates were used. All the samples were easy to take and showed no signs of sticking to the aluminum sheets used in their manufacture.

The excellent structural strength properties of the particle plates obtained, as shown by the high fracture modulus listed in Table VI, are very advantageous when compared to the low value of this parameter (175 2 kg / cm) determined for a commercially available plate. 15 prepared from the same type of planer shavings using a phenol-formaldehyde resin binder.

Table VI

Plate AA_BB CC

20 planer shavings 955 955 955 weight of water in shavings 45 45 45 polyisocyanate1 19.1 50 50 lauryl pyrophosphate 2.5 6.5 6.5 (as in Example 2) 25 K% polyisocyanate (w / w) 2 5.2 5 , 2 K% water (w / w) 4.7 4.7 4.7 K% pyrophosphate (w / w) 0.26 0.68 0.68 forming time (min) 4.5 4 4.5 sheet thickness, mm 12.7 12.7 12.7 Density, g / cm3 0.736 0.688 0.720 Breaking modulus, kg / cm2__512.19 556.22 760.20 x calculated on the dry weight of the chips 1 polymethylene-polyphenyl-polyisocyanate, eq. weight 139, functionality 3.0, viscosity at 25 ° C 700 cp, containing approx. 35% methylene bis (phenyl isocyanate).

150195 35 0

Example 7

This example illustrates the preparation of a series of particle plates using polyisocyanate binders in combination with various commercially available phosphates in amounts corresponding to about 0.7% (w / w) phosphorus in the binder resin combination.

The various samples were prepared using the components and amounts listed in Table VII (all in parts by weight) and the procedure described in Example 1, except that no emulsifier was used and that the chips first sprayed the water and then the isocyanate mixed with the release agent. All the samples were easy to take and showed no sign of sticking to the steel sheets used in their manufacture. In contrast, a control plate made in exactly the same way but without the use of a phosphate release agent was found to adhere to the steel plates used for its manufacture and could not be removed without damage to the plate. surface.

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37 150195

Footnotes to Table VII

^ Alkyric acid phosphate derived from lauryl alcohol, already reacted with 3 moles of ethylene oxide, from the Texas Division of Henkel Inc., Hawthorne, California.

2 5 Lauryl Acid Phosphate from Emery Industries Inc., Maul din, South Carolina.

3

Alkyric acid phosphate derived from ethoxylated lauryl alcohol, Emery Industries Inc.

4

Alkyric acid phosphate derived from ethoxylated branched chain medium chain aliphatic alcohol, Emery Indu stries, Inc.

Alkylated acid phosphate derived from n-octyl alcohol, Textiliana as above.

g

Alkyric acid phosphate derived from ethoxylated lauryl alcohol from Emery Industries Inc.

7

Prepared as described in Preparation 5.

Calculated on the dry weight of the wood shavings.

Example 8 A further series of particle plate samples is prepared using the same phosphate releasing agents and process as in Example 7, but with lower concentrations in the binder resin combination. The various components and amounts thereof (all in parts by weight) are listed in Table VIII together with the physical properties determined for some of the samples. All the samples could easily be taken out without damage to the plate or apparent attachment to the forming plates. The samples prepared using the higher concentrations of 30 phosphate release agent could, upon withdrawal, slip out between the forming plates, while some of the samples prepared with the lower concentrations of phosphate release agent (OO, QQ and UU ), required assistance, e.g. knocking of the forming plates to promote release. All the samples had a thickness of 12.7 mm in the finished plate.

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H -rirn ®Αί = ®0) ®® · ΗΛ '^ \ ΟβΛ-Ρί-ιΟ G * ^ ® (nwM' '' 'HSiotJ> biS'Hlo <tf' & '- f

-H> d ^ CM 3 13 A! , ¾ Μ Λ 4-> G 4-1 <SJ

ij G 4-1 - ιη ^ ωϊ-ιΗ '· ®1 · 4-1 -H 13 Ή

• ffl «3 fa3 = CMfiOrt! BrOR®- ®c3 ^ Æ3M

4J '> G Ό in (¾ * ί O C in ® -H ® 13 H 4J M -H S ® Π) 3GCM' i-IOCM134-10iH3-H®4J 0 04-> SMMMi-iRinOOOEroGWONiS O +>

®30> Beer Cji in—! -H Beer> M o -Η R M RS

4JG O OMMO>, OÆR®®B-lJ-rlØ-rlØ

ΐ3 · ι3βΒΙ · Ρί8ω®ιΰϋΐβ -rlAiW-ØW

G Ο, Φ-rl 3144-14-1144 ®U4'rl GW ®3 3 ^) 00, ¾ O'W-PIS-tWil-lWRr-lOr ^ B * rl3p, rT "& G ^ 4 ·> SEARCH? r4! L, OORT4MjftM®S91 U 4) 3 i ft ti Π GSO -H E4 fa fo E4 M Bl O> i P. ~ row 4-3> O, 4-1 5 - =: ÉH l I df 14 ft , CMCMCM fciHCM 2

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39 150195

Example 9

This example illustrates the use of a binder agent resin combination of the invention together with a prior art phenol-formaldehyde resin binder.

All the samples (with a thickness of 12.7 mm) prepared are conducted in the manner described in Example 1 with the exceptions given below and using the reactants and weight amounts listed in Table IX (all in parts by weight). To prepare the plates YY and ZZ, the phenol-formaldehyde resin was incorporated into the emulsion of the isocyanate, while the chips for preparing the plate AAA were first sprayed with the indicated amount of added water, then with the phenol-formaldehyde resin and finally with the polyisocyanate. . To prepare the control panel BBB, the chips were first sprayed with water and then with phenol-formaldehyde resin. Plates XX and ZZ showed no appreciable attachment to the forming plates, while plates YY, AAA and BBB presented serious attachment problems. Table IX also lists the physical properties of the different plates, and it will therefore be seen that the properties of plates XX and ZZ, both within the scope of the present invention, are clearly better than for plates YY, AAA. and BBB, all of which are outside the scope of the invention.

25 0 40 150195

Table IX

Plates_XX_YY_ZZ AÅA BBB

Materials wood shavings 1920 1920 1920 1920 1920 5 the weight of water in the shavings 80 80 80. 80 80 ^ phenol formaldehyde resin - 96 96. 96 192 polyisocyanate (as in Example 1) 96 48 48 48 added water 208 160 160 160 112 2 emulsifier 2.4 2.4 2.4 - - 3 10 lauryl pyrophosphate 9.6 - 4.8

X

% resin (w / w) 55555 X% water (w / w) 15 15 15 15 15% phosphate (w / w) 0.5 - 0.25 plate temp., ° C 177 177 177 177 177 15 molding time (min .) _ 5.5_5.5_5.5_5.5 5.5

Physical properties density, · g / cm ^ 0.667 0.685 0.714 0.712 0.662 ^ breaking modulus, kg / cm2 255.5 210.0 232.4 227.5 17.3.9 4 2 3 modulus of elasticity, kg / cm x 10 21.70 21, 00 24.85 22.33 21.07 4 2 20 dry internal bonding, kg / cm 11.90 11.06 10.64 11.76 7.00 5. 2 watt internal bond, kg / cm_5.46 4.48 4.27_3.50 1.54 ^ PB-65, Borden, aqueous suspension, 50% dry matter 2 aqueous solution, the sodium salt of a styrene / maleic anhydride copolymer, 30% dry matter, Monsanto 25 3 prepared as described in Preparation 4 4 the tests performed according to ASTM-1037-72 5 the tests carried out according to German V-100 specifications based on the dry weight of the wood particles.

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41 150195

Example 10

A number of samples on wood particle boards were prepared using a combination of a polymethylene polyphenyl polyisocyanate and an acid phosphate as the binder. The polyisocyanate used in all cases was polymethylene polyphenyl polyisocyanate containing ca. 48% by weight of methylene bis (phenyl isocyanate) and having an isocyanate equivalent of 134.5 and a viscosity at 25 ° C of 173 cp. Acidic phosphate-two phates were used differently in each case, but all of the acid phosphates were mixtures of the diacid phosphates 0 0 ell t R0-P (OH) 2 and monoacid phosphates (RO ^ PiOH), where R had the value given in Table X below. .

In all cases, the procedure for preparing the particle plate sample was as follows:

A portion of 2500 g of Douglas fir chips was sprayed with a mixture of 112 g of the above polyisocyanate, the acid phosphate in an amount corresponding to the proportion set forth in Table X below, and 40-50 g of "Freon Ril" (trichlorofluoromethane) using The method and apparatus described in Example 1. When the spraying and rotating with polyisocyanate was complete, an aliquot (2156 g) of the treated chips was used to prepare a 9.5 mm thick particle plate using the procedure described in Example 1 but using cold rolled steel sheets with a dimension of 60 x 90 cm and a molding frame with internal dimensions of 47 x 76 cm. A sheet of aluminum foil 30 is inserted between each steel plate and the adjacent surface of the particle plate mat. The plate temperature was approx.

175 ° C and the pressing time was 2.5 minutes at a minimum o 2 pressure of approx. 35 kg / cm in all cases. Thus, after the particle plate, together with the aluminum sheets in contact, was removed from the press plates, the relative

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42 150195 ease with which the aluminum foil is separated from the particle plate as either "excellent" (no resistance to removal), "good (no resistance to pulling of the foil) or" roughly "(some resistance, but the foil can be pulled off without to be torn to pieces or otherwise damaged) ·

Table X

% w / w% w / w £ Acid Phosphate R in Binding Acid Phosphate in Binder Release 2 C12H25 (OCH2CH2 ^ T ~ 0.6 "9.1 excellent 3ci2S25 ^ 0CH2CH2 ^ T" 0.6 10.6 excellent - - 4C12H25 (OCH2CH2 -) - g-0.6 13.6 excellent C_H - 0.5 4.6 excellent 15-o X / 2-ethylhexyl 1.2 10 good 6 tridecyl_0.8_10_ excellent

Footnotes: 1: binder = polyisocyanate + acid phosphate 20 2 in "Fosterge A2523", Textilana 3: "Tryfac 325A", Emery Industries 4: "Tryfac 525A", Emery Industries 5; Mobile Corporation 6: Mobile Corporation 25

Example 11

Using the same method as described in Example 10 with the one exception that the polyisocyanate was sprayed onto the wood shavings during a first spraying 3Q and rotary operation and the treated shavings were then sprayed during a special operation with 15.27 g bis-0 -2-ethylhexylpyrophosphoric acid [R0-P-O-P-RR; R = 2-ethylhexane

OH OH

35 µl] in 50 g of "Freon Ril". The particle produced thereby

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43 150195 plate easily released the aluminum foil and the release was rated "excellent".

Claims (5)

A process for the preparation of particle plates in which particles of organic material which can be compressed are added to polyisocyanate and the treated particles are then formed into plates by application of heat and pressure, characterized in that said particles are additionally added to a phosphate in an amount of between 0.1 and 20 parts by weight for every 100 parts by weight of the 10 polyisocyanate, which phosphate is selected from the following groups: (a) acidic phosphates of the formulas? * RO-P-OH or (RO) 9P-OH! OH (I) (XI) 20 and the ammonium, alkali metal and alkaline earth metal salts thereof, (b) pyrophosphates corresponding to those derived from the acidic phosphates I and II and mixtures of I and II, (c) the O-monoacyl derivatives of the acidic phosphates I and II 25 of the formulas 0 O RO-P-OCOR1 or (RO) ~ P-OCOR1 in 30 (V) (VI) (d) carbamoyl phosphates of formula O 150195 O 2 t R NHCO-OP (OR) Ih 5 (VII) and ammonium, the alkali metal and alkaline earth metal salts of these compounds, two (e) branched polyphosphates of the formulas 0 0 0 0 0 ^ / j \ Φ RO-P-0-P (OR) 2 or (RO) 2P-0-P-0 -P (OR) 2 OP (OR) 2? 15 ψ 0-P (OR) ~ 0 Z (VIII) (IX) (f) polyphosphates corresponding to formula 20? [ROP-O] n (X) including the cyclometaphosphates (n = 3), and (g) mixtures of two or more of the above compounds, in the formulas given, each R is selected from alkyl groups of 8-35 carbon atoms, alkenyl groups having 8-35 carbon atoms and groups of formula 30 R '- (O-CH-CH-),. . n AB where R * is alkyl of 8-35 carbon atoms, one of the groups A and B is hydrogen, while the other is 150195 o is hydrogen or methyl, and n is a number having an average value of 1-5, while R is hydrocarbyl of 2 1 to 12 carbon atoms, R is hydrocarbyl of 1 to 12 carbon atoms or hydrocarbyl substituted by at least one additional group of the formula -NHCOO - ^ (OR) 2, where R an integer. Process according to claim 1, characterized in that the polyisocyanate is a polymethylene-polyphenyl 1-polyisocyanate containing from 25 to 90% by weight, preferably from 35 to 65% by weight, methylene bis (phenylsocyanate), while the remainder of the mixture are oligomeric polymethylene'-polyphenyl polyisocyanates having a functionality of more than 2. Process according to claim 1, characterized in that the polyisocyanate and the phosphate are applied simultaneously to the particles in the form of an aqueous emulsion. Method according to claim 1, characterized in that the particles are contacted with the polyisocyanate and the phosphate separately, either in the form of aqueous emulsions or after the particles have been contacted with water. 5. Stable binder for the preparation of particle plates, characterized in that it comprises a mixture of (a) a polymethylene-polyphenyl-polyisocyanate containing from 25 to 90% by weight of methylene bis (phenylisocyanate), while the remainder of the mixture are oligomeric polyethylene-polyphenyl-polyisocyanates having a functionality greater than 2.0, and