DD147339A5 - METHOD FOR PRODUCING PLATES COMPRISING PARTICLE FABRIC MATERIALS - Google Patents

Abstract

The invention relates to a process for the production of teilchenfoermigen substances plates in which a solidifiable teilchenfoermiges organic material is brought into contact with a polyisocyanate composition and formed under heat and pressure to form sheets. The aim of the invention is a simplification of the manufacturing process, wherein the task is to be solved in a rational manner to prevent sticking of the plates to the pressing heating plates. For this purpose, the particulate material according to the invention is brought into contact, in addition to the treatment with the polyisocyanate composition, with 0.1 to 20 parts of one or more particular phosphates. Examples of the phosphates used are mono-O-octyl, mono-O-nonyl, mono-O-heptadecyl or mono-O-docosenyl phosphate, O, O-di (octyl) -, O, O-di (nonyl) , Tetraoctyl or tetra (heneikosyl) phosphate.

Description

The invention relates to binder or Leimmassen for consisting of particulate plates, in particular the use of organic polyisocyanates as binder or Leimmassen for joining particulate matter to plates, the relevant binder or Leimmassen and the prepared from their use ^ of particulate matter existing panels. ,

Characteristic of the known technical solutions; The use of organic polyisocyanates, in particular of toluene diisocyanate, methylenebis (phenyl isocyanate) and polymethylene polyphenylene polyisocyanates, as binders or components of binder or adhesive compositions in the production of particulate materials is known (see US Pat. No. 3,428,592, 3 440 189, 3 557 263, 3 636 199, 3 870 665, 3 919 017 and 3 930 110).

In a typical process, the resin binders are optionally applied in the form of a solution, aqueous suspension or emulsion, on particles of cellulosic material or other types of materials from which (particulate) sheets can be made, or blended with these particles. For this one uses a tumble mixer, another mixer or a stirrer. Thereafter, the mixture of particles and binder or glue is formed into a mat and heated by means of. Heated plates under pressure. Such a process can be carried out batchwise or continuously. In order to

"To

To avoid the resulting plate-shaped objects on the heated plates (the press), it has heretofore been necessary to arrange an isocyanate-impermeable film between the surface of each formed plate-shaped article and the heating plates or the surface of the heating plates before each forming operation to coat with a suitable release agent or to apply to the surface of the particles as such a material that does not adhere to the heating plates. All of these alternative measures are cumbersome, especially when the process is carried out continuously. Also, these measures constitute a significant drawback in a process which is otherwise very well suited for the production of particulate panels of particularly good tensile strength properties

aim

It has now surprisingly been found that the disadvantages of the use of organic isocyanates as a binder or glue for the production of particulate plates can be largely avoided by incorporating certain phosphorus-containing compounds as internal release agents into the isocyanate compositions used. Although it is known from US Pat. No. 4,024,088 to use phosphorus-containing compounds as internal release agents in the preparation of polyether polyurethanes, the phosphorus compounds used in the above, however, are not suitable as internal release agents in the process according to the invention.

.. a. 215754

of the essence?

The subject of the invention is an improved process for the production of particulate plates in which a solidifiable particulate organic material is brought into contact with a polyisocyanate composition and thereafter the treated telicelliform material is thermoformed into plates which is characterized in that, in addition to the treatment with the polyisocyanate composition, the particulate material comprises, with respect to 100 parts by weight of polyisocyanate, from about 0.1 to about 20 parts of a phosphate consisting of

a) a phosphoric acid derivative of the formulas;

RO

^0H or (RO) ₂ fr -OH

or

OH (I) (II)

wherein each R is an alkyl radical having 8 to 35 inclusive carbon atoms, an alkenyl radical having 8 to 35 inclusive carbon atoms or a radical of the formula:

ι t ⁿ

A B.

in which R ^{1 represents} an alkyl radical having 8 to 35 inclusive of carbon atoms, one of the radicals A and B represents a hydrogen atom and the other represents a hydrogen atom or a

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Is methyl and η is an average number of 1 to 5

or their ammonium, alkali metal or alkaline earth metal salt}

b) a pyrophosphate derived from the phosphoric acid derivatives of formulas I and / or II;

c) an O-monoacyl derivative of the formulas derived from the phosphoric acid derivatives of the formulas I and / or II:

O O

1 ΐ

RO p OCOR _{1 or} (RO) ₂ P OCORi

(V) (VI)

wherein R has the meaning given and R ^{1 represents} a monovalent hydrocarbon radical having 1 to 12 inclusive carbon atom (s);

d) a carbamoyl phosphate of the formula:

R ₂ NHCO-O-P (OR)

OH (VII)

- 's - 215 7 5 4

wherein R has the meaning given and Rp is a monovalent hydrocarbon radical having 1 to 12 carbon atom (s) or a by

at least one further group of the formula 0

-NHCOO-P (OR) ₂ represents hydrocarbon radical substituted by R as indicated,

or its ammonium, alkali metal or alkaline earth metal salt j

e) a branched-chain polyphosphate of the formulas: OO

ί- / Κ. O (

- Ο-P (OR) ₂ . , t '

(RO) ₂ P-0-I

0 0 0

0-P (OR) ₂ or

> -Ο-P

P (ix)

O 0-P (OR) ₂

(VIII)

wherein R has the meaning given; f) a polyphosphate of the general formula:

ΐ.

[ROP-O] _n (X)

wherein R has the meaning given and η is an integer (including a Cyclometaphosphats with η »3) or

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g) a mixture of two or more of the said compounds,

in contact, -

The invention also relates to novel (binder or glue) compositions with organic polyisocyanates which contain at least one of the phosphorus-containing compounds mentioned. Furthermore, the invention relates to the particle-shaped plates produced by the process according to the invention.

By "alkyl radicals having 8 to 35 carbon atoms" are meant saturated monohydric aliphatic straight or branched chain radicals having the specified number of carbon atoms in the molecule, examples of such radicals being octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, pentaeosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, · And pentatriacontyl radicals and their isomers.

"Alkenyl radicals having 8 to 35 carbon atoms" are to be understood as monovalent, straight-chain or branched-chain aliphatic radicals having at least one double bond and the stated number of carbon atoms in the molecule. Examples of such radicals are octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, Tricosenyl, pentacosenyl, tria-

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Contenyl and Pentatriacontenylreste and their isomers.

By "pyrophosphates ... derived from acidic phosphates of formulas I and / or II" is meant the following: The acidic phosphates of formulas I and II are generally obtained in the form of mixtures of incorporating phosphate of formula II and dibasic Phosphate of the formula I. These mixtures are obtained by reacting the corresponding alcohol of the formula ROH in which R has the meaning indicated, with phosphorus pentoxide according to known processes customary for the preparation of acid phosphates (cf., for example, Kosolapoff "Organophosphorus Compounds", pages 220) to 221, John Wiley and Sons, Inc., New York, 1950). Optionally, the mixture of the resulting dibasic and dibasic phosphates can be separated, for example by fractional crystallization of the barium salts or similar salts (cf references cited above). In the process according to the invention, both the individual acid phosphates and geras of two or more of the same can be used. The pyrophosphates of formulas III and IV are readily obtained from the corresponding acidic phosphates of formulas II and I by reacting the latter with a dehydrating agent, eg carbonyl chloride, an aryl or alkyl monoisocyanate or polyisocyanate, N, N'-dihydrocarbylcarbodiimide and the like according to known methods ( See, for example, F. Cramer and M. Winter "Chem. Ber.", Vol. 94, page 989 (1961); ibid Vol. 92, p. 2761 (1959); M. Smith, JG Moffat and 'HG Khorana in »J. Amer. Chem. Soc ", Volume 80, page 6204 (1958) and F. Ramirez, ^'1 JF Marecek and I. Ugi in" J. Amer.

Chera. Soc., Vol. 97, page 3809 (1975)). The individual acidic phosphates of the formulas I and II can be converted separately into the corresponding pyrophosphates. Mixtures of the two types of acidic phosphates of the formulas I and II lead to the corresponding pyrophosphate mixtures.

Starting from the acidic phosphates of the formula II, the corresponding pyrophosphates of the formula are obtained:

(RO)

OO ₂ P_Ö-]

P (OR)

(III)

wherein R has the meaning given. Starting from the acid phosphates of formula I, the corresponding pyrophosphates consist of a complex mixture whose average composition is represented by the formula:

HO

O t P- I η is OR DR

OH

(IV)

wherein χ represents a number of an average value of 1 or above and R has the meaning given.

By a "monovalent hydrocarbon radical having 1 to 12 carbon atoms inclusive" is the number of carbon atoms removed by removing a hydrogen atom from the parent hydrocarbon.

2 ί 5 7 S 4

to understand the meaning of a monovalent remainder. Examples of such radicals are alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl or dodecyl radicals or their isomers ©, alkenyl radicals, such as vinyl, allyl, butenyl, Pentenyl, hexenyl, octenyl, decenyl or dodecenyl radicals or their isomers, aralkyl radicals, such as benzyl, phenylpropyl, phenethyl or naphthylmethyl radicals, aryl radicals, such as phenyl, tolyl, xylyl, naphthyl or biphenylyl radicals, cycloalkyl radicals, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radicals or their isomers, and cycloalkenyl radicals, such as cyclopentenyl, cyclohexenyl, cycloheptenyl or cyclooctenyl radicals or their isomers.

By "alkali metal" is meant, for example, lithium, sodium, potassium, rubidium and cesium. By "alkaline earth metal" is meant, for example, calcium, strontium, magnesium and barium.

The process according to the invention is carried out essentially in the same way as the relevant known processes in which an organic polyisocyanate is used as resin or glue binder or constituent thereof (cf., for example, DE-OS 2,610,552 and US Pat. No. 3,428,592). The only exception is that a phosphate of the type described is used in combination with the isocyanate composition used to treat the particulate matter to be joined together to form a sheet.

Sp is obtained by the process of the invention by joining particles of wood or other cellulosic materials or organic substances, which are

heating under pressure in the presence of a binder or sizing system in the form of a combination of an organic polyisocyanate and a phosphate of the type described (hereinafter referred to as "phosphate release agent ¹¹ ) particulate disc-shaped articles or plates.

The polyisocyanate and the phosphate release agent can be contacted with the particles in separate form as individual components. Preferably, the polyisocyanate and phosphate release agent are contacted with the particles either simultaneously or after mixing. When the polyisocyanate and phosphate release agents are added separately or in admixture, they may be blank, i. without dilution or solvent used. On the other hand, the one and / or other Beatandteil can be used in the form of an aqueous dispersion or emulsion.

The polyisocyanate constituents contained in the binder or size systems which can be used according to the invention may be any organic polyisocyanates containing at least two isocyanate groups per molecule. Examples of organic polyisocyanates are diphenylmetiandiisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, cc, α-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures of these two isomers, which are commercially available, triphenylmethane triisocyanates, 4,4 '. Diisocyanatodiphenyl ether and polymethylene polyphenyl polyisocyanates. The latter polyisocyanates provide blends of about 25 to about 90 % by weight of methylenebis (phenyl isocyanate) and the balance of poly (ethylene oxide) polyphenyl polyisocyanates of functionality

λ η τ η -ν £) .4 *}

-Ai-

215 7 5 4

Such polyisocyanates and processes for their preparation are known (see, for example, U.S. Patents 2,683,730, 2,950,263, 3,012,008 and 3,097,191). These polyisocyanates are available in a wide variety of modified forms. Such a form consists in a Polymethylenpolyphenylpolyisocyanat the specified type, which has been subjected to a heat treatment, usually at a temperature of about 150 ° to about 30O ⁰ C until its viscosity, determined at a temperature of 25 ⁰ C, to a Value has risen in the range of about 800 to 1500 mPa.s. Another modified polymethylene polyphenyl polyisocyanate is one which has been treated with minor amounts of an epoxide to reduce its acidity (see U.S. Patent 3,793,362).

Preferred polyisocyanates for use in the binders or sizing systems of this invention are the polymethylene polyphenyl polyisocyanates, especially polymethylene polyphenyl polyisocyanates having from about 35 to about 65 weight percent methylene bis (phenyl isocyanate).

When the organic polyisocyanate to be used as a binder or sizing system is to be used according to the invention in the form of an aqueous emulsion or dispersion, the aqueous emulsion or dispersion can be more commonly used as a binder or glue in the preparation of such aqueous emulsions or dispersions prepare well-known way. Thus, for example, the polyisocyanate can be dispersed in water in the presence of an emulsifier. Suitable emulsifiers are customary emulsifiers, for example of anionic and nonionic nature. examples for

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Nonionic emulsifiers are polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more reactants, namely ethylene oxide, propylene oxide, butylene oxide, and styrene, alkoxylated alkylphenols, such as ftonylphenoxypoly- (ethyleneoxy) ethanols, alkoxylated aliphatic alcohols, such as ethoxylated and propoxylated aliphatic alcohols about 4 to 18 carbon atoms, glycerides of saturated and unsaturated fatty acids, such as stearic, oleic and ricinoleic acid and the like, polyoxyalkylon esters of fatty acids, such as stearic, lauric and oleic acid, fatty acid amides, eg the dialkanolamides of fatty acids + such as stearic, lauric and oleic acids. A detailed description of such emulsifiers can be found in "Encyclopedia of Chemical Technology", 2nd ed., Vol .19, pp. 531-554 (1969), published by Int.Serience Publishers, New York.

The emulsion or dispersion may be prepared at any time prior to its use as a binder or glue, but preferably it will occur within about 3 hours before use. For the preparation of the aqueous polyisocyanate emulsions which can be used in the process according to the invention, it is possible to use all known processes customary for the preparation of aqueous emulsions. For example, the emulsion is obtained by introducing the polyisocyanate, emulsifier and water under pressure into the mixing chamber of the spray gun by means of a conventional spray gun in which the streams of water and polyisocyanate meet and are mixed under turbulent conditions. The resulting emulsion is sprayed in the form of a spray

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material auszuformenden cellulose particles is applied, drained.

As already mentioned, the phosphate release agent can be brought into contact with the particles as a separate or separate component. In this case, it comes in bare form, ie without diluent _t or as an aqueous solution or dispersion used. Preferably, when used alone in bare or diluted form, ie separately from the polyisocyanate, the phosphate release agent used is applied to the particles in the form of a spray jet. However, according to a preferred embodiment, the phosphate separating agent and the polyisocyanate are applied together in a single mass. This can be done in different ways. When the polyisocyanate is to be used as a resin or glue binder without a diluent such as water, the phosphate release agent may be incorporated into the polyisocyanate by mere admixing. When the polyisocyanate is to be used as a resin binder or size in the form of an aqueous emulsion, the phosphate release agent may be added as a separate component during or after preparation of the emulsion. In a particularly advantageous variant, the phosphate is premixed with the organic polyisocyanate prior to its emulsification. Thus, therefore, the organic polyisocyanate and the phosphate separating agent can be premixed and stored any time before the emulsion preparation. If an emulsifier is used in the preparation of the emulsion, this can also be added to the mixture of organic polyisocyanate and phosphate separator. Here, too, a storage-stable mass is obtained, which can be converted at any time by mere mixing with water into an aqueous emulsion which can be used as a resin binder or glue.

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When the polyisocyanate to be used as a binder or glue is used in the form of an aqueous emulsion, the proportion of the organic polyisocyanate contained in the aqueous emulsion is desirably about 0.1 to about 99 »preferably about 25 to about 75 wt.

When the phosphate separating agent is supplied as a separate component or in combination with the polyisocyanate, the amount of phosphate separating agent used per 100 parts of polyisocyanate is suitably about 0.1 to about 20, preferably about 2 to about 10, weight parts. The amount of emulsifier needed in the preparation of the aqueous emulsion is not critical and may vary widely depending on the particular emulsifier. In general, it is based on the polyisocyanate, about 0.1 to about 20 wt .-%.

The starting material used to make the particulate plates consists of particles of cellulosic materials and similar materials which can be plate-solidified and bonded. Typical such materials are wood particles from the wood and furniture industry, e.g. Wood shavings, veneer chips and the like, as well as particles of other cellulosic materials, such as shredded paper, pulp or vegetable fibers, such as cornhouses, straw, bagasse and the like, as well as non-cellulosic materials, such as wastes of polyurethanes, polyisocyanurates and foam polymers. Methods for producing suitable particles are known. Optionally, mixtures of particles of different cellulosic materials may be used. For example, particulate plates have become

- AS -

15 75

already successfully made from wood particle mixtures with up to about 3096 tree bark.

The moisture content of the particles may suitably range from about 0 to about 24 parts by weight. Typically, lumber waste particles contain about 10 to 20% moisture, they can be used without pre-drying.

The particulate panels are obtained by spraying the particles with the constituents of the binder or adhesive mass (either separately or in combination) while circulating or agitating the particles in a mixer. For example, based on the weight of the "bone-dry" particles, a total of about 2 to 8 weight percent binder system (excluding any water contained therein) is added, but in a given case, higher or lower levels of resin binder may also be added. Further, other additives such as wax sizing agents, fire retardants, pigments and the like can be incorporated into the particles during the mixing process.

After a uniform mixture is obtained by sufficient mixing, the coated particles are formed into a loose mat or felt having preferably between about 4 and about 18 weight percent moisture content. The mat or felt is then placed in a heated press between polished sheet metal plates and pressurized to solidify the particles to a plate. The .Preßdauer, pressing temperature and the pressing pressure can, depending on the thickness of the desired plate, the desired density of Plat-

5 7

te, the size of the particles used and other factors known to be very different. Thus mm thick, for example, about 12.7, from particulate medium density boards pressures of about 294 to 686 bar and emperaturen of about .162 ° to 191 ⁰ C are typical. The pressing time is typically about 2 to 5 minutes. Since some of the moisture contained in the respective mat or felt reacts with the polyisocyanate to form polyurea, the moisture content of the mat in isocyanate binders or sizing materials is not as critical as in other binder or size systems.

The described process can be carried out in batches whereby individual layers of particulate plates are formed by treating a suitable amount of particles with the resin binder or glue combination and heating the treated material under pressure. On the other hand, the process can also be carried out continuously by treating treated particles in the form of a continuous belt or a continuous mat through a heating and pressing zone, which are supplied by upper and lower continuous belt, which and the required heat and the required pressure , is set to be run.

Irrespective of whether the process according to the invention is carried out batchwise or continuously, it has been found that the particle-shaped plates obtained using the combination of polyisocyanate and phosphate separating agent according to the invention are readily separated from the metal plates of the press used in their manufacture and

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show no tendency to stick or stick to the plates concerned. This is in direct contrast to previous experience in the sole use of polyisocyanates as binders or glues.

In the process according to the invention, all phosphate separation agents of the specified type can be used either alone or in combination. Preference is given to the pyrophosphates of the formulas III and IV or mixed pyrophosphates of mixtures of the acidic phosphates of the formulas I and II. In this way, the free hydroxyl radicals present in the pyrophosphates or any free hydroxyl radicals present in the as yet unconverted acidic phosphate starting material may be present in usually sufficiently hindered, so that they do not react at room temperature with the particular polyisocyanate used. Consequently, the pyrophosphates in combination with the polyisocyanate itself can be stored for extended periods of time without any sign of impairment or degradation. When the mixture of pyrophosphate and polyisocyanate is emulsified and used in the process according to the invention, presumably the treatment temperature and the vapor produced by the formation of the particulate plates lead to hydrolysis of the pyrophosphate to reformation of the corresponding acidic phosphates then facilitate the subsequent separation of the particulate plate from the plates of the press. However, this theory is merely an attempt to explain it.

As already mentioned, the monobasic substances used in the process according to the invention are obtained

Phosphates of the formula II and dibasic phosphates of the formula I and salts thereof by customary known processes, for example by reacting the corresponding alcohol of the formula ROH, wherein R has the meaning given, with phosphorus pentoxide (cf., Kosolapoff, supra). For the skilled person, it should be understood that when using mixtures of two or more different alcohols in the described reaction, a corresponding mixture of acidic phosphates of the formulas I and / or II, in which the different mixture components have different radicals R receives. As already stated, the mixture of monobasic and dibasic phosphates obtained in the described reaction can be prepared in a conventional manner, e.g. by fractional crystallisation and the like, into its individual components. The individual components obtained in this case can also be used in the context of the method according to the invention. On the other hand, and preferably, the mixture of monobasic and dibasic phosphates obtained in the above-described reaction without separation into its individual components is used in the process according to the invention or it is converted into the corresponding pyrophosphate mixture in the described manner. The latter mixture is then used in the context of the method according to the invention.

Examples of acid phosphates of the formula I which can be used according to the invention, alone or in combination with other acidic phosphates, are 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-heptade

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cyl, mono-O-octadecyl, mono-O-nonadecyl, mono-O-eicosyl, mono-O-heneikosyl, mono-O-docosyl, mono-O-tricosyl, mono-O-pentacosyl , Mono-O-hexacosyl, mono-O-heptacosyl, mono-O-octacosyl, mono-O-nonacosyl, 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-eicosenyl, mono-orthhenoicosenyl, mono-O-docosenyl, mono-O-tricosenyl, mono-O-pentacosenyl, mono-O-triacontenyl and mono-O-pentatriacosenyl dihydrogen phosphates, and the dibasic Phosphates wherein the esterifying moiety consists of a moiety derived from lauryl alcohol or a similar monohydric alcohol capped with from 1 to 5 moles of ethylene oxide.

Examples of acid phosphates of the formula II which can be used alone or in combination with other acidic phosphates are: O, O-di (octyl) -, O-di- (nonyl) -, O, O-di (decyl) - , Ο, Ο-diCundecyl), 0,0-di- (dodecyl) -, O, O-di (tridecyl) -, O ₁ O -di (tetradecyl) -, 0,0-di (pentadecyl) -, 0,0-Di (hexadecyl) -, O, O-di (heptadecyl) -, O ₁ O-di (octadecyl) -, O, O-di (nonadecyl) -, O, O-di (eicosyl) -, O, O-di (heneicosyl) -, O, O-di (docosyl) -, O, O-di (tricosyl) -, O, O-di (pentacosyl) -, O, O-di (hexacosyl) -, O, O-di (heptacosyl) -, OjO-di-octacosyl) -, O, O-di (nonacosyl) -, 0,0-di (triacontyl) -, O, O-di (pentatriacontyl) -, O, O- Di (dodeeenyl) -, O, O-di (tridecenyl) -, O, O-di (tetradecenyl) -, O, O-di (pentadecenyl) -, O, O-di (hexadecenyl) -, O- Di- (heptadecenyl) -, O, O-di (octadecenyl) -, O, O-di (nonadecenyl) -, O, O-di (eicosenyl) -, O, O-di (heneikosenyl) -, 0.0 -di (docosenyl) -, O, 0-di (tricosenyl) -, O, 0-di (pentacosenyl) -, O, 0-di (triacontenyl) - and O ₁ O-di (pentatriacosenyl) ·

- IO -

hydrogenphosphates and the double esterified hydrogenphosphates in which the esterifying moiety consists of a moiety derived from lauryl alcohol or a similar "monohydric" alcohol capped with from 1 to 5 moles of ethylene oxide.

Examples of the latter types of phosphates are commercially available in admixture with the corresponding zwibibasic phosphates.

Examples of pyrophosphates of the formula III which can be used alone or in combination with other pyrophosphates are tetraoctyl, tetranonyl, tetradecyl, tetraundecyl, tetradodecyl, tetra (trldecyl) -, tetra (tetradecyl) -, tetra (pentadecyl) -, tetra (hexadecyl), tetra (heptadecyl), tetra (octadecyl), tetra (nonadecyl), tetra (ecosyl), tetra (heneicosyl), tetra (docosyl), tetra (tricosyl), Tetra (pentacosyl), tetra (hexacosyl), tetra (heptacosyl), tetra (octacosyl), tetra (nonacosyl), tetra (triacontyl), tetra (pentatriacontyl), tetra (dodecenyl), tetra ( tridecenyl), tetra (tetradecenyl), tetra (pentadecenyl), tetra (hexadecenyl), tetra (heptadecenyl), tetra (octadecenyl), tetra (nonadecenyl), tetra (eikosenyl), tetra ( heneikosenyl), tetra (docosenyl), tetra (tricosenyl), tetra (pentacosenyl), tetra (triacontenyl) ~., and tetra (pentatriacosenyl) pyrophosphates.

Examples of pyrophosphates of the formula IV which can be used according to the invention, alone or in combination with other pyrophosphates, are di (octyl) -, di (nonyl) -, di- (decyl) -, di (undecyl) -, di (dodecyl) -, di (tridecyl ) -, di (tetradecyl) -, di (pentadecyl) -, di (hexadecyl) -, di-

-U-

215 7 5 4

(heptadecyl) -, di (octadecyl) -, di (nonadecyl) -, di (eicosyl) -, di (heneikosyl) -, Dl (docosyl) -, di (tricosyl) -, di (pentacosyl) -, 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 (eicos.enyl) -, di (heneikosenyl) -, di (docosenyl ) -, di- (tricosenyl) -, di (pentacosenyl) -, di (triaeontenyl) - and di (pentatriacosenyl) pyrophosphates.

The O-monoacyl derivatives of the acidic phosphates of the formulas I and II, which can likewise be used in the context of the process according to the invention and correspond to the formulas V and VI, can be prepared without difficulty by customary known processes. Thus, for example, the particular acidic phosphate of the formulas I or II in the form of its silver salt or other metal salt with a suitable acyl halide of the formula R ₁ COHaI, wherein Hal is a chlorine or bromine atom and Rj has the meaning given, after that of Kosolapoff, loc. Cit implemented on page 334. Examples of O-monoacyl derivatives of the acid phosphates of the formulas I and II are the 0-acetyl, 0-propionyl, 0-octanoyl, 0-decanoyl, 0-dodecanoyl, O-benzoyl, O-toluoyl, O-phenacetyl derivatives of the various (stated) acidic phosphates of the formulas I and II.

The usable in the process according to the invention carbamoyl phosphates of the formula VII-can be readily by reacting a suitable acidic phosphate of the formulas I or II with a suitable

Hydrocarbyl mono- or polyisocyanate, for example according to that of F. Cramer and M. Winter in Chem. Ber., Vol. 92, page 2761 (1959) Examples of such carbamoyl phosphates are the methyl-ethyl, propyl, hexyl, decyl, dodecyl, allyl, hexenyl, octenyl, decenyl -, dodecenyl, phenyl, tolyl, diphenylyl, benzyl or Fhenylpropylcarbamoyl- and similar hydrocarbamoylderivats of monobasic phosphates (stabilized in the form of their ammonium or alkali metal salts) of the specified type. The carbamoyl phosphates of formula VII may be due to incomplete conversion of the acid Because of the low reactivity of the OH radicals in question with the isocyanate, phosphates still contain free OH radicals in the reaction with the particular hydrocarbyl isocyanate. Residues are used with the isocyanate without unwanted side reactions used.

The polyphosphates of the formula X which can be used in the process according to the invention can readily be prepared by reacting a suitable trialkyl phosphate of the formula (RO) .PH, where R has the meaning given, with phosphorus pentoxide according to the process described by Kosolapoff, supra win. The polyphosphates are usually complex mixtures whose composition is generally represented by the formula X. These include cyclic compounds (n = 3) with 6-membered rings of alternating phosphorus and oxygen atoms. -

: s - 215754

The polyphosphates of the formulas VIII and IX which can be used in the process according to the invention are readily obtained by reacting a suitable di- or trialkyl phosphate with a suitable

Halophosphate of the formula (RO ₁ -P-Hal ₁ in which Hal is a chlorine or bromine atom, for example according to the process described by Kosolapoff, supra on page 338. This process results in the elimination of alkyl halides.

In the context of a further advantageous embodiment of the method according to the invention, the combination of polyisocyanate and phosphate release agent used as a binder or glue can be used together with a heat-fixable resin binder which is also already usable, for example a phenol / formaldehyde, resorcinol / formaldehyde, melamine / formaldehyde, urea / Formaldehyde or urea / furfural resin or a condensed furfuryl alcohol. By using such combinations, on the one hand, the adherence of the finished particulate plates to the platens of the press, which has hitherto been a problem when using a mixture of isocyanate and thermosetting resin binders of the type described, can be avoided, on the other hand, using such combinations made of particulate plates significantly improved physical properties.

The following preparation examples illustrate the preparation of phosphate separators usable according to the invention.

Production Example 1

Preparation of Acid Lauryl Phosphate Pyrophosphate

A mixture of 70 g of acidic lauryl phosphate (commercial mixture of 0.0-dilauryl hydrogen phosphate and 0-lauryl dihydrogen phosphate) and 60 g of phenyl isocyanate is placed in a dry equipped with a stirrer, condenser and drying tube flask, whereupon the flask in an 80 ⁰ C. pre-heated oil bath is dipped. While the temperature of the oil bath is slowly raised to 115 ⁰ C, the contents of the flask is stirred. About 1 h carbon dioxide escapes. After the cessation of carbon dioxide leakage, the reaction mixture is cooled to room temperature and diluted with 100 ml of chloroform. The resulting mixture is filtered. The remaining on the filter 24.8 g of Ν, Ν'-diphenylurea are washed with chloroform. The combined with the Vaschaschasch filtrate is concentrated in a rotary evaporator at a bath temperature of 50 ⁰ C. After evaporation of the major part of the solvent, crystalline N, N ^1, N "-Trlphenylbiuret after which the evaporation is interrupted for filtering off the precipitating 6.6 g of crystals separates out. After filtering off the solids, the filtrate is evaporated to dryness, and finally at exposed to a temperature of 5O ⁰ C to remove excess phenyl isocyanate reduced pressure. the obtained 70 g of residue consisting of the desired pyrophosphate in the form of a colorless to pale yellow liquid. the IR spectrum of the product obtained in CHCl ₃ is not for P-0H Bindings charac-

215 7 5 4

teristic gangs, but a strong 940 -1 band

cm, which is typical for P-O-P bonds.

Preparation of a pyrophosphate from acid lauryl phosphate:

A total of 70 g of the, used in Preparation Example 1 acidic Laurylphosphats be filled into a container provided with a stirrer, a reflux condenser and a gas inlet tube flask and heated therein to melting under nitrogen to a temperature of 65 ° to 75 ⁰ C. The melt is stirred for a total of 2.5 hours while a slow stream of phosgene is introduced. During the introduction of the phosgene, the temperature is kept within the specified range. In the first hour of phosgene addition, a vigorous escape of gas from the reaction mixture, then gradually escapes gradually less gas from the reaction mixture until the escape of gas from the reaction mixture at the end of the phosgene addition is only very weak. After the addition of phosgene is complete, the mixture is purged with nitrogen for 15 hours at a temperature within the specified range. Thereafter, the pressure in the reaction flask is gradually lowered to about 1.3 mbar to drive off gaseous hydrochloric acid and gaseous carbon dioxide. On standing overnight, the resulting viscous residue solidifies completely. There are obtained 66 g of pyrophosphate in the form of a solid which melts gradually at about 6O ⁰ C,. ^v ·

- it, - 215 7 5 4

Preparation Example .. ^

Preparation of a pyrophosphate from acidic oleyl phosphate s

A mixture of 200 g of acidic oleyl phosphate (commercial mixture of 0,0-Dioleylhydrogenphosphat and 0-Monooleyldihydrogenphosphat) is reacted at a temperature of 85 ° to 9O ⁰ C according to Preparation Example 1 5.5 h with 160 g of phenyl isocyanate. After the reaction mixture was diluted with 200 ml of chloroform, 68 g of N, N ^f -Diphenylharnstoff filtered off. The filtrate is concentrated by means of a rotary evaporator, the excess and unreacted phenyl isocyanate is distilled off under reduced pressure. On standing at room temperature, N, N ¹ , N "~ triphenylbluret are crystallized from the oily residue, and after filtering off the crystals, 196 g of a liquid product are obtained whose IR spectrum shows a band characteristic of POP bonds at 94-0 cm -1. but does not have a band typical of P-0H bonds.

Production Example 4 ".

Preparation of a pyrophosphate from acid lauryl phosphate:

A solution of 30.4 parts by weight of the acid lauryl phosphate used in Preparation Example 1 in 21 parts by weight of toluene is charged into a dry nitrogen-purged reactor. Thereafter, the solution is heated to 40 ^° C. with stirring. When this temperature has been reached, a solution of 7.6 g

215 7 5 4

weight of polymethylene polyphenyl polyisocyanate of equivalent weight 133 and a functionality of 2.8 with about 50% methylenebis (phenyl isocyanate) in 5 parts by weight toluene. The resulting mixture is stirred while a Phosgenatrom initiated (about 0.1 part by weight per min) and the temperature is slowly raised to 80 ⁰ C. While maintaining this temperature, phosgene is continuously fed until a total of 20 parts by weight of phosgene are introduced. The total duration of the phosgene addition is 5 h, 50 min. After completion of the addition of phosgene, the reaction mixture is left for a further 40 minutes at the same temperature, then heated to 90 ° to 95 ⁰ C and finally rinsed with nitrogen to remove excess phosgene for 2 h. Thereafter, the pressure in the reactor is reduced until the toluene begins to flow back. The purging with nitrogen is continued for another 2 h. Finally, the toluene is distilled off under reduced pressure, the last traces (toluene) are removed in vacuo. The evaporation residue is cooled to room temperature, treated with commercially available diatomaceous earth and filtered after being stirred for 30 minutes. This gives 23.7 parts by weight of a mixture of lauryl pyrophosphate and polymethylene polyphenyl polyisocyanate containing 6.08 wt .-% phosphorus.

Production Example j ? ,

Preparation of pyrophosphate from lauric acid phosphate:

According to Preparation Example 4, However, replacing the polymethylene polyphenyl polyisocyanate by an αςμ! Ν3-lente amount (6.8 parts by weight) of phenyl isocyanate to obtain a further batch of lauryl pyrophosphate.

The following examples are intended to illustrate the invention in more detail.

Example I ₁

Using the ingredients indicated in the following Table I in the indicated amounts (all parts "parts" means "parts by weight"), plate-shaped test pieces are made of wood particles by the method described below.

The wood chips are filled into a rotary drum mug. After the drum mixer has been set in rotary motion, the particles therein (wood chips) are sprayed with an aqueous emulsion containing the polyisocyanate water, a phosphate and an emulsifier. The particular emulsion is obtained by mixing the various ingredients using a commercial mixer.

The resulting emulsion is sprayed onto the wood chips or particles with the aid of a paint spray gun, while these are circulated for homogeneous coating for 45 to 120 s. The coated chips are formed into a matted mat using a plywood manufacturing frame on a 305 mm χ 305 mm stainless steel plate. After removal of the frame for plywood preparation, steel strips of a height or thickness corresponding to the desired final thickness of the plate consisting of wood chips (6.35 mm) are set up along the two opposite edges of the steel plate, whereupon the mat is fitted with a second 308 mm 8 308 mm large plate made of cold-rolled steel

, ,.,. 2 15754

is covered. The entire structure is then placed on the lower plate of a commercial press with a printing capacity of 45.4 t, whereupon both plates of the press are preheated to a certain temperature (see the following Table I). Now pressure is applied to the mold. Thereafter, the standing time indicated in Table I below is calculated at a point where the pressure applied to the mat is 34.5 bar. After completion of standing time (see the following Table I) is relaxed, whereupon the existing of the wood particles plate-shaped molding is removed from the mold. In all cases, it has been found that the demolding can be carried out without difficulty, without the plate-shaped molding has a tendency to stick to the plates with which it is in contact. This is in direct contrast to the behavior of a plate-shaped sample prepared under identical conditions, but in the absence of the acidic lauryl phosphate in the emulsion used as a binder in plate making.

The various plate-shaped samples are then subjected to a series of physical tests. "The properties thus determined are shown in the following Table I. The values for the respective properties show that the plate-shaped samples have excellent structural strength properties.

Table I

plate-shaped test piece BC D

used substances 644 644 644 644 or substances 56 56 · 56 56 wood chips 19.2 19.2 19.2 19.2 Weight of water in the wood chips 51 51 51 51 Polyisocyanate ' 1.9 1.9 1.9 1.9 Water content of the emulsion 0.1 0.1 0.1 0.1 acid lauryl phosphate ² 3.0 3.0 3.0 3.0 emulsifier 17 17 17 17 * Wt. % Polyiso cyanate 0.3 0.3 0.3 0.3 * Wt% water 0.016 0.016 0.016 0.016 * Wt% phosphate 171.1 171.1 171.1 171.1 * Wt. % Emulsifier 1.5 2.0 2.5 3.0 Plate temperature in OC Idle time in min Physical Eigen .6408 .6568 .6568 .6408 companies 260.8 255.1 302.3 314.2 Density (g / cnr) 35.3 33.2 38.0 38.2 Fracture modulus (kp / cm) 7.2 7.3 7.9 6.3 Young's modulus (kp / cm ² ) 4 χ icK Internal binding in dry state (kp / cm ² ) ^

Inner binding in the wet state (kp / cm ² ) 5.

1.6

1.7

1.7

1.6

IfM IQ

215754

footnotes:

1: polymethylene polyphenyl polyisocyanate of equivalent weight of 133 and a functionality of 2.8 with about 50% methylenebis (phenyl isocyanate)

Zx mixture of dibasic lauryl phosphate (lauryl dihydrogen phosphate) and monobasic dilauryl phosphate (dilauryl hydrogen phosphate)

3: Commercially available ethoxylated, propoxylated butanol

4: the tests are carried out according to the US standard specification ASTM-IO37-72

5: the investigations are carried out in accordance with German regulation V-100.

*: calculated on the dry weight of the wood chips. Example 2.

According to the method described in Example 1, a plurality of plate-shaped test pieces of wood particles are produced using the components indicated in the following Table II in the quantities also indicated (all "parts" mean "parts by weight"). The stand-by time given in the table for the plate-shaped samples E and F is the time that the respective bar reached a pressure of 34.4 bar after reaching an internal temperature (of the mat) of 54.4 ° C. determined with the aid of an inserted thermocouple is exposed. The plate-shaped test piece G is a comparison test piece produced according to Example 1. The physical properties determined for the individual plate-shaped test specimens

215 7 5 4

can be found in the following Table II, they prove the excellent structural strength of the various specimens. All samples are easy to demold and show no tendency to stick to the steel plates used in their manufacture.

Table II plate-shaped specimen EF G 644 644 56 56 used substances and sub 42 21 punch 644 56 56 wood chips 56 4.2 2.1 Water content of wood chips 21 0.1 0.1 Polyisocyanate (corresponding to Example 1) 56 6.6 3.3 Water content of the emulsion 2.1 17.4 17.4 Laurylpyrophosphat 0.1 0.65 0.33 Emulsifier (corresponding to example 1) 3.3 0.016 0.016 * Wt -.% Of polyisocyanate 17.4 179.4 179.4 * Wt .-? 6 water 0.33 2 2 * Wt .- ^ pyrophosphate 0.016 * Wt% emulsifier 179.4 1 0.6568 0,672i Plate temperature ( ⁰ C) 2 357.8 374.6 Standing time (min) 36.1 36.6 Physical Properties O, £ 656 9.9 9.3 Density (g / cm ⁵ ) 360.6 2.7 2.2 Fracture modulus (kp / cm) 35.5 Young's modulus (kp / cm) χ ick 9.0 Inner binding pin dry state (kp / cm) ² 2.2 Inner binding in wet state (kp / cm ^) 3

21 5 7 54

footnotes:

1: Prepared according to Preparation Example 1

2: the tests are carried out according to the US standard specification ASTM 1037-72

3: the investigations are carried out in accordance with German regulation V-100

*: calculated on the dry weight of the wood chips. Example 3

According to Example 1 indicated by the op ingredients in the supra stated amounts of plate-shaped specimens are prepared, however, the plate-th of the press to a temperature of 204.4 ⁰ C pre-heated and maintained for the indicated in the following Table III dwell times at this value become. The physical properties of the obtained samples are also shown in Table III, which shows that the various samples all have excellent structural strength. None of the samples showed any tendency to stick to the mold plates during demoulding.

5 4

Table III

plate-shaped specimen H I J K L

Time in minutes 1.0 1.5 2.0 2.5 3.0

Physical Properties

Density (g / cm ³ ) 0.6408 0.6408 0.6568 0.6408 0.6408 Fracture modulus (kp / cm ² ) ¹ 194.0 248.2 221.4 225.7 236.9

modulus of elasticity

(kp / cm ^z ) 1 χ iq ·? 28.8 33.2 31.0 30.8 31.9

Internal binding in the dry state (kp / cm ² ) ¹ 6.6 7.2 6.2 7.5 7.5

Inner binding in

wet condition '

(kp / cm ² ) ² 1.6 1.7 1.6 1.8 1.7

footnotes:

1: the investigations are carried out according to the US standard

Standard ASTM 1037-72

2: the investigations are carried out in accordance with German regulation V-100.

Example 4

However, using various polyisocyanates and instead of the acidic lauryl phosphate of the acidic oleyl phosphate derived pyrophosphate prepared in Preparation Example 3, various plate-shaped test pieces are made of wood chips. The various ingredients and their amounts (all parts "parts" means "parts by weight") are given in the following Table IV. Table IV contains

215 7 5 4

furthermore, information about the physical properties determined on the finished test specimens. The thickness of the plate-shaped specimens is in each case 9.5 mm (Abstreifzbänder appropriate strength used). None of the samples showed any tendency to stick to the mold plates during demoulding. The physical properties of the various samples show that all have excellent structural strength.

Table IV

plate-shaped specimen H NO P Q R ST U

used substances and 644 644 644 644 644 644 644 644 644 substances 56 56 56 56 56 56 56 56 56 wood chips Water content of wood snippets 21 21 polyisocyanate: 21 21 A ¹ B ² 21 21 21 21 'D ⁴ 21 F ⁶ G ⁷ H ^ 47 47 47 47 47 47 47 47 47 I ⁹ 2.1 2.1 '2.1 2.1 2.1 • 2.1 2.1 2.1 2.1 Water content of the Snul- sion pyrophosphate

Emulsifier (corresponding to.

Example 1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Continuation Table IV

* Wt .- # isocyanate 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3

* Wt -.% Water 16 16 16 16 16 16 16 16 16

* Wt -.% Pyrophosphate 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33

* Wt .- # Emulsifier 0.016 0.016 0.016 0.016 0.016 0.016 0.016 0.016 0.016 Plate Temperature (° C) 171.1 171.1 171.1 171.1 171.1 171.1 171.1 171.1 171.1 Staging Time (min ) 4 4 4 4 4 4 '4 4 4

Physical properties n

Density (g / cm ⁵ ) 0.6568 0.6408 0.6728 0.6568 0.6568 0.6728 O, 64o8 0.6568 O, 64o8

Breaking modulus (kp / cm ² ) ¹⁰ 283.3 358.5 384.5 310.0 378.2 438.7 417.6 433.0 208.1

modulus of elasticity

(kp / cm ² ) ¹⁰ χ ICK 32.7 38.1 38.9 30.4 34.7 37.1 41.0 42.3 34.9

Inner binding in dry condition

(kp / cm ² ) ¹⁰ .. · 5.3 8.9 9.6 5.8 5.8 6.6 11.8 11.6 3.3

38 ,1 38 9 30 4 34 7 37, 1 41 , 0 42 3 8th , 9 9 6 5, 8th 5, 8th 6 11 ,8th 11 6 1 , 9 2, 2 1, VJL 1, VJL 1, 5 2 , 5 2, 3

Inner binding in

wet state

(• kp / cm ² ) Ti 1.3 1.9 2.2 1.5 1.5. 1.5 2.5 2.3 1.1 ^

* based on the dry weight of the wood chips

footnotes:

1ϊ liquid prepolymer of methylenebis-phenyl isocyanate) of equivalent weight 181

2s polymethylene polyphenyl polyisocyanate with about 65% methylenebis-phenyl isocyanate) of equivalent weight of 133

3: polymethylene polyphenyl polyisocyanate with about 45% methylenebis-phenyl isocyanate) of equivalent weight of 133.5

4: liquid methylenebis-phenyl isocyanate) prepared according to U.S. Patent 3,384,653, having an equivalent weight of 143

5: polymethylene polyphenyl polyisocyanate with about 35% methylenebis-phenyl isocyanate) of equivalent weight of 140

6: polymethylene polyphenyl polyisocyanate with about 35% methylenebis-phenyl isocyanate) of equivalent weight of 140

7: polymethylene polyphenyl polyisocyanate with about 70% methylenebis-phenyl isocyanate) of equivalent weight of 133

8th; according to Example 1 9: Toluene diisocyanate

10: The tests are carried out according to the US standard specification ASTM 1037-72

11: the investigations are carried out in accordance with German regulation V-100. '

Example ^

This example illustrates the invention

- .39 -

2157 54

Preparation of particulate panels using a binder or glue composition which does not contain an additional emulsifier and wherein the polyisocyanate is in the blank form, i. not in the form of an aqueous emulsion.

Using the different components given in the following Table V in the quantities indicated above, all statements "parts." mean "parts by weight") are prepared according to Example 1 different plate-shaped specimens of wood chips, but the wood chips are first sprayed with the specified amount of water and then with a mixture of the polyisocyanate and the phosphate release agent. The physical properties determined in the final particulate test specimens are also given in Table V, showing the excellent structural strength of the various specimens. All samples can be demolded without difficulty and show no tendency to stick to the steel plates used in the production.

Table V

plate-shaped specimen V / X Y Z ZZ

and substances _;

Wood chips 644 544 644 644 644

Vasser content of

Wood chips 56 56 56 56 56

Polyisocyanate (corresponding to Example 1) 38.6 38.6 38.6 38.6 38.6

Water 56 56 56 56 56

Laurylpyropho sphat (corresponding to example Z) 3.9 3.9 3.9 3.9 3.9 * Wt .- ^ Polyisocya nat 6 6 6 6 ' 6 * Weight -% water 17.4 17.4 17.4 17.4 17.4 * Ge \}, -% pyrophosphate 0.6 0.6 0.6 0.6 0.6 Standing time (min) 2 2.5 3.0 2.0 2.5 Plate thickness (mm) 9.52 9.52 9.52 12.7 12.7 Physical Eigen companies

Density (g / cm ³ ) 0.6728 0.6568 0.6728 0.6408 0.6568 Fracture modulus (kp / cm ² ) ¹ 374.0 364.6 406.8 304.0 338.1

modulus of elasticity

(kp / cm ² ) "· χ io ~ 35.2 35.9 39.6 26.5 25.7

Internal bond in dry state (kp / cm ² ) ¹ 9.5 9.3 9.9 12.9 12.5

Inner binding in wet condition

(kp / cm 2) 2 _{3> 0 2} , 9 _3t 2 3.5 3.4

footnotes:

* i calculated on the dry weight of the wood chips

- Ai - 2157 54

1: the tests are carried out according to the US standard specification ASTM 1037-72

2: the investigations are carried out in accordance with German regulation V-100.

Example 6

This example illustrates the production according to the invention of three plates of commercial "plate wastes ^{11 of} different dimensions (50.4 × 50.4 × 0.8 mm) consisting of particulate materials. In the present case, no extraneous water or emulsifier is used, ie the polyisocyanate and the phosphate release agent are used in bare form.

From the "plate wastes" using the ingredients listed in the following Table VI in the amounts also specified in aaO (all parts "parts" means "parts by weight") three plate-shaped specimens prepared. For this purpose, the procedure of Example 1, but using the "wood plate waste" with a mixture of the polyisocyanate and the phosphate release agent and not sprayed with an aqueous emulsion as in Example 1 and aluminum mold plates are used. All samples are easy to demold and show no tendency to stick to the aluminum plates used in their manufacture. The excellent structural strength properties of the resulting plate-shaped specimens, as they result from the high modulus of rupture (see Table VI), are in marked contrast to the low

Value of this parameter (175.8 kp / cm) of a commercial plate made from the same plate wastes using a phenol / formaldehyde resin binder. ,

Table VI

plate-shaped AA BB 955 Test item CC Äauivalent plate waste 955 45 955 Water content of the snippets 45 50 45 polyisocyanate 19.1 6.5 50 Lauryl pyrophosphate (corresponding to Example 2) 2.5 5.2 6.5 * Wt .-% polyisocyanate 2 4.7 5.2 * Ge \ i .-% water 4.7 0.68 4.7 * Ge \ f, -% pyrophosphate 0.26 4 0.68 Standing time (min) 4.5 12.7 4.5 Plate thickness (mm) 12.7 .6888 12.7 Density, g / cnr .7369 558.6 .7209 Fracture modulus, kp / cm 514.4 763.5 Footnotes? *: calculated on the dry weight of the wood chips 1: PolvraethvlentJOlvDhenvl-DC > Lvisocvan £ it one

weight of 139 and a functionality of 3.0, which contains about 35 ^ Methylenbis- (phenyl isocyanate) and at a temperature of 25 ⁰ C has a viscosity of 700 mPas.

This example illustrates the preparation of a

- Hi - 21 5 7 5 4

A series of particulate panels using polyisocyanate binders in combination with a variety of commercial riophates in amounts corresponding to about 0.7% by weight of 6 phosphorus in the binder / size / resin combination.

The various samples are in accordance with the aaO specified in Table VII ingredients (all parts "parts" mean "parts by weight") according to Example 1, with the exception that no emulsifier mitverwendet and first on the snippets of water and then the isocyanate mixed with the release agent is sprayed. All samples are easy to demold and show no tendency to stick to the steel plates used in their manufacture. In contrast, a comparative plate prepared in a similar manner but without the use of a phosphate release agent adheres to the steel plates used in its manufacture and can not be demolded without damaging the plate surface.

Table VII

plate-shaped test piece DD EE FF GG-HH II JJ KK

Wood chips (corresponding to Example 1) 1440

Water content of wood chips 60

Polyisocyanate (corresponding to Example 1) 86.4

added water 120

Acid tridecyl phosphate 8.33 *

Release agent I ¹ 11,66

Release Agent II ² 8.64

Release agents.III ⁵ , 12,96

1440 , 4 1440 1440 4 1440 , 4 1440 .1440 , 4 1440 60 60 60 60 60 60 60 86 86.4 86 86 86.4 86 86.4 120 120 120 120 120 120 120

Release agent VT 6 6 6 6 17.28 5.75 16.4 8.6 Release agent V ⁵ 12 12 12 1.2 6 Release agent VI 4 4 4 4 6 12 V lauryl pyrophosphate 12.7 12.7 12.7 12.7 6 12 4 * Wt .-% polyisocyanate 6 12 4 12.7 * Wt% water 12 4 · 12.7 Steepness (min) 4 12.7 Plate thickness (mm) 12.7

- '45 - -

footnotes:

1: acidic alkyl phosphate of lauryl alcohol previously reacted with 3 parts by mole of ethylene oxide

2: Acid lauryl phosphate

3: acidic alkyl phosphate of ethoxylated lauryl alcohol

4? acidic alkyl phosphate of an ethoxylated, branched in the middle of the chain aliphatic alcohol

5: acidic alkyl phosphate of n-octyl alcohol

6: acidic alkyl phosphate of ethoxylated lauryl alcohol

7: prepared according to Preparation Example 5

*: 'calculated on the dry weight of the wood chips.

Example 8

Using the phosphate release agents of the example and using the procedure set forth in Example 7 but with lower levels of the release agents in the binder / size / resin combination, further plate-shaped specimens were prepared. The various constituents and their amounts (all parts "parts" mean "parts by weight") are as well as the information about the physical properties of different test pieces in the following Table VIII. All specimens can be removed from the mold plates without damage and without noticeable sticking. The specimens prepared using higher concentrations of phosphate release agents slip out of the die plate interior when removed from the mold, made using the lower concentrations of phosphate release agents

DUTs (00, QQ and UU) require assistance in demolding, e.g. a knock out of the mold plates to ensure an effective © separation. All, finished plate-shaped specimens have a thickness of 12.7 mm.

Table VIII

plate-shaped sample LL MM NlT OO PP QQ RR SS TT UU W VW

used - substances and 920 920 920 920 920 - 920 920 920 L. 920 920 substances 80 80 80 80 80 80 SSO 80 80 80 HolzschniO 'sei ' 920 46 46 46 46 46 920 46 46 46 46 46 What is the subject of wood chips 80? 58 58 58 58 58 80 58 58 58 58 58 polyisocyanate (see Example 1) 46 46 added water 58 58

Release agent VI (corresponding to Example 7) - - - 4.83 2.3

Release agent V (corresponding to Example 7). - - 1,6 0,78 - - - - · - - - -

Release agent I (according to Example 7). 3.36 1.62 - - -.-..- - - - - - -

Release agent ·

IV (according to example 7) - - - - - - - - - - 5,11 2,42

Continued Table VIII

monobasic tridecyl

phosphate ·

(according to example 7) ---___-- 3,67 1,136 -

Release agent ·

III (according to example 7) - ----- 3,67 1,77 - -

% P in the bin.

demeter "0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2

Standing time (min) 4 4 4 4 4 4 4 4 44 4

Physical,. ι

Properties . »

Density, g / cm ³ 0,6953 not 0,7369 not 0,7353 not 0,6984 not 0,7 ² K) I not 0,71 ^ 5 not

under sub- sub- ¹ searches add searches add searches searches

modulus of rupture

(kp / cm ^). 457.0 »416.2" 446.4 "424.6» 437.3 "462.6"

! Young's modulus 2 2 "*) (kp / cm) χ 10 ^ 30,5» 29,0 »29,3" 29,3 "29,9" 30,2 »

Inntere binding in trokkenen supply _oo *? * stood (kp / cm ^ r '^^ »14.6» 13.6 "11.7 ⁿ .15.0" 12.6 ⁿ

footnotes:

1: % P in the combination polyisocyanate / phosphate

2: the tests are carried out according to the US standard specification ASTM 1037-72.

Example 9

This example illustrates the use of a binder / size / resin combination of the invention together with a known phenol / formaldehyde resin binder or size.

All 12.7 mm thick specimens are prepared according to Example 1 except that the modifications described below are carried out and the various constituents shown in Table IX are used in the amounts indicated above (all parts "parts" mean "parts by weight"). For specimens YY and ZZ, the phenol / formaldehyde resin is incorporated in the isocyanate emulsion. In the case of the sample AAA, the chips are first sprayed with the specified amount of water, then with the phenol / formaldehyde resin and finally with the polyisocyanate. In the case of the comparison plate BBB, the chips are sprayed with water and then with the phenol / formaldehyde resin. The plate-shaped specimens XX and ZZ show no appreciable adhesion to the mold plates after molding, while severe adhesion problems occur with the plate-shaped specimens YY, AAA and BBB. The physical properties of the various plate-shaped samples are also shown in Table IX. It turns out that the plate-shaped, specimens XX and

ZZ properties, as they have inventively produced plate-like structures of particulate matter possess. Therein they are clearly superior to the plate-shaped Vergleichsprüflingen YY, AAA and BBB.

Table IX

XX plate-shaped YY ZZ 5 1920 Test piece AAA BBB • 80 used substances and 15 80 192 substances - 96 wood chips 1920 1920 , 7 176.7 48 1920 1920 112 Water content of wood snippets 80 80 5.5. 160 80 Phenol / formaldehyde resin - 96 2.4 96 - Polyisocyanate (corresponding to Example 1) 96 48 4.8 48 5 added water 208 160 5 160 15 emulsifier 2.4 2.4 15 - - Laurylpyrophosphat 9.6 - 0.25 176.7 * Wt .- # resin 5 176.7 5 5.5 * Wt% water 15 5.5 15 * Wt. 9o phosphate 0.5 - Plate temperature ( ⁰ C) 176 176.7 Standing time (min) 5.5 5.5

Physical traits

Density (g / cm ³ ) 0.6680 0.6857 0.71 ^ 5 0.7129 0.6632 Fracture modulus (kp / cm ² ) ⁴ 256.6 211.0 233 * 4 228.5 194 * 7

modulus of elasticity

(kp / cm ² rx 105 -21.8 21.1 25.0 22.4 21.2

Inner tie in the

dry state.

(kp / cm ^z r 12.0 11.1 10.7 11.8 7.0

Inner tie in the. · .. ,, ·

wet condition

(kp / cm 2) 5 5.5 "4.5 4.3 3.5 1.5

footnotes:

1: commercial product in the form of an aqueous suspension of a solids content of 50%

2: aqueous solution of the sodium salt of a styrene / maleic anhydride Mlschpolymerisats a solids content of 30%

3: prepared according to Preparation Example 4

4: the tests are carried out according to the US standard specification ASTM-1037-72

5: the investigations are carried out in accordance with German regulation V-100

*: calculated on the dry weight of the wood chips;

Claims (17)

Anspruch [en] A process for the manufacture of particulate slabs in which a solidifiable particulate organic material is contacted with a polyisocyanate composition and the treated particulate material is thereafter heat and pressure formed into sheets, characterized by additionally comprising the particulate material for the treatment with the polyisocyanate composition with, based on 100 parts by weight of polyisocyanate, about 0.1 to about 20 parts of a phosphate consisting of a) a phosphoric acid derivative of the formulas: or (RO) ₂ P-OH (I) (ID wherein each R is an alkyl radical having 8 to 35 inclusive carbon atoms, an alkenyl radical having 8 to 35 inclusive carbon atoms or a radical of the formula: Ri- (O-CII-ClH ^, A B in which R ^{1 represents} an alkyl radical having 8 to 35 inclusive of carbon atoms, O". OU-ui7Q * Ri A ^ Ji ;) 5,754 one of A and B represents a hydrogen atom and the other represents a hydrogen atom or a methyl radical and η represents an average value of 1 to 5 or their ammonium, alkali metal or alkaline earth metal salt; b) one derived from the phosphoric acid derivatives of formulas I and / or II Pyrophosphatj c) an O-monoacyl derivative of the formulas derived from the phosphoric acid derivatives of the formulas I and / or II: t R ₀ 1> -OCORi _or (RO) ₂ P OCORi; OH
(V) (VI) wherein R has the meaning given and R ^{1 represents} a monovalent hydrocarbon radical having 1 to 12 inclusive carbon atom (s); d) a carbamoyl phosphate of the formula: R ₂ NHCO-O P (OR) OH (VII) wherein R has the meaning given and Rp is a monovalent hydrocarbon radical having up to 12 carbon atoms or a by "^ at least one more group of the formula -NHCOO-P (OR) ₂ represents hydrocarbon radical substituted by R as indicated, or its ammonium, alkali metal or alkaline earth metal salt; e) a branched-chain polyphosphate of the formulas: O -ρ-Ο- ί 0 0 0 RO-P - 0-P (OR) ₂ 4 ^{s / <s} I (RO) ₂ f 1 .p-o-I -0-P (OR) ₂ -P (OR) 2 or ψ O 0-P (OR) ₂ (VIII) wherein R has the meaning given} f) a polyphosphate of the general formula; O [ROP-O] _n (X) wherein R has the meaning given and η is an integer (including a cyclometaphosphate with η = 3) or (IX g) a mixture of two or more of said compounds, brings into contact. 2. The method according to item 1, characterized in that is used as the polyisocyanate a Polymethylenpolyphenylpolyisocyanat with about 25 to about 90 wt .- ^ Methylenbis- (phenyl isocyanate) and the remainder oligomeric Polymethylenpolyphenylpolyisocyanaten a functionality about 2 used. 3. The method according to item 2, characterized in that one uses a Polymethylenpolyphenylpolyisocyanat with about 35 to about 65 wt .-% methylenebis (phenyl isocyanate). 4. The method according to item "1", characterized in that the phosphate used is a mixture of dibasic Laürylphosphat (Lauryldihydrogenphosphat) and monobasic Dilaurylphosphat (dilauryl hydrogen phosphate). 5. The method according to item 1, characterized in that one uses as a phosphate by removing the water of condensation from a mixture of dibasic Laürylphosphat (Lauryldihydrogenphosphat) and monobasic Dilaurylphosphat (dilauryl hydrogen phosphate) formed pyrophosphate. 6. The method according to item 1, characterized in that a mixture of dibasic oleyl phosphate (oleyl dihydrogen phosphate) and monobasic Dioleylphosphat (Dioleylhydrogenphosphat) is used as the phosphate. "· · 7. A method according to p _un kt !, characterized in that one uses as phosphate by removing the water of condensation from a mixture of dibasic oleyl phosphate (oleyl dihydrogen phosphate) and monobasic Dioleylphosphat (Dioleylhydrogenphosphat) formed pyrophosphate. 8. The method according to item 1 », characterized in that at the. Production of particulate plates as particulate matter. Wood chips used. 9. The method according to item 1, characterized in that the polyisocyanate and the phosphate in the form of an aqueous emulsion simultaneously applied to the particulate matter. 10. The method according to item 9 », characterized in that one uses an additionally containing an emulsifier aqueous Polyisocyanatemulslon. 11. The method according to item 1 », characterized in that bringing the particulate substances separately with the polyisocyanate and the phosphate in contact. 12. A method according to p _U nkt 11 »characterized in that one brings the polyisocyanate and phosphate each in the form of an aqueous dispersion are used. 13. The method according to item 11 », characterized in that the particulate substances are brought into contact with the polyisocyanate and the phosphate with water before being brought into contact. - .si - 2157 54 14. Storage stable mass in the form of a mixture of a) a Polymethylenpolyphenylpolyisocyanat with about 25 to about 90 wt .-% Methylenbis- (phenyl isocyanate) and the remainder oligomeric Polymethylenpolyphenylpolyisocyanaten a functionality above 2.0 and b) from about 0.1 to about 20 parts by weight per 100 parts by weight of polyisocyanate of one of the formulas by removal of water of condensation from a phosphoric acid derivative: t f R ₀ t »OH _or (RO) ₂ P OH OH · wherein each R is an alkyl radical having 8 to 35 inclusive carbon atoms, an alkenyl radical having 8 to 35 inclusive carbon atoms or a radical of the formula: ι ⁿ AB wherein R ^{1 represents} an alkyl group having 8 to 35 carbon atoms inclusive, one of A and B represents a hydrogen atom and the other represents a hydrogen atom or a methyl group, and η represents an average value of 1 to 5; Mixture of two or more of these phosphoric acid derivatives formed pyrophosphate. - · 15. Mass according to item '14, characterized in that the pyrophosphate is obtained by removing the water of condensation from a mixture of dibasic lauryl phosphate (lauryl dihydrogen phosphate) and monobasic dilauryl phosphate (dilauryl hydrogen phosphate)
is formed. 16. A composition according to item 14, characterized in that the pyrophosphate is formed by removing the water of condensation from a mixture of dibasic oleyl phosphate (oleyl dihydrogen phosphate) and monobasic diolyl phosphate (Dioleylhydrogenphosphat). 17. Mass according to item 14, characterized in that it additionally contains an emulsifier.