CS221524B2 - Method of making the boards from bonded parts - Google Patents

Abstract

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

Description

The present invention relates to a method for producing bonded particle boards. Emphasis is placed on binders for bonded particle boards and in particular on the use of organic polyisocyanates as binders for these boards.

It is now widely recognized that organic polyisocyanates, and especially toluene diisocyanate, methylene bis (phenylene cyanate) and polymethylene polyphenyl polyisocyanates, may be used as binders or as components thereof for the production of bonded particle boards, see, for example, U.S. Pat. Nos. 3,428,592, 3,4010189;

557,263, 3,636,199, 3,870,665, 3,919,017 and 3,930,110.

In a typical procedure, the binder resin, particularly in the form of a solution or an aqueous suspension or emulsion, applied to the particles of cellulosic material, or · for other types of material capable of ^{1 * 3} form a slab of bonded particles, or these materials are mixed using a drum or mixer equipment or other forms of mixing. The mixture of particles and binder is then shaped in a mat and heated using heated plates under pressure. The process may be carried out either batchwise or continuously. In order to avoid adherence of the resulting plates to heated plates, it has hitherto been necessary to apply a sheet of impervious isocyanate sheet between the surface of the bonded particle board and heated plate during the forming process or to coat the surface of the heating plates with a suitable release agent or coating prior to each pressing operation. of the particles themselves with a material which is not adherent to the heating plates. Each of these alternatives, especially when the process is carried out on a continuous basis, is both difficult and disadvantageous in an otherwise very satisfactory method of producing bonded particle boards having very advantageous structural strength properties.

We have now found that the above-mentioned disadvantages of using organic isocyanates, as binder foams of bonded particle boards, can be minimized in a very satisfactory manner when certain phosphorus compounds are used as internal release agents in the isocyanate mixtures used. The authors are aware of US Patent No. 4,024,088, which discloses the introduction of phosphorus-containing compounds as internal release agents for the production of polyether polyurethanes. We have found that the phosphorus compounds mentioned in this publication are not suitable for use in the process of the invention.

The present invention encompasses an improved process for the production of bonded particle boards, wherein the particles of organic material capable of binding are contacted with the polyisocyanate and ammonium salts, alkali salts and alkaline earth salts of these compounds of formula VII,

e) the branched poles of the phosphates of formula (VIII) and the treated particles are then shaped into plates by heat treatment under pressure, the improvement being that the particles are brought into contact with the polyisocyanate with about 0.1 to 20 parts per 100 parts by weight of polyisocyanate, phosphate. selected from the group consisting of

(a) the acid phosphates of the formula I

O t

RO - p - OH I

Ό O í f

RO-P-O-P ORU

AND

O - i ^г PíORh of (VIII) and formula IX and formula II

Ot (RO ^ P - OH (II) and their ammonium, alkali and alkaline earth salts,

(b) pyrophosphates derived from acidic phosphates of formulas I and II and mixtures of compounds of formulas I and II,

c) O-monoacyl derivatives of the acid phosphates of the formulas I and II having the formula V

O

RO —-- OOOORf

OH (V) and formula VI

O Ť (RO- ^ P — OCOR!

(VI)

d) carbamoyl phosphates of formula VII

o oo

I Ť (( ^R 0 ° PO- ^{p -} o- ^p < ^{or) z}

O— CHOR),> (IX)

(f) polyolphosphates corresponding to formula X

O

(ROO-O) n (X) including cyclometaphosphates. (N. - 3) a

g) mixtures of two or more of these compounds, in the various formulas mentioned above

R is independently selected from the group consisting of alkyl of 8 to 35 carbon atoms, including alkenyl of 8 to 35 carbon atoms, inclusive, and a group of the formula

Л-Ю - CH - CH — H I i h

A B where

R‘ is alkyl of 8 to 35 carbon atoms inclusive, one of A and B is hydrogen and the other is selected from the group consisting of. hydrogen and methyl, n stands for an average value of 1 to 5,

R1 is alkyl, alkenyl, aralkyl, aryl, cycloalkyl or cycloalkenyl of up to and including 12 carbon atoms each,

R 2 is alkyl, alkenyl, aralkyl, aryl, cycloalkyl. or cycloalkenyl of up to 12 carbon atoms each and alkyl, alkenyl, aralkyl, aryl, cycloalkyl or cycloalkenyl of up to 12 carbon atoms each substituted by at least one additional group of the general formula t

- NHCOO - P (OR - where

R is as defined above and n is an integer.

The invention also relates to novel compositions comprising organic polyisocyanates with at least one compound mentioned above, and further to bonded particle boards produced according to the following process.

^In ýraz · "alkyl 8-35 Shalom ^y alkyl" refers to a saturated aliphatic monovatentní IKA-series with ^L · pnmým or branched chain having the indicated number of carbon atoms in the molecule. Illustrations of these groups are octylmonyl, decyl, undecyl, dodecyl, tridecyl, telradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, iricosyl, pentacosyl, hexaclosyl, hexaclosyl, heptacosyl, octosecyl, octosecyl, octosecyl, octosecyl, octosecyl, octosecyl, ^octosecyl, octosecyl, decoratively including their ístomerrnch forms. ^'In ýraz ", and] [ken ^yl with ^{8 and 35} carbon atoms, ^Y' represents a monovalent straight or branched aliphatic radical containing at least one double bond, having the number of carbon atoms in the molecule. Illustrative of such groups · is nonenyl, decenyl · undecenyl, dodecene ^yl, tridecenyl, lelradecenyl pentadecenyl, hexadecenyl, hepladecehyl, octadecenyl, · шопаdecenyl eicosenyl, heneicosenyl, dekosenyl tricosenyl · Penta · triacontenyl, pentatriakiontenyl 'and likewise, including their isomeric forms.

The term "derived from acidic pyrophosphates fosfáfo community ^ formulas ¹ and ¹¹ and mixtures of compounds of formulas ¹ and II 'M, ^and the following meaning: K ^y removing said acid phosphates of the general formulas I and II ·' ^s OBV is He. ^{characterized} ráběj ^and in admixture ^y drogenfosfátu monohydrochloride of formula II and of formula I. dihydrogenfosfálu · Mixtures are. are produced by reacting the corresponding alcohol of the general formula

ROH, by crystallizing the barium and the like salts as described in the above references. Single-sensitive acid phosphates or mixtures of the two. The compounds may be used in the process according to the invention. Ш pyrophosphates of the formula I and ^V is readily získ.aj ^I from the corresponding acid phosphates of the formula I and II. their reaction with dehydralačním agent such as carbonyl chloride, or aryl and alkylmonoisokyanáty -polyisokyanáty ^to arbodi ^and bn ^y · NX-substituted hydrocarbon radicals, and the like, according to methods well mark in the field ^{in |} z napnkiad

F. Cramer and M. Winter, Chem. Ber. 94, 989 (1961); ibid. 92, 2761 (1959); Srni M., J.

G. Moffal and H. G. Khorana, J. Amer. Chem. Soc. 80, 6204 (1958) and F. Rarnirez, J. F. Marecek and I. Ugi, J. Amer. Chem. Soc. 97, 3809 (1975).

The individual acid phosphates · general formulas I and II can be separately converted to the corresponding pyrophosphates or • with a mixture of both types selých ^alkyl phosphate of the formula ^I may be converted to П correspond mixture · ^ ^y p rofosfátů.

In the case of the hydrogenphosphates of the general formula II mentioned above, the corresponding pyrophosphotides of the general formula III correspond accordingly

OO t ^f (RO) _Z P — O-PiOR ^ (dl) where

R is as defined above.

When · . dihydrogenfosfálů general formula ^E · ^I mentioned above corresponding p ^y rofcsfáty constitutes a complex mixture · · an average composition expressed by the general formula IV

W kde

X is an average of 1 or greater; and

R is as defined above.

The term "hydrocarbon radical having 1 to 12: ^y uhhku including hydrogen" means ^a monovalent radical derived by removal of a hydrogen from the hydrocarbon base of the number of carbon atoms ·. Illustrative coating groups are alkyl .As · methyl · ethyl, propyl, butyl, hinges ^{1 hour} ex ^y I oct ^{y1, y1} ec ^d, ^ and to spare dodec

R has the abovementioned meanings, with carbon fosfoιrečným, ^{according p} rocedure well known in the production of phosphoric ^y acidly see e.g. ^O rus rganophospho Compounds, SITR. 220 and 221, John Wiley and Sons In.c ^ "· New York ^1950th · ^{S I} ck admixture, a phosphate obtained in this manner may optionally sep! ^{1, for} example fractionally, including their isomeric forms. alkenyl such as vinyl, allyl, butenyl, pentenyl, hexenyl, loktenyl, decenyl, dodecenyl and the like, including isomeric forms thereof, aralkyl such as benzyl, phenylpropyl, phenethyl, naphthylmethyl and the like, aryl such as phenyl, tolyl, xylyl, naphthyl, biphenylyl and the like, cycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,. cyclooctyl and the like, including isomeric forms thereof; and cycloalkenyl, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and the like, including isomeric forms thereof.

The term "alkali metal" has its own. known meaning, which includes lithium,. sodium, potassium, rubidium and cesium. . The term "alkaline earth metal" also has its well-known meaning, including calcium, strontium, magnesium and barium.

The process according to the invention is essentially carried out according to the methods previously described in the field of organic polyisocyanates. used as a binder resin or component thereof [see, for example, German Patent Publication No. 2,610,552 and. U.S. Pat. No. 3 428 592) with this. the main difference is that it is phosphate. as defined herein uses a mixture of the isocyanate used to process the particles to be bound to each other to form a bonded particle board.

The bonded particle board is produced according to the invention by binding particles of wood or other cellulosic or organic material capable of being solidified by applying heat and pressure in the presence of a binder system comprising a mixture of organic polyisocyanate and phosphate as defined above and hereinafter referred to as "composition". phosphate-producing ".

The polyisocyanate and the phosphate-providing agent can be contacted with the particles as separate, individual components or, preferably, as a separate component. design. The polyisocyanate and the phosphate are contacted. with particles simultaneously or after. mixing. If. the polyisocyanate and the phosphate are introduced separately or in a mixture, they can be used neat, i.e. without diluents or. solvents, or. at least one; or. both components. may be used in the form of aqueous dispersions or emulsions.

Polyisocyanate component. The binder system may be any organic polyisocyanate containing at least two isocyanate groups per molecule. Illustrations of organic polyisocyanates are diphenylmethane diisocyanate, m- and. p-phenylene diisocyanates, chlorophenylene diisocyanate, α, α-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, and mixtures of the two commercially available isomers, triphenylmethane triisocyanates, 4,4‘-diisocyanate diphenyl ether and polymethylene polyisocyanide-polyisocyanato-phenyl polyisocyanate. The latter polyisocyanates form mixtures. containing from about 25 to about. about 90% by weight of methylenebisphenylthiocyanates). and the remainder of the mixture are polymethylene polyphenyl polyisocyanates having a functionality greater than 2.0. These polyisocyanates and methods for their preparation are well known in the art. see, for example, U.S. Patent Nos. 2,683,730; 2,950,263, 3,012,008. a. These polyisocyanates are also available in a number of modified processes. One of these procedures is. in that the polymethylene polyphenyl polyisocyanate as described above is subjected to a heat treatment, usually at a temperature of about 150 to about 300 ° C, unless the viscosity (at 25 ° C) has risen to a value in the range of about 800 to 1500 mPa. Another m. modified polymethylene polyphenyl polyisocyanate is a substance obtained by treatment with less. an amount of epoxide to reduce the acidity according to U.S. Patent No. 3,793,362.

Polyethylene polyphenyl polyisocyanates are preferred polyisocyanates which are used in binder. systems according to the invention. Particularly preferred polymethylene polyphenyl polyisocyanates are those containing from about 35 to about 65% by weight of methylene bis (phenyl isocyanate).

If used. the organic polyisocyanate as a binder system in the form of an aqueous emulsion or dispersion. according to the invention, the aqueous emulsion or dispersion can be prepared for use. . any of the techniques known in the art for making aqueous emulsions or dispersions prior to using the composition as a binder. By way of illustration, the polyisocyanate is dispersed in water. in the presence of an emulsifying agent. Any emulsifying agent known in the art, including ammonium and non-ionic agents, may be used as the composition. Illustrative of nonionic emulsifiers are polyoxyethylene, polyoxypropyl alcohols and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide and styrene. alkoxylated alkylphenols such as nonyiferyl oxypoly (ethyleneoxy) ethanols, alkoxylated. aliphatic alcohols such as. ethoxylated and linked aliphatic alcohols containing from about 4 to 18 carbon atoms, saturated and unsaturated fatty acid glycerides such as stearic acid,. oleic and ricinoleic and the like polyoxyalkylene esters of fatty acids such as stearic, lauric, oleic and the like amides. fatty acids such as dialkanolamides of fatty acids such as. stearic acid,. lauras, oats and the like. A detailed listing of these materials is given in Encyclopedia af Chemical Technology, Second Edition, Cheese. 19, pp. 531-554 (1969), Interscience Publishers, New York, USA.

The preparation of the emulsions or dispersions can be carried out at any time before use in the form of a binder mixture, but is preferably carried out during. about 3 hours before use. Any method customary for preparing aqueous polyisocyanate emulsions can be used in the preparation of the aqueous o ^, o ^, lysocyanate emulsions used in the process of the invention. As an illustration of the preparation of emulsions indicates a case where the pely221524 isocyanate, emulsifying agent and water · are brought into st ^yk u ^p from Hal ^ using conventional · spraying device, which combines the flow of water and polyisocyanate and both substances are mixed under conditions turbulent flow in the spray chamber mixing chamber. The emulsion thus formed is discharged in the form of a spray, which scrubs the cellulose particles so that the spray enters the base plate in the manner discussed below.

As discussed above, the phosphate delivery composition can be contacted with the particles as a separate component. In this case, it is used in pure form, i.e. without diluents, or as an aqueous solution or dispersion. Preferably, the phosphate is used either in pure form or in diluted form. When used alone, i.e. separately from the polyisocyanate, it is present on the particles in the form of a spray. However, in a preferred embodiment the composition and providing a phosphate · polyisíokyanát used together in a single mixture which is ^already e m ^{p BC} and ^y Ravita decisive fashion. ^T and ^the p ^ oužije If a polyisocyanate as a binder resin without diluents Insert the like, and means providing a phosphate may be incorporated into the polyisocyanate · zamícMrnm simple. is a ^{p-lyisotyaniít} ojivová resin in an aqueous emulsion, then the composition may be added to provide phosphate chloride as a separate component during the preparation of the emulsion or after its formation, or in a particularly preferred embodiment the phosphate is pre-mixed with the organic poilyisokyanátem, followed by emulsification. The organic polyisocyanate composition and providing a phosphate may be premixed and stored for any time obdoW ^{p p} efore ^at pH iavou emulsion. Furthermore, if an emulsifier is used to prepare the emulsion, it can also be incorporated into the mixture of the organic polyisocyanate and the phosphate-providing composition to form a storage-stable mixture that can be converted into an aqueous emulsion at any time by simply adding water. These emulsifiers can be used ^of: j and ^k by ^p · ojiv.ov ^and resins.

When using a polyisocyanate as a binder in the form of an aqueous emulsion, the proportion of organic polyisocyanate present in the aqueous emulsion is preferably about ^0, Ia ^from about 99 wt% and preferably ^even with 25 to 75% by weight.

When the phosphate delivery agent is introduced as a separate component or in combination with a polyisocyanate, the phosphate delivery agent is used in the range of about 0.1 to about 20 parts by weight per 100 parts of polyisocyanate and preferably in the range of about 2 to 10 parts by weight. per 100 parts of polyisocyanate. After ^ i ^ -l emulsifying agent required to prepare the aqueous emulsion is not rozhoduprn and changes ^dL e ^p of a single emulsifying agent is usually in the range but ^{at about 0.1 and} about ^{20% by} weight, based on the ^{p ly y} Isoka anát.

^The material ýchoz ^{d p} ro ^p Desk ^{characterized} ojených ^CA stic tvoH cellulose particles and the like, which can be solidified and bound in the form of plates. Typical materials are wood particles arises during the preparation stavebrnho as before ^ · ^ rovmné hoblrn ^y sk ^three veneers and the like. Particles of other cellulosic materials, such as cut paper, paper or vegetable fibers, such as corn stalks, straw, bagasse (pressed sugarcane or beet pulps) and the like, and non-cellulosic materials such as polyurethane, can also be used. polyisocyanurate waste and waste of similar foam-forming polymers. Methods for producing vhoidnýc ^h particles are well Zn ^and m ^s and n ^{e of} BE. Mixtures of cellulose particles can be used as desired. · The plates of bonded Mstic are preferably produced, for example mixtures of Mstic dгe = ^{va, k} are exercised • comprising ^I and ^Z · ° about 3% of the plant bark.

^C ontents Mstic moisture may be: Preferably, the ^pH in the range of about ^d · 0 to ^24% by weight. Obv ^y kle. particles made of waste material in the production of timber and contained about ^{10% Z 2} 0 in ^lhk · Osti and may be used without prior drying ·.

The boards of bonded particles are produced by spraying. Mstic sliožkami ^p ojivové mixtures either sweep or in tomMnaci ^p Rice ^from the particles rotate or tumble mixed in a blender or similar mixer. For example, there is added about 2-8 ^p rocent weight binder s ^y s ^t emu (outside · water that is present therein) relative ^Ž ENO to "completely · dry" weight of the particles, but for * any application can use higher or a smaller amount of binder · ^{p y} r ^ly SK-resins. К částimm ^run with EM mixing can also be added as necessary other material such as glutinous · means the character of waxes, flame retardants, pigments and the like.

After mixing sufficient to obtain uniform mixtures · the coated particles are formed into a loose mat or felt · Preferably, when contained in about ^{4 hours and} about ¹⁸ ° / o moisture íotnostní. The mat is then placed in a heated press between the board in a mold customary for pressing curved veneers and pressed to solidify the particles. Pressing time, temperature and ^pressure are my widely depending on the thickness ^y ^ CE Raben desk ^{Y, Z} and its crosslinked with ^d ^ ^é specificity weight- size ^ u ^ and those Mstic ^d ic ^h and ^Oth circumstances well known in the art . For example, in the manufacture of a board in bonded particles having a mesh of ^12.7 mm and a medium sieve, a pressure of about 20 to 20 bar and a temperature of about 163 to 191 ° C are commonly used. The pressing time is usually about 2 to 5 minutes. Since some of the moisture present in the mat reacts with the polyisocyanate to form a polyurea as described previously, the level of occupied moisture is not critical to the isocyanate binder as well as to other binder systems.

The above process can be carried out on a batch basis, i.e., the individual sheets of binder plates can be pressed after processing a suitable amount of particles with a binder resin mixture and the treated material can be heated under pressure. Optionally, the process can be carried out continuously by introducing the treated particles in the form of a continuous network, or a mat into the heating and pressing zone defined above, along the upper and lower continuous steel strips to provide the necessary heat and pressure.

It has been found that when the process according to the invention is carried out by batch or continuous process, the board particles produced using the mixture of polyisocyanate and phosphate-providing agent of the invention are easily released from the metal plates of the press used in their manufacture and have no tendency to stick or adhere to said plates. This is in direct contrast to the prior experience of using the polyisocyanate itself as a binder resin, as mentioned above.

While the phosphate-providing means defined above, either alone or in combination, may be used, it is preferred in the method of the invention to use pyrophosphates of formula III and IV or mixed pyrophosphates derived from a mixture of acidic phosphates of formula I and II. The free hydroxy groups present in the pyrophosphates or certain hydroxy groups present in the form of unconverted acid phosphate of the starting material are usually sufficiently prevented to be unreactive at ambient temperature with the polyisocyanate used in the process and pyrophosphates can be stored in combination with the polyisocyanate for any deterioration was evident. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and used in the process of the invention, the process temperature and steam generated in the bonded particle board production, we believe, results in phosphate hydrolysis upon regeneration of the corresponding acid phosphates, which then serves to facilitate subsequent release of the board. from bonded particles from press plates. It is to be understood that the theory set forth above is described for the purpose of explanation and is not intended to limit the scope of the invention in any way.

As described above, the monohydrogenphosphates of formula (I) and the dihydrogenphosphates of formula (I) and salts thereof used in the process of the invention are obtained by conventional methods, such as by reaction of the corresponding alcohol of formula (I).

ROH, wherein R is as defined above, with phosphorus pentoxide as described by Kosolapoff (cited). How obvious to experts? It is possible to use mixtures of two or more different alcohols in the above reaction to obtain a corresponding mixture of acidic phosphates of formula I or formula II in which the different components of the mixture have different R meanings. The dihydrogen phosphates obtained in the above reaction may be separated into the individual components by conventional methods such as fractional crystallization and the like, and the individual compounds thus obtained may be used according to the invention. Alternatively, the mono- and dihydrogenphosphate mixture obtained by the above reaction may be used as such without separation into its constituents directly in the process of the invention, or it may be converted to the corresponding pyrophosphate mixture used in the processes discussed above. in the process according to the invention.

Illustrative of the dihydrogenphosphates of formula (I) above, which may be used singly or in combination with other acidic phosphates in the process of the invention, are mono-O-octyl-, muono-O-nonyl-, methyl-0-decyl-, mono-O -undecyl-, mono-O-dodecyl-, mono-O-tridecyl-, mono-O-tetradecyl-, mono-O-pentadecyl, mono-O-hexadecyl-, mono-O-heptadecyl-, mono-O-octadecyl mono-O-nonadecyl-, mono-O-eicosyl-, mono-O-heneicosyl-, mono-O-docosyl-, mono-O-trtcosyl-, mono-O-pentacosyl-, mono-Ο-hexaclosyl- mono-O-heptacosyl-, mono-O-octacosyl-, mono-O-nonacosyl-, mono-O-trlacontyl-, mono-O-pentatriaciontyl-, mono-O-dodecenyl-, mono-O-trldecenyl-, mono-O-tetradecenyl-, mono-O-pentadecenyl-, mono-O-hexadecenyl-, mono-O-heptadecenyl-, mono-O-octadecenyl-, mono-O-nonadecenyl-, monO-O-eicosenyl-, mono -O-henoicosenyl-, mono-O-doscosenyl-, miono-O-tricosenyl-, mono-O-pentacosenyl-, monio-O-triacontenyl- and mono-O-pentatriaciosenyldihydrogenphosphates and -dihydrogenphosphates in which: ch esteťifikující radical derived from laurylalkohiolu monohydric alcohol or the like which has been treated from and using about 1-5 moles of ethylene oxide.

Illustrative of the monohydrogen phosphates of formula (II) above, which may be used singly or in combination with other acidic phosphates in the process of the invention, are 0,0-di (octyl) -, O, O-di (nonyl) -, O, O-di (decyl) -, 0,0-di (undecyl) -, O, O-di (dodecyl) -, Ο, Ο-di (tridecyl) -, O, O-di (tetradecyl) -, O, O-di (pentadecyl) -, Ο, Ο-di (hexadecyl) -, Ο, Ο-di (heptadecyl) -, O, O-di (octadecyl) -, Ο, Ο-di (nonadecyl) -, Ο, Ο-di (eicosyl) -, O, O-dl (heneiciosyl) -, O, O-di (dacosyl) -, 0,0-dl (tricosyl) -, 0,0-dl (pentacosyl) -, O, O-di (hexacosyl) -, O, O-di (heptaciosyl) -, Ο, Ο-di (octaciosyl) -, Ο, Ο-di (nonacosyl) -, Ο, Ο-di (triacontyl) -, O, O-di (pentatrilacantyl) -, O, O-dl (dodecenyl) -, 0,0-di (tridecenyl) -, 0,0-di (tetradecenyl) -,

0,0-di (pentadecenyl) -, 0,0-dihexadecenyl) -,

0 ^{, 0} -di ( ^h e ^p ta decenyl)

0,0-di (fo-ktacdeceixyl) -, 0,0-di (nonadecene ¹⁾ -, 0,0-di (eicosenyl) -, 0,0-di (heneicosenyl) - ^0,0 - ^di - ( docosenyl) ^-, 0,0-di (tricosenyl) -, ^0, 0-di ^(p-1 e ntakosen) ^-, 0,0-di (trlakontenyl) - and 0,0-di (di-esterified and pentatniakosenyl jmonohydrogenfosfáty -monohydrlogenfosfáty in which the esterifying radical is derived from lauryl alcohol, or the like of a monohydric alcohol which has been treated with 1 to 5 moles of ethylene oxide. Illustrative of this latter type of phosphate which is useful in admixture with the corresponding dihydropyrimidine ^y dro ^g enfosíát ^y jslou sold under trade called Try ^f ac by Emery Indrustries' Inc.

Illustrative of the pynophosphates of formula (III) above which may be used singly or in combination with other pyrophosphates in the process of the invention are tetraoctyl-, tetranonyl-, tetradecyl-, tetraundecyl-, tetradodecyl-, tetra (tri- decyl) -, tetra ( tetradecyl-, tetra (pentadecyl) -, tetra (hexadecyn-, tetra (heptadecyl) -, tetrajoctadecyl) -, tetra (nonadwyl) -, tetra (eicosyl) -, tetra (heneicosyl) -, tetra (dokbsyl) -, tetra (tricosyl) -, tetra (pentacosyl) -, tetra (hexacosyl) -, tetra (heptacosyl) -, tetra (octacosyl) -, tetra (nonacosyl) -, tetra (№3 ^ 01 ^) -, tetra (pentatriacontyl) - ^{volatilization} (dodecyl rates) tetra ^ '(tridecenyl) ^-,' tetra (tetradecenyl) -, tetra (pentadecenyl) _Ί tetra ^(d ecenylj- hexamethylene ^tetra (heptade№ny1), tetra (octadecenyl) -. Tetra (nonadecenyl) -, tetra (eicosenyl) -, tetra (heneicosenyl) -, tetra (docosenyl) -, tetra (tricosene ^{1) -,} tetradJentakosenyl) -, tetra (trifluoro akontenyl) - and tetra (pentatriakosenyl jpyrtofosfáty.:

Illustrative pyroíosfátů of formula IV, εντ ^^ which can 'only the ^I jednotli.v ^of vat or komWnaci jrnými pyrophosphate with the process of the present invention are di (octyl) ^-, di (nonyl) -, d i ^(decyl) - , dijundecylK di ^(l odecy1) ^-, di ^{(tridecyl) -,} di ^{(tetradecyl) -,} di (p ⁱ entadecyl) - ^{d i} (hexadecyl) ^{-, di} (heptadecyl) - dl (octadecyl) - di- (nanodecyl) -, dl (eicosyl) -, di (heneicosyl) -, di (dto ^ γΙΕ di (tricose ^l ) - ^, dl (ρβηίβ ^ οβ ^) -, ^di ^^ scyly) ^ di (heptacusyl) ^{-, di} (octacosyl) - ^d (n ^ onakosf ^ i) -, di (tгiakonty ^l) - ^d i (pentatriacontyl) -, dijdodecenyl) -, di (tridecenyl) -, di (tetradecenyl) -, di (pentadecenyl) -, di (hexadecenyn-, di (heptadeoeiyl) -, di (octadecenyl) - ^{, di} (nona ^d ecenyl) - ^, diOeicosenyl) - ^, di (heneicosenyl) - ^, di (docosenyl) -, di-thiosenyl) - di ^(p entakosenyl) ^-, di (triacontenyl) - and .dl (pentatriakosenyl) pyrophosphate ^t y.

O-Monoacyl derivatives^andt^y to^yselých fos^FThe compounds of formula (I) and (II) which may be used in the preparation of the compounds of formula (I)^postu^pu po^daccording to the invention, and^toter^E are depicted by the general formulas (V) and (VI) above, and procedures well known in the art are readily prepared. For example, the corresponding acid phosphate of formula I or II in the form of its silver or other metal salt is reacted^Gwith the corresponding acylhaiogenide of the general formula ce

RlCOHal, where

Hal is chlorine or bromine

R 1 is as described above, as described by Kosiolaplrff on page 334 above. As an illustration mnoacylových O-derivatives ^of the acidic phosphate-cimho formulas I and II is ^also stated O-acetyl, 0-pnopiOnyl-, O-octanoyl, decanoyl-O, ^O -dιod> e] Cano ^'y L- ^, Wbenzoyl-, O-toluoyl ^- and 0-fenacetylderiváty obeoiého various acid phosphates of the formula I and IL examples are mentioned above.

Carboxyoyl phosphates of formula VII used in the process^paccording to the invention, they are readily prepared by reacting a suitable acidic phosphate^FThe compounds of formula (I) or (II) with the appropriate monio or polyisocyanate having a hydrocarbon group located therein, for example using the procedure described by F. Cramer and M. Winter in Chem. Ber. 92, 2761 (1959). Illustrations of such caramoyl phosphates are methylcarbamoyl-, ethylcarbamoyl-, propyl^toar^Oamo^yl-^, hex '^yAND^toar^Oamo^yl-^, Dec^y1-carbamoyl-, dodecylcarbamoyl-, allylcarbamoyl-, hexenylcarbamoyl-, oiktenylcarbamoyl-, decenes^lkarlamιαy ^^dodecenyl^toar^,bamlo^yl-^, phenylcarbamoyl-, tolyl- caroanoyl-, diphenylylcaramoyl-, benzylcarbamoyl-, phenylpropylcarbamoyl- and the like monohydrophosphate monohydrate derivatives (stabilized either in the form of their ammonium or alkali S (Cll ·))^, as exemplified above.^TOar^{> b}amoyl '^Fosfát^y of the general formula VH can vote for voteé h^ydrox^ywith^toupiny v^dherring^tou nevy^pFree conversions to^yselých^Fpers^fát^at in reaction with vho^dfinancial isok^yAnatene is a substituted hydrocarbon group, due to the low degree of reactivity of the hydroxy groups with the isocyanate. Such compounds which contain free h^ydrox^ysku^pin^y, can be used by the process of the invention without causing undesirable effects^dLej^withlow degree of actionⁿ reactivity h^yisocyanate tem.

Polyphosphates corresponding to the formula, X, ^kt ns to ^P oužívají at from ^p Úsobí ^p ccording to the present invention are readily prepared by reacting the appropriate tríialkyffosfátu general formula (RO) SPO, wherein R is as defined above, with kysliční ^to em phosphorous procedures which ^p o ^P, and ^L Kosdapoff in the cited publication, pp. 341. ^P av ^f sown ^Y form obv ^ le směsL complex whose general composition represented by formula X summarizes the cyclic compound (n - = 3) with a six-membered ring composed of alternating carbon phosphorus and oxygen.

The polyphosphates corresponding to formulas VIII and IX used in the process of the invention are readily prepared by reaction of a suitable one. di- or trialkylphosphate and the corresponding halophosphate of the general formula

O (RO) _Z P - Hal wherein Hal represents chlorine or bromine, for example using the procedure described by Kososolapoff in the cited publication, page 338. The procedure involves the elimination of an alkyl halide.

Another feature of the invention is that the mixture of the polyisocyanate and the phosphate-providing agent as binder in the process of the invention can be used together with thermosetting resin binders hitherto used in the art such as phenol formaldehyde, resorcinol formaldehyde, melamine disiormialdehyde, urea formaldehyde, and urea formaldehyde furfurf. Using takiové combination avoids adhesion problems of end panels of bonded particulate к plates of the press, said problems have already occurred in mixtures ísofcyanátu and mimicking thermoset resin ¹ binders, but the physical properties of the sheets of bonded particles which were thus produced are clearly better when using the combination.

The following preparation examples, as well as the examples per se, describe the method of making and using the invention. They disclose the best method expected in the practice of the present invention, but the data is not intended to limit the invention.

Preparation Example 1

Production of pyrophosphate from acidic lauryl phosphate

A mixture of 70 g of acidic lauryl phosphate (a mixture of O, O-lauryl dihydrogen phosphate and O-lauryl dihydrogen phosphate, manufactured by Hiooker Chemical Company) and 80 g of phenyl isocyanate are placed in a dry flask equipped with a stirrer, condenser and drying tube; the cell is immersed in an oil bath preheated to 80 ° C. The cell contents were stirred until the oil bath temperature slowly rose to 115 ° C. Carbon dioxide evolved for one hour. When the evolution of carbon dioxide ceased, the reaction mixture was cooled to room temperature and diluted with 100 mL of chloroform. The resulting mixture was filtered and the collected solid (24.8 g of Ν, Ν-diphenylurea) was washed with chloroform. The combined filtrate and washings were evaporated on a rotary evaporator at a bath temperature of 50 ° C. After evaporation of a larger portion of the solvent, the crystals of N, N &apos;, N &apos; -triphenylbiuret are separated, the evaporation is stopped and 6.6 g of solid material are filtered off. The filtrate was evaporated to dryness and then worked up under reduced pressure at 50 ° C to remove excess phenyl isocyanate. The residue (70 g) forms the desired pyrophosphate as a colorless to pale yellow liquid. The infrared spectrum of the product (in chloroform) shows no bands characteristic of P-OH bonds, but has a strong band at 940 cm ^-1 characteristic of POP bonds.

Preparation example 2

Production of pyrophosphate from acidic lauryl phosphate

A flask equipped with a stirrer, a reflux condenser and a gas inlet was charged with a total of 70 g of acidic lauryl phosphate (the same starting material used in Preparation Example 1j) and heated under nitrogen at 65-75 ° C until it melted. A slow stream of phosgene is introduced into the melt for 5 hours while maintaining the above temperature range during the addition, during the first hour of phosgene addition, vigorous gas evolution occurs in the reaction mixture, but gas evolution gradually fades and is very slow at the end of phosgene addition. the addition was complete, the mixture was purged with nitrogen for 15 hours at a temperature maintained in the above range At the end of this period, the flask pressure was gradually reduced to about 133 Pa to remove hydrogen chloride and carbon dioxide gas. standing overnight to give 66 g of pyrope osphate as a solid, which gradually melts at about 60 ^° C.

Preparation example 3

Production of pyrophosphate from acid oleyiphosphate

A mixture of 200 g of acidic oleyl phosphate (consisting of a mixture of Ο, Ο-dioleyl hydrogen phosphate and O-monooleyl dihydrogen phosphate supplied by the Hooker Chemical Company) is reacted with 160 g of phenyl isocyanate at 85-90 ° C for 5.5 hours as described in the preparation example. 1. The reaction mixture is then diluted with 200 ml of chloroform and filtered off with 68 g of N, N'-diphenylmethyl. The filtrate was evaporated on a rotary evaporator and excess unreacted phenylisocyanate was removed by distillation under reduced pressure. N, N ', N'-triphenylbiuret crystallizes from the oily residue on standing at room temperature. The crystals are filtered off to give 196 g of a liquid product, the infrared spectrum of which shows a band at 940 cm * ¹ characteristic of POP bonds, but no bands characteristic of P-OH,

2.1 5 24

W

Preparation example ⁴

Production of pyrophosphate from acidic lauryl phosphate

A solution of 30.4 parts by weight of acidic lauryl phosphate (same starting material matted as in Preparation Example 1) in 21 parts by weight of toluene is added to the reactor pre-purged nitrogen ^streams . The solution is heated to 40 ° C with stirring and at this point a solution of 7.6 parts by weight of polymethylene polyphenyl polyisocyanate (equivalent weight 133, functionality 2.8, methylenebis (phenyl isocyanate) content of about ⁵⁰ %) in 5 ^{parts by} weight of toluene is added. Do the resulting mixture! Phosgene is introduced with stirring at a rate of about 0.1 parts by weight per minute, and the temperature is allowed to slowly rise to 80 ° C. The temperature is maintained at this level with the continuous introduction of phosgene until a total of 20 parts by weight is introduced. The total time for phosgene introduction is 5 hours 50 minutes. The reaction mixture was heated at the same temperature for a further 40 minutes after the ¹ phosgene addition was complete and then heated to 90-95 ° C and purged with nitrogen for 2 hours to remove excess phosgene. The reactor pressure was then reduced · ^until · for ^{which no} not return it ^to toluene and sweet wine ^Advanced nitrogen and U is ^{d 2} hodtay ^{LSI. The} toluene is then distilled under reduced pressure and its last traces are removed under vacuum. The residue was cooled to room temperature, treated with lime soil (Celite 545), stirred for 30 minutes, and further filtered. 23.7 parts by weight of a mixture of lauryl pyrophosphate and polymethylene polyphenyl polyisocyanate are obtained. It was determined ^that the composition comprises ⁶ 08 wt% phosphorus.

Preparation example 5

Other examples of production of acidic pyrophosphate laurylfosfátu ^Z and using procedure ^L San ^é after him ice preparation of ^Examples 4, but with the difference that instead ^{of p} Olym ^ et ^ h ^ ll ^ i ^ l ^^^ a ^ ^ ^y ^ i enylpol sokyanátu there used by an equivalent quantity (6.8 parts by weight) obtained fenylisokyanáse ^d and l ^{'to the} crowd and TEUR ^ yrofosfátu.

Example 1

Using the procedure described below, a series of samples of bonded wood particle boards are made up to form components in their amount. (all parts are by weight) shown in Table 1 below.

Even ^DR splinters ^E · ^y (,, soustr.užnic ^Ké turnings ^y ") were placed in a rotary drum, and a drum mixer is rotated by spraying an aqueous emulsion of particles · ^s pol ^yi of ^{alkyl diisocyanate, water,} phosphate and emulsifier, ^G and ^C whom you means. The emulsion was prepared by mixing the SiO ^for use as ^h ^ MIC (ACE Turrex). The resulting emulsion was sprayed paint ^Rik st ation Pistoia particles ^{f eva,} pHčemž rotating drum · for 45-120 selkund reaches homogeneity. The coated particles are formed into a loose mat into a cold rolled steel plate of dimension 305 XX by 305 mm, using a plywood frame structure. After removal of the frame structure, steel baffles having a thickness corresponding to the desired thickness (6.3 mm) of the final bonded particle board are placed on both opposite ends of the steel plate already mentioned, and a second cold rolled steel plate of 305 X 305 dimension is placed above. mm. The entire assembly is then placed on a lower press plate (Dake) capable of exerting a force of 45,360 kg. Both plates of the press are preheated to the selected temperature indicated in Table 1 below. Then a press and compressing said time ^and Table ¹ PoC ^counts from the moment when the pressure exceeds 3.5 MPa mat.

After the pressing time indicated in Table 1, the pressure is released and the bonded particle board is stopped. In all cases, it was found that the release from the press took place easily without the tendency to adhere to the press plates with which the plate to be produced was in contact. This is in direct contrast to the behavior of the plates prepared under the same conditions, except that acidic lauryl phosphate was not present in the emulsion used as the binder in the preparation of the plates.

^Watch Out Pattern ^ky follows ^conn terror ^to ravených of bonded particles are then subjected to a series of f ^{y IKA} lmch tests vtastoosti thus determined · are given in Table 1. These characteristics also dioctyl ^Lád · ^s in it and ^{to s} c ^s strutaurrn strength plates .

Table 1

Plate AND В C D Used material Wood chips 644 644 644 644 Weight of water in chips 56 56 56 56 Piolyisocyanate ^υ 19.2 19.2 19.2 19.2 Water in emulsion 51 51 51 51 Acidic lauryl phosphate ²⁾ 1.9 1.9 1.9 1.9 Emulsifier ³⁾ 0.1 0.1 0.1 0.1 % polyisocyanate- tu ^x) 3.0 3.0 3.0 3.0 % By weight of water * ¹ 17 17 17 17 ° / o phosphate mass ^x) 0.3 0.3 0.3 0.3 o / o emulsifying by weight means ^x) 0.016 0.016 0.016 0.016 Plate temperature, ° C 171 171 171 171 Press time, min. 1.5 2,0 2.5 3.0 Physical properties Density kg / m ³ 648.4 664.6 664.6 648.4 Breaking modulus ⁴⁾ kPa 26 085 25 312 30 233 31 428 Modulus of elasticity ⁴⁾ MPa 3530 3319 3797 3818 Internal dry limit ⁴⁾ kPa 717 731 787 633 Inner limit per miokra ⁵⁾ kPa 162 168 168 162

Notes to Table 1:

^υ Polymethylene ^polyphenyl polyisocyanate: 133 weight equivalent, functionality 2.8, methylenebis (phenylisocyanate) content of about 50 o / o.

²⁾ A mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate manufactured by Hioioker Chemical Company.

³⁾ Ethoxylated p-butoxylated butanol: Witconol APEB; from Witco Chemical Company.

⁴⁾ Test conducted according to American Standard ASTM-1037-72.

⁵¹ Test carried out according to German technical specifications V-100.

^x) Based on dry weight of wood particles.

A series of samples of bonded wood particle boards using different components and amounts (all parts are by weight) as shown in Table 2 below. The pressing time given in the table for samples E and F is the time for which the mat is maintained at a pressure (3.5 MPa) after the initial mat temperature (determined by the thermocouple inserted therein) reaches 54 ° C. Sample G is a control and pressed as described in Example 1. The physical properties determined for each bonded particle board are shown in Table 2 and demonstrate the excellent structural strength of the various samples. All samples were easily released from the press and showed no sign of adherence to the steel plates used in their manufacture.

Example 2

The procedure described in Example 1 produced Table 2

Plate E F G

Wood chips 644 644 644 Weight of water in chips 56 56 56 Polyisocyanate (same as in example 1) 21 42 21 Water in emulsion 56 56 56 Acidic lauryl phosphate ¹¹ 2.1 4.2 2.1 Emulsifying agent (same as in example 1) 0.1 0Д 0.1 % polyisocyanate- tu ^x) 3.3 6.6 3.3 % by weight of water ^x) 17.4 17.4 17.4 % pyrophosphate ^x) 0.33 0.65 0.33

% emulsifying

Plate E F G means ^x) 0.016 0.016 0.016 Plates temperature ° C 179 179 179 Press time, min. 2 2 2 Physical properties Density, kg / m ³ 665 665 680 Breaking modulus 2) kPa 36 069 35-788 37 405 Modulus of elasticity ²⁾ MPa 3551 3607 3663 Dry internal limit ²⁾ kPa 900 991 928 Inner wet limit ^υ kPa 225 267 218

Notes to Table 2:

^υ Made as described in Preparation Example 1.

2) Test conducted according to American Standard ASTM-1037-72.

3) The test was carried out according to German technical specifications V-100.

x) Based on dry weight of wood particles.

Example 3

Prepared series of samples of sheets of bonded wood particles using exactly the same reagents and Piim ^ i ^ ^r Ru as jsiou described in Example 1 and using exactly the procedure described in this example except that the plates of a press preheated to 204 degrees Celsius and keep on. during different pressing times, which are shown in Table 3 below. The physical properties of the samples so produced are shown in Table 3 and show that these samples always have excellent structural strength. None of the samples showed any sign of adhesion to the press plates during the press release.

Table 3

Plate

H

K L

Press time, min. Physical properties 1.0 1.5 2,0 2.5 3.0 Density, kg / m ³ 648.4 648.4 664.6 648.4 648.4 ^Breaking modulus ^υ kPa 19 405 24 819 22 148 22 569 23 694 Modulus of elasticity υ MPa 2876 3319 3101 3080 3192 Inner dry limit ^υ kPa 661 717 618 752 752 Inner wet limit 2) kPa 162 169 162 176 IRT

Table notes. 3:

υ Test carried out according to American standard ASTM-1037-72.

2) The test was carried out according to German technical specifications V-100.

Example 4

A series of samples of bonded wood particle boards were made using the procedure described in Example 1, but with different polyisocyanate properties, and instead of acidic lauryl phosphate, pyrophosphate derived from acidic oleyl phosphate produced as described in Preparation Example 3 was used. The following are the different components and their ratios (All parts are by weight), together with the physical properties determined for the final samples. The thickness of the board samples is 9.5 mm in all cases (more spacious frame structures of appropriate thickness were used). The physical properties of the various samples show that all samples have excellent structural strength.

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Notes to Table 4:

^(x) Based on oven-dried wood.

^υ liquid prepolymer methyilenbis ^ fenylisíokyanátu) equivalent weight 181st

²⁾ Polymethylene polyphenyl polyisocyanate containing methylene bis (phenyl isocyanate) in an approximate amount of 65%, equivalent weight 133.

³⁾ Polymethylene polyphenyl polyisocyanate containing methylenebis (phenyisocyanate) in an approximate amount of 45%, equivalent weight 133.5.

^4} Liquid methylenebis (phenylene cyanate) produced according to U.S. Patent No. 3,314,653, equivalent weight 143i.

⁽⁵⁾ Polymethylene polyphenyl polyisocyanate containing methylene bis (phenylene cyanate J in an approximate amount of 35%, equivalent weight 140).

⁶⁾ Polymethylene polyphenyl polyisocyanate containing about 35% methylene bis (phenyl isocyanate), equivalent weight 140.

⁷⁾ Polymethylene polyphenyl polyisocyanate containing methylenebis (phenyl isocyanate) in an approximate amount of 133.

⁸⁾ Same as Example 1.

⁹⁾ Toluene diisocyanate.

¹⁰⁾ Test conducted according to American Standard ASTM-1037-72.

ⁿ⁾ The test was performed according to the NSR technical conditions V-100.

Example 5

This example illustrates the production of bonded particle boards according to the invention, using a binder mixture in which no particular emulsifier is present and the polyisocyanate is used neat, ie not in the form of an aqueous emulsion.

A series of samples of bonded wood particle boards are made using the various components and amounts (all parts by weight) shown in Table 5 below and using the procedure described in the Example, except that the wood particles are first sprayed with the indicated amount water and then sprayed with a mixture of a polyisocyanate and a phosphate-providing agent. The physical properties determined for each bonded particle board are also shown in Table 5, and demonstrate the excellent structural strength of the various samples. All samples were easy to release from the press and showed no signs of adhesion to the steel plates used in their manufacture.

Table 5

Plate W X Y OF zz Used material Wooden shavings 644 644 644 644 644 Weight of water in chips 56 56 56 56 56 Polyisocyanate (same as as in example 1) 38.6 38.6 38.6 38.6 38.6 Water 56 56 56 56 56 Acidic laurylpyrophosphate (same as example 2) 3.9 3.9 3.9 3.9 3.9 % polyisio- nátu ^x) 6 6 6 6 6 % by weight of water ^x) total 17.4 17.4 17.4 17.4 17.4 % pyrophosphate- fátu ^x) 0.6 0.6 0.6 0.6 0.6 Press time, min. 2 2.5 3 2 2.5 Plate thickness, mm 9.5 9.5 9.5 12.7 12.7 Physical properties Density, kg / m ³ 680.8 664.6 680.8 648.4 664.6 ^Breaking modulus ^υ kPa 36 772 36 463 40 688 30 409 33 819 Modulus of elasticity ^υ MPa 3522 3586 3965 2651 2566 Inner dry limit ⁿ kPa 949 935 991 1287 1252 Inner wet limit ^2> kPa 302 295 323 351 345

Notes to Table 5:

^x) Based on dry weight of wood particles.

^υ Test carried out according to American standard ASTM-1037-72.

²⁾ The test was carried out according to German technical specifications V-100.

Example 6

This example illustrates the production of three bonded particle boards, which is carried out according to the invention from "wafer" shavings of various sizes up to 50.8 X 50.8 X 0.8 mm, available from Weldwood of Canada, Ltd. No special water or emulsifier is used, and the polyisocyanate and the phosphate release agent are used pure.

A series of samples of bonded particle boards from the above shavings are made using various components and amounts (all parts by weight) as shown in Table 6 below and using the procedure described in Example 1 except that the shavings are sprayed blends of a polyisocyanate and a phosphate-providing agent, and not an aqueous emulsion as in Example 1, and aluminum die plates are used. All samples were removed easily from the press and no signs of adhesion to the aluminum plates used in their manufacture were found. The excellent structural strength properties of the resulting bonded particle boards are apparent from the high breaking modulus given in Table 6. The comparison is very favorable given the low value of this parameter (97,576 kPa) determined on boards available commercially and made from the same type of shavings using a phenol-formaldehyde resin binder.

Table 6

Plate AA . G3 cc Used material Shavings 955 955 955. Weight of water in shavings 45 45 45 Polyisocyanate ^υ 19.1 50 50 Acidic lauryl phosphate (same as as in example 2) 2.5 6.5 6.5 % polyisocyanate- tu ^x) 2 5.2 5.2 % by weight of water ^x) total 4.7 4.7 4.7 % pyrophosphate ^x) 0.26 0.63 0.68 Press time, min. 4,5 4 4,5 Plate thickness, mm 12.7 12.7 12.7 Physical properties Density, kg / m ³ 745.7  697.0 72'9,5 Breaking modulus, kPa 51 446 55,863 · 73 357

Notes to Table 6:

^(x) Based on dry weight of the shavings.

^υ Polymethylene polyphenyl polyisocyanate: weight equivalent: 139, functionality 3.0, viscosity at 25 ° C 700 mPa. s, the content of methylenebis (lisocyanate phenyl) was approximately 35%.

Example 7

This example illustrates the production of a series of bonded particle boards using polyisocyanate binders containing various commercially available phosphates in an amount corresponding to about 0.7% by weight of phosphorus in the binder resin mixture.

Different samples are prepared using different components and amounts (all parts are by weight) as shown in Table 7, as described in Example 1 except that no emulsifier is used and water is sprayed onto the chips before isocyanate mixed with a phosphate-providing agent is added. All types were removed from the press easily and no signs of adhesion to the steel plates used in their manufacture were found. In contrast, control boards manufactured in exactly the same way, but without the use of a phosphate-providing agent, were found to adhere to the steel plates used in manufacturing and molding could not be terminated without damaging the surface of the plates.

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Notes to Table 7:

^υ Alkylhydrogenfosfát derived from lauryl alcohol which had been reacted with 3 moles of ethylene oxide, manufactured Textilana Division of Henkel, Inc., Hawthiorne, California.

²⁾ Lauryl hydrogen phosphate, manufactured by Emery Industries Inc, Mauldin, South Canolina.

^υ Alkylhydrogenfosfát derived lauryl alcohol ethoxylate, manufactured by Emery Industries Inc., Mauldin, South Carolina.

⁴⁾ Alkyl hydrogenphosphate derived from a branched ethoxylated aliphatic alcohol of a branched nature, manufactured by Emiery Industries Inc, Mauldin, South Carolina.

⁵⁾ n-octyl alcohol-derived alkyl hydrogen phosphate, a product of Textilana Division of Henkel Inc, Hawthorne, California.

⁽⁶⁾ Ethylated lauryl alcohol-derived alkyl hydrogen phosphate, manufactured by Emery Industries Inc, Mauldin, South Carolina.

⁷⁾ Manufactured as described in Preparation Example 5.

^x) Based on dry chip weight.

Example 8

A further series of samples of bonded particle boards are made using the same phosphate-providing means and the same procedure as used in Example 7, but at a lower level of binder resin mixture concentration. Table 8 lists the various components and their ratios (all parts by weight), together with the physical properties determined for some samples. All samples could be removed from the press without damaging the plates or significant adhesion to the press plates. Samples made using a higher concentration of phosphate delivery agents slipped between the press plates when they were removed, while some samples made using a phosphate delivery agent concentration (00, QQ and UU) required help, such as tapping the press plates to achieve release. All samples have a final plate thickness of 12.7 mm.

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Notes to Table 8:

^υ% phosphorus in the mixture of polyisocyanate and FO-SFAT.

^2} Test conducted according to American Standard ASTM-1037-72.

N = material not tested.

Example 9

This example illustrates the use of the binder resin composition of the invention in conjunction with a prior art phenol-formaldehyde binder resin.

All samples [12.7 mm thick] were made from the procedure described in Example 1 with the differences below and using the reagents and their proportions (all parts by weight) shown in Table 9. For plates

YY and ZZ the formaldehyde resin is introduced into the isocyanate emulsion, while in the case of the AAA plate, the chips are first sprayed with the indicated amount of added water, then with phenol formaldehyde resin and finally with the polyol isocyanate. In the case of the BBB control board, the chips are sprayed with water and then phenol-formaldehyde resin. Plates XX and ZZ do not have significant adhesion to the press plates after pressing, while a number of adhesion problems occur with YY, AAA and BBB.

Table 9 also lists the physical properties of the various plates. From these data, it is apparent that the properties of the boards XX and ZZ which fall within the scope of the invention are clearly superior to those of the YY, AAA and BBB boards which were manufactured differently from the invention.

Table 9

Plates XX YY Z 7 AAA. BBB Used material Wood chips 1920's 1920's 1920's 1920's 1920's Weight of water in chips 80 89 80 80 80 Phenolformaldehyde resin ^υ - 96 96 96 192 Polyisocyanate [same as in example 1) 96 48 48 48 - Water to be added 208 160 160 160 112 Emulsifying agent ²⁾ 2.4 2.4 2.4 - - Acidic lauryl phosphate ³⁾ 9.6 - 4.8 - - % by weight of resin rice ^x) 5 5 5 5 5 % by weight of water ^x) 15 Dec 15 Dec 15 Dec 15 Dec 15 Dec % phosphate ^x) 0.5 - 0.25 - - Plates temperature ° C 159 159 159 159 159 Press time, min ' 5.5 5.5 5.5 5.5 5.5 Physical properties Density, kg / m ³ 676.0 693.8 723.0 721.3 671.1 Burst module ⁴⁾ kPa 25 663 21093 23 343 22 851 19 476 Modulus of elasticity ⁴⁾ MPa 2180 2109 2496 2243 2116 Internal dry limit ⁴⁾ kPa 1195 1111 1069 1181 703 Inner wet limit ⁵⁾ kPa 548 450 429 352 155

Notes to Table 9:

^υ PB-65: Borden, aqueous suspension, 50% solids.

²⁾ Aqueous solution of sodium salt of styrene-maleic anhydride copolymer, 30% solids: Monsanto.

³⁾ Manufactured as described in Preparation Example 4.

⁴⁾ Test conducted according to American Standard ASTM-1037-72.

⁵⁾ The test was carried out according to German technical specifications V-100.

^x) Based on dry weight of wood particles.

Claims (10)

OBJECT OF THE INVENTION A method for producing bonded particle boards, wherein the particles of organic material capable of being bonded are contacted with the polyisocyanate mixture and the treated particles are then formed into the panels under heat and pressure, characterized in that 100 parts are added to the polyisocyanate mixture during processing. % polyisocyanate 0.1 to 100 wt. 20 parts by weight of phosphate selected from the group consisting of 1) - acid phosphates of the formula I O-RO-P-OH-OH (I) and the general formula Ot (RO ^ P - OH (II) and their ammonium, alkali and alkaline earth salts, (b) pyrophosphates derived from acidic phosphates of formulas I and II and mixtures of compounds of formulas I and II, c) O-monoacyl derivatives of the acid phosphates of the formulas I and II having the formula V O - OCOR » OH O « R = NHCO-O-p (OR) OH (VIII and ammonium, alkaline and alkaline earth salts of these compounds of formula VII, e) r-branched polyphosphates of the general formula VIII O o «F RO-P-O-P (ORL AND O — P (OR)? o (VIIa) and formula IX 0 00 t tt (RO LP-O-PO — Ρ (OR), A _O O O- ^O (OR) ^ (IX) (f) corresponding to the general formula X O t (ROP - O) ^ (V) and formula VI O ((RO) .P - OCORf (VI) (X) including cyclometaphosphates. (n = 3J and g) mixtures of two or more of these compounds, wherein in the various formulas mentioned above R is independently selected from the group consisting of alkyl of 8 to 35 carbon atoms inclusive, alkenyl of 8 to 35 carbon atoms inclusive, and a group of the formula (d) the formula of formula (VII) R - (O-CH-CH- + _n I I А В where R ‘denotes alkyl having 8 to 35 carbon atoms inclusive, one of the symbols A and V being hydrogen and the other selected from the group consisting of hydrogen and methyl, n being a number having an average value of 1 to 5, R1 is alkyl, alkenyl, aralkyl, aryl, cycloalkyl or cycloalkenyl of up to and including 12 carbon atoms each, R @ 2 is selected from the group consisting of alkyl, alkenyl, aralkyl, aryl, cycloalkyl or cycloalkenyl of up to 12 carbon atoms each and alkyl, alkenyl, aralkyl, aryl, cycltoalkyl or cycloalkenyl of up to 12 carbon atoms each substituted with at least one additional radical formulas O «- NHCOO— P (OR) _? where R is as defined above and n is an integer. 2. The process of claim 1 wherein the phosphate is a mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate. 3. The process of claim 1 wherein the phosphate is pyrophosphate formed by the condensation of water from a mixture of lauryl dihydrogen phosphate and dilauryl monohydrogen phosphate. 4. A process according to claim 1, wherein the phosphate is a mixture of loleyldihydrogen phosphate and dioleylmohohydrogen phosphate. 5. The process of claim 1, wherein the phosphate is pyrophosphate derived from the removal of condensation water from a mixture of oleyl dihydrogen phosphate and dioleyl monohydrogen phosphate. 6. The process of claim 1 wherein the polyisocyanate and phosphate are applied simultaneously to the particles in the form of an aqueous emulsion. 7. A process according to claim 6, wherein an aqueous emulsion of a polyisocyanate containing an emulsifying agent is also used. 8. The method of claim 1, wherein the particles are contacted separately with the polyisocyanate and the phosphate. 9. The process of claim 8, wherein the polyisocyanate and the phosphate are each used in the form of an aqueous dispersion. 10. The method of claim 8, wherein the particles are contacted with water and only thereafter with the polyisocyanate and the phosphate.