HU183031B - Binding material required for chipboard production and method for producing chipboard - 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

BACKGROUND OF THE INVENTION The present invention relates to chipboard binders, in particular chipboard binders containing organic polyisocyanates. It is widely known that organic polyisocyanates, in particular toluene diisocyanate, methylene bis (phenyl isocyanate), polymethylene polyphenyl polyisocyanates, have been used as binder or binder component in the manufacture of chipboard. See, for example, 3,428,592; 3, 440189; 3,557,263; 3,631,199;

870,665; U.S. Patent Nos. 3,919,017 and 3,930,101.

Typically, the binder resins are optionally applied as a solution, aqueous suspension or emulsion, or mixed with particles of cellulosic material or other material capable of forming a particle board, while using a mixing device of some form. The mixture of particles and binder is then molded and then subjected to heat and pressure using heated pressure plates. The process can be performed continuously or batchwise. In order to avoid adhesion between the heated pressure plates and the plate, a plate which is not permeable to isocyanate and which is located between the plate and the pressure plate during the molding process or before the molding process had to be inserted. had to be coated with a suitable agent or the particles themselves had to be coated with a material that did not adhere to the pressure plate. The above solutions, particularly in the case of a continuous process, are very cumbersome and have the disadvantage of producing an otherwise satisfactory particle board in order to produce a particle board with very good structural strength properties.

It has been found that the above drawbacks can be minimized with the use of organic isocyanates as chipboard binders by the use of certain phosphorous compounds in the internal separating eyes in the isocyanate compositions. For this purpose, phosphorous compounds have been used in the preparation of polyether polyurethanes

U.S. Patent No. 024,088. However, it has been found that the phosphorus compounds described herein are not applicable to the process of the invention.

Thus, according to the present invention, a particle board is prepared in which the pressable organic material is contacted with a polyisocyanate, and the treated particles are pressed and heat-formed into sheets and treated with 0.120 parts by weight of phosphate per 100 parts by weight of polyisocyanate in addition to polyisocyanate.

a) Phosphates of the formulas I and II or an equimolar mixture thereof.

b) pyrophosphates derivative of the formulas I and II and pyrophosphates derivable from the mixture of the compounds I and II.

c) A mixture of two or more of the above compounds, wherein R is independently C 8 -C 15 alkyl, C 8 -C 20 alkenyl, and a group of Formula I wherein R 'is C 8 -C 35 alkyl, A and B is hydrogen, n is an average of 1 to 5.

The present invention relates to novel compositions comprising one or more of the above compounds and organic polyisocyanates. The invention also relates to particle boards produced by the above process.

C 8 -C 15 alkyl means a saturated monovalent radical which is linear or branched and has the same number of carbon atoms. Such groups include, for example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and their isomers.

The term C 8-20 alkenyl means a monovalent linear or branched aliphatic group containing at least one double bond. Such groups include, for example, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl and isomers.

The term pyrophosphate derived from phosphoric acid esters of formula (I) and (II) and a mixture of compounds of formula (I) and (II) means that the phosphoric acid esters of formula (I) and (II) are generally diester and a mixture of the phosphoric acid ester of formula (I) with the corresponding alcohol ROH, wherein R is as defined above, and prepared by reaction of phosphorus pentoxide in a manner known in the art, e.g. Kosolapoff: Organophosphorus Compounds, 220- 221st John Wiley and Sons, Inc., New York, 1950. The mixture of the phosphoric acid esters and diesters thus obtained may, if desired, be separated by fractional crystallization of, for example, barium or the like, see above. The individual phosphoric acid esters or a mixture of the two can be used in the process of the invention. The pyrophosphates of formulas (III) and (IV) can be readily obtained from the corresponding phosphoric acid esters of formulas (II) and (I) by treatment with dehydrating agents such as carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates, NN'-dihydrocarbyl -carbodiimide etc. reacting in a manner known in the art; see, for example, F. Cramer and M. Winter, Chem. 94, 989 (1961); 92, 2761 (1959); M. Smith, J. G. Moffat and H. G. Khorana, J. Amer. Chem. Soc., 80, 6204 (1958); F. Ramirez, J. F. Marecek and I. Ugi, JACS 97, 3809 (1975). The acid phosphates of the formulas I and II can be separately converted to the corresponding pyrophosphates or the mixture of the phosphoric acid esters of the formulas I and II can be converted into the corresponding pyrophosphates.

In the case of the phosphoric acid alkyl esters of formula (II), the corresponding pyrophosphates may be represented by the formula (III), wherein R is as defined above. In the case of the phosphoric acid alkyl esters of formula (I), the corresponding pyrophosphate may be characterized by the complex mixture of formula (IV), where * is one or more average values, R is as defined above.

The process according to the invention is carried out essentially as described above, using in the literature an organic polyisocyanate as a binding resin or component, e.g. U.S. Patent No. 2,610,552; and U.S. Patent No. 3,428,592, with the significant difference that, together with the isocyanate composition, defi-21

183,031 nickel phosphate is used to treat the particles, which need to be bonded together to form chipboard.

Thus, in accordance with the present invention, the chipboard is made by coupling the wood or cellulosic or organic pressable material using heat and pressure in the presence of a bonding system consisting of an organic polyisocyanate and a phosphate as defined above, which is referred to hereinafter as phosphate separating grains.

The polyisocyanate and the phosphate resolving agent may be used separately in contact with the particles, either in the form of individual components or in a preferred embodiment mixed with the polyisocyanate and the phosphate. Regardless of whether the polyisocyanate and the phosphate are added separately or mixed to the particles, they may be used alone, without diluent or solvent, either or both in the form of an aqueous dispersion or emulsion.

In the binder system, any organic polyisocyanate component having at least two isocyanate groups per molecule may be used as a polyisocyanate component. Examples of such organic polyisocyanates include diphenylmethane diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, α, α-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and the two isomers thereof. commercially available mixtures thereof, triphenylmethane triisocyanates, 4,4'-diisocyanate diphenyl ether, polymethylene polyphenyl polyisocyanates. The latter polyisocyanates contain from 25 to 90% by weight of mixtures of methylene bis (phenyl isocyanate) and the remainder of the mixture is composed of polymethylene polyphenyl polyisocyanates containing more than 2 functional groups. Such polyisocyanates and processes for their preparation are known, for example, from U.S. Patent Nos. 2,683,730, 2,950,263, 3,012,008 and 3,097,191. These polyisocyanates can also be found in their various modified forms. One such form consists of polyphenyl polyisocyanate which has been subjected to a heat treatment, usually at 150-300 ° C, until at 25 ° C the viscosity has not increased to 800-1500 centipoise. Another modified polymethylene polyphenyl polyisocyanate treated with a small amount of epoxide to reduce the acidity according to U.S. Patent No. 3,793,362.

Polymethylene polyphenyl polyisocyanates are preferably used in the binder systems of the present invention. Particularly preferred are polyethylene polyphenyl polyisocyanates containing from about 35% to about 65% by weight of methylene hist (phenyl isocyanate).

Since the organic polyisocyanate is used as an aqueous emulsion or dispersion in the binder system of the present invention, the aqueous emulsion or dispersion may be prepared by any known technology before being used as a binder. For example, the polyisocyanate is dispersed in water in the presence of an emulsifier. The latter may be selected from any emulsifier, including anionic and non-anionic. Non-ionic emulsifiers include, for example, polyoxyethylene and polyoxypropylene alcohols, copolymers of two or more ethylene oxides, propylene oxide, butylene oxide and styrene, alkoxylated alkylphenols such as nonylphenoxy-poly (ethyleneoxy) ethoxylated and propoxylated C4-C18 aliphatic alcohols, glycerides of saturated or unsaturated fatty acids such as stearic acid, oleic acid and ricinoleic acid, fatty acids such as stearic acid, lauric acid, oleic acid and the like. esters of polyoxyalkylene, fatty acid amides such as dialkanol amides of fatty acids such as stearic acid, lauric acid or oleic acid. Such materials are described in detail in Encyclopedia of Chemical Technology, Volume II. Volume 19, Vol. 531-554. page, 1969, Inter-. Science Publishers, New York.

The emulsion or dispersion may be prepared at any time before use in the binder, but preferably within 3 hours before use. The aqueous polyisocyanate emulsion may be prepared using any of the known aqueous emulsion formulations. For example, the emulsion may be prepared by pressurizing the polyisocyanate, emulsifier, and water in a conventional spray gun where the streams of water and polyisocyanate are contacted and mixed under turbulent conditions in the spray gun mixing chamber. The emulsion is released as a spray and applied to the cellulose portions to form sheets as follows.

As noted above, the phosphate releasing agent may be contacted with the particles as a single component. In this case, it can be used either in an aqueous solution or in a dispersion without diluent. When the phosphate is used alone or in diluted form, i.e. separately from the polyisocyanine, it is preferably applied as a spray to the particles. However, in a preferred embodiment of the process of the invention, the phosphate releasing agent and the polyisocyanate are used together in a composition. This can be done in different ways. so if the polyisocyanate. as a Binding resin used without diluent such as water, the phosphate lubricant can be incorporated into the polyisocyanate by simple mixing. When the polyisocyanate is used as a binder resin in the form of an aqueous emulsion, the phosphate lubricant may be added as a separate component during or after formation of the emulsion, or it is particularly preferred to mix the phosphate with the organic polyisocyanate before emulsifying the organic polyisocyanate and phosphate. can be stored for any length of time. Further, if an emulsifier is used in the preparation of the emulsion, it may be mixed with a mixture of organic polyisocyanate and phosphate releasing agent to give a stable permanent formulation which can be converted into an aqueous emulsion at any time simply by mixing with water for use as a binder.

When the polyisocyanate is used as a binder in the form of an aqueous emulsion, the proportion of organic polyisocyanate in the aqueous emulsion is preferably 0.1 to 99% by weight, more preferably 25 to 75% by weight.

Regardless of whether the phosphate releasing agent is used alone or in combination with the polyisocyanate, the phosphate releasing agent

The ratio of 183,031 is 0.1 to 20 parts by weight per 100 parts polyisocyanate, preferably 2 to 10 parts by weight per 100 parts polyisocyanate. In the preparation of an aqueous emulsion, the ratio of emulsifier is not critical and varies according to the emulsifier used, but is generally 0.120% by weight of the polyisocyanate.

The starting material for making the chipboard consists of cellulose particles or similar pressable materials. Typical of these are wood waste, such as planed waste, sawdust, etc. Waste from other cellulosic materials, such as strips of paper, pulp or vegetable fibers such as corn stalks, straw, sugar cane extruded stalks, etc. non-cellulosic materials such as polyurethane, polyisocyanurate shavings, etc. as well as polymeric foams may also be used. Methods for preparing such particles are well known in the art. If desired, mixtures of cellulose moieties may also be used. For example, particle board has been successfully produced from wood mixtures containing up to 30% bark.

The moisture content of the particles can range from 0 to 24% by weight. Particles made from sawdust scrap material generally contain 10 to 20% moisture and can be used without prior drying.

Wood chips are prepared by spraying the particles with the binder composition, individually or in combination, while mixing the particles in a mixer. With the removal of water, the binder system is added in an amount of 2 to 8% by weight, based on the bone dry weight of the particles, but optionally higher or lower amounts of binder resin may be used. If desired, other materials, such as wax glues, anti-inflammatory agents or pigments, may be added during the mixing step.

Stir the mixture until a homogeneous mixture is obtained and then form the coated particles into a loose matrix or felt, which are preferably

They contain 4-18% moisture. This die is then placed between heated fumigation molding plates and then pressed into a sheet. The pressing time, temperature and pressure may vary within wide limits, depending on the thickness of the sheet produced, the desired density of the sheet and the size of the particles used, and other known factors. For example, a 1.27 cm thick chipboard with a medium density is produced using a pressure of 0.204-0.476 atm and a temperature of 160-195 ° C. The pressing time is usually 2-5 minutes. Because some of the moisture present in the matrix reacts with the polyisocyanate to form polyurea, the moisture in the matrix is less critical for isocyanate binders than for other binder systems.

The process described above can be carried out in batches, so that one sheet of chipboard is mixed with an appropriate amount of binder resin combination, and the resulting material is heated and pressed. Alternatively, the process may be performed continuously by applying the mixed particles in a continuous mesh or die form through a heating and pressing zone, applying the required heat and pressure to an upper and lower continuous steel zone.

Regardless of whether the process according to the invention is carried out batchwise or continuously, it is found that by using a combination of a polyisocyanate and a phosphate releasing agent, the chipboard easily separates from the metal sheets of the press and does not adhere to the sheets. This is quite surprising compared to the experience so far. When polyisocyanates alone were used as the binder resin, adhesion occurred.

All of the above phosphate resolving agents can be used alone or in combination, but preferably pyrophosphates of formulas III and IV or mixed pyrophosphates derived from mixtures of phosphoric acid esters of formulas I and II are used. The free hydroxyl groups present in the pyrophosphates or the free hydroxyl groups present in the unmodified phosphoric acid ester starting material are generally hindered from being reactive at room temperature and thus unable to react with the polyisocyanate used in the present invention to without experiencing signs of damage. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and used in the process of the invention, the vapor and temperature created during chip forming results in the hydrolysis of the pyrophosphate thereby regenerating the corresponding phosphoric acid esters and facilitating the separation of the chipboard. This theory is provided for explanatory purposes only and is not intended to limit the present invention in any way.

As described above, the phosphoric acid diesters of formula (II) and the phosphoric acid esters of formula (I) and their salts may be prepared in conventional manner, for example by reaction of the corresponding alcohol of formula ROH wherein R is as defined above with phosphorus pentoxide. (Kosolapoff). One skilled in the art will recognize that mixtures of two or more different alcohols may be used in the above reaction to provide appropriate mixtures of the phosphoric acid esters of formulas I and II wherein R is different in the various components of the mixture. The mixture of phosphoric acid esters and diesters obtained in the above reaction may be separated into its components by conventional methods such as fractional crystallization and the individual compounds obtained may be used in the process of the present invention. The mixture of the mono-and diacid phosphates obtained above can preferably be used without separation, or can be converted to the corresponding pyrophosphate mixture as described above and then used in the process of the invention. The phosphoric acid esters of formula (I) which may be used alone or in combination with other phosphoric acid esters include, for example:

mono-O-octyl, mono-O-monyl, mono-O-decyl, mono-O-undecyl, mono-O-dodecyl, mono-O-tridecyl, mono-O-tetradecyl, mono-O-pentadecyl, mono- 0-hexa-41

183,031 decyl, mono-O-heptadecyl, 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-O-heneikosenyl, mono-O- docosenyl, mono-O-tricosenyl, mono-O-pentacosenyl, mono-O-triacontenyl, and mono-O-pentatriacosenyl, phosphoric acid esters and diesters in which the esterification group can be derived from lauryl or similar monohydric alcohol and from 1 to 5 moles of ethylene oxide we get.

The following examples of phosphoric acid esters of formula (II), which may be used alone or in combination with other phosphates:

0,0-di (octyl), 0,0-di (nonyl), O, O-di (decyl), 0,0-di (undecyl), 0,0-di (dodecyl), O, O-di (tridecyl), O, O-di (tetradecyl), O, O-di (pentadecyl), 0.0-di (hexadecyl), 0.0-di (heptadecyl), 0.0-di (octadecyl), O , 0-di (nonadecyl), 0.0-di (eicosyl), 0.0-di (heneeikosyl), 0.0-di (docosyl), 0.0-di (tricosyl), 0.0-di ( pentacosyl), 0.0-di (hexacosyl), 0.0-di (heptacosyl), 0.0-di (octacosyl), 0.0-di (nonacosyl), 0.0-di (triacontyl), 0-di (pentatriacontyl), 0.0-di (dodecenyl), 0.0-di (tridecenyl), 0.0-di (tetradecenyl), O, O-di (pentadecenyl), 0.0-di (hexadecenyl) ), 0.0-di (heptadecenyl), 0.0-di (octadecenyl), 0.0-di (nonadecenyl), 0.0-di (eicosenyl), 0.0-di (heneikosenyl), 0.0 -di (docosenyl), 0,0-di (tricosenyl), 0,0-di (pentacosenyl), 0,0-di (triacontenyl) and 0,0-di (pentatriacosenyl) phosphoric acid diesters and diesterified mono-acid phosphates, wherein the esterification group is derived from lauryl or similar monovalent alcohols and is coated with 1-5 moles of ethylene oxide.

The latter type of phosphates, which are commercially available, mixed with the appropriate phosphoric ester, are known under the trademark Tryfac and are manufactured by Emery Industries.

Pyrophosphates of formula (III); which may be used alone or in combination with other pyrophosphates, for example:

tetraoctyl, tetranonyl, tetradecyl, tetraundecyl, tetradodecyl, tetra (tridecyl), tetra (tetradecyl), tetra (pentadecyl), tetra (hexadecyl), tetra (heptadecyl), tetra (octadecyl), tetra (nonadecyl), tetra tetra (heneikosyl), 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 (eicosenyl), tetra (henad), tetra (docosenyl), tetra (tricosenyl), tetra (pentacosenyl), tetra (triacontenyl) and tetra (pentatriacosenyl) pyrophosphates.

Examples of pyrophosphates that can be used alone or in combination with other pyrophosphates of the formula (TV) include:

di (octyl), di (nonyl), di (decyl), di (undecyl), di (dodecyl), di (tridecyl), di (tetradecyl), di (pentadecyl), di (hexadecyl), di (heptadecyl), di (octadecyl), di (nonadecyl), di (eicosyl), di (heneikosyl), di (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 (eicosenyl), di (heneeikosenyl), di (docosenyl), di (tricosenyl), di (pentacosenyl), di (triacontenyl) and di (pentatriacosenyl) pyrophosphate.

According to a further embodiment of the process of the invention, it has been found that. the combination of the polyisocyanate and phosphate separator of the present invention can be combined with a thermosetting resin binder as a binder. Examples of such resins include phenol-formaldehyde, resorcinol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, urea-furfural and condensed furfuryl alcohol derivatives. Such a combination not only prevents the finished chipboard from adhering to the pressure plates that had previously been present in the mixture of isocyanate and the thermosetting resin binder of the above type, but also significantly improves the physical properties of the resulting chipboard.

The following preparation examples illustrate the process of the invention.

Production Example 1

Preparation of pyrophosphate from phosphoric acid lanyl ester A mixture of g phosphoric acid lanyl ester, phosphoric acid 0.0-dilanyl ester and phosphoric acid O-lanyl ester; Hooker Chemical Company) and 60 g of phenyl isocyanate were placed in a flask equipped with an anhydrous stirrer, condenser and dryer. Immerse the flask in an oil bath preheated to 80 ° C and stir the contents of the flask until the temperature of the oil bath is slowly raised to 115 ° C. Within about 1 hour, carbon dioxide is evolved. When the evolution of carbon dioxide ceases, the reaction mixture is cooled to room temperature and diluted with 100 ml of chloroform. The resulting mixture was filtered and the resulting N, N'-diphenylurea (24.8 g) was washed with chloroform. The combined filtrate and washed material were concentrated on a rotary evaporator at a bath temperature of 50 ° C. When most of the solvent has evaporated, the Ν, Ν ', Ν' '- triphenylburet crystals are separated and the

6.6 g of solid product are filtered off. The filtrate was evaporated to dryness and finally pressurized at 50 ° C to remove excess phenyl isocyanate. The remaining 70 g of the desired pyrophosphate was a colorless to pale yellow liquid. The infrared spectrum of the product in chloroform did not show P-OH bond bands, but strong

It exhibited 183,031 bands at 940 cm ^_1 , typical of P-O-P bonds.

Production Example 2

Preparation of pyrophosphate from phosphoric acid lanyl ester The phosphoric acid lauryl ester used in Preparation Example 1 was placed in a flask with stirring, reflux and gas inlet, and heated at 65-75 ° C under a stream of nitrogen until melted. The melt is stirred for a total of 2.5 hours, while phosgene is slowly bubbled through. The temperature is maintained at the same level during the addition. The reaction mixture evolves into vigorous gas during the first hour, then gradually decreases and slows strongly during the final phase of phosgene addition. After the addition was complete, the mixture was purged with nitrogen for 15 hours while maintaining the temperature above. Over time, the pressure in the reaction vessel was gradually reduced to 1 mmHg to remove hydrochloric acid and carbon dioxide gas. The resulting viscous residue solidifies completely at night. 66 g of pyrophosphate are thus obtained in the form of a solid which gradually melts at about 60 ° C.

Production Example 3

Preparation of pyrophosphate from phosphoric acid oleyl ester

200 g of phosphoric acid oleyl ester (a mixture of phosphoric acid 0.0-dioleyl ester and phosphoric acid O-monooleyl ester, Hooker Chemical Company) were reacted with 160 g of phenyl isocyanate at 85-90 ° C for 5.5 hours.

Production Example 1. The resulting 68 g of N, N'-diphenylurea was filtered off after the reaction mixture was diluted with 200 ml of chloroform. The filtrate was concentrated on a rotary evaporator and the excess unreacted phenyl isocyanate removed by distillation under reduced pressure. The resulting Ν, Ν ', Ν''triphenylbiuret crystallizes from the oily residue upon standing at room temperature. The crystals were collected by filtration to give 196 g of a liquid product having an infrared spectrum at 940 cm * ¹ showing a P-O-P bond but no P-OH bond.

Production Example 4

Preparation of pyrophosphate from lanyl phosphoric acid

30.4 parts of the lanyl phosphoric acid ester (see Preparation Example 1) are introduced into 21 parts by weight of a dry reactor previously purged with nitrogen. The solution was heated to 40 ° C with stirring and at this point

A solution of 7.6 parts of polymethylene polyphenyl polyisocyanate (equivalent weight = 133, value 2.8; 50% methylene bis (phenylisocyanate)) in 5 parts by weight of toluene is added. The resulting mixture was stirred while a stream of phosphene was introduced (6 parts per minute) and the temperature was slowly raised to 80 ° C. The temperature is maintained at this level while phosgene is continuously introduced until 20 parts by weight of phosgene have been introduced. The addition of phosgene takes a total of 5 hours and 50 minutes. The reaction mixture was heated at this temperature for an additional 40 minutes after the addition of phosgene was complete and then heated to 90-95 ° C and purged with nitrogen for 2 hours to remove excess phosgene. The pressure in the reactor is then reduced until the toluene reflux begins and nitrogen purge is continued for 2 hours. The toluene is then removed by distillation under reduced pressure, the last traces being removed in vacuo. The residue was cooled to room temperature, treated with diatomaceous earth (Celite 545) and filtered after stirring for 30 minutes. This gives 23.7 parts by weight of a mixture of lauryl pyrophosphate and polymethylene polyphenyl polyisodanate containing 6.08% w / w phosphorus.

Production Example 5

Preparation of pyrophosphate from phosphoric lauryl ester

Preparation Example 4 uses an equivalent amount of phenyl isocyanate (6.8 parts by weight) instead of polymethylene polyphenyl polyisocyanate to give an additional dose of lauryl pyrophosphate.

Example 1

From the components listed in Table 1, a series of chips samples were prepared by the following procedure.

The wood chips (Twmer chips) are placed in a rotating mixing barrel and the barrel is rotated while the particles are sprayed with an aqueous emulsion of polyisocyanate, water, phosphate and emulsifier. The emulsion was prepared by mixing the components in a Turrex mixer. The resulting emulsion was sprayed onto the wood particles with a spray gun while shaking for 45 to 120 seconds to obtain a homogeneous mixture. The coated particles were molded into a felted die on a 30x30 cm cold rolled steel sheet with a finishing frame. After removing the molding frame, 0.6 cm thick steel rails corresponding to the desired thickness of the wood chips to be formed are placed on both ends of the aforementioned steel sheet and a second 30 x 30 cm cold rolled steel sheet is placed on top of the die. The whole is then placed on the lower pressure plate of the Dake press (45,000 kg force capacity). Both plates of the press are preheated to the temperature shown in Table 1. Pressure was then applied and the forming time (see Table 1) calculated at the point at which the pressure on the die reached 34 atm. After the molding time (see Table 1), the pressure was released and the wood chips were solidified. In all cases, we have found that hardening is easy

183,031 was completed without the chips adhering to the plates they were in contact with. This phenomenon is in stark contrast to what was observed under the same conditions in the absence of the phosphoric acid lauryl ester in the emulsion, i.e. the binder used in the previous production of chipboard.

Various specimens of the chipboard produced in accordance with the present invention were subjected to a number of physical tests, and physical properties were determined according to Table 1, which show excellent structural strength properties.

for samples E and F, the time taken to keep the die under pressure of 34 atm after raising its internal temperature to 54.4 ° C (thermocouple inserted). Sample G served as a control sample formulated as in Example 1. The physical properties of the finished particle board are shown in Table 2 and show the excellent structural strength properties of the product. All samples were easily removed from the mold and showed no sign of adherence to the steel sheets used in the manufacture.

Table 1

Particleboard

THE B C D Used materials wood chips 644 644 644 644 The weight of the water in the shavings 56 56 56 56 ¹ Polyisocyanate 19.2 19.2 19.2 19.2 ² Water in the emulsion 51 51 51 51 Phosphoric laurilészter 1.9 1.9 1.9 1.9 ³ Emulsifier 0.1 0.1 0.1 0.1 x Polyisocyanate % W / w 3.0 3.0 3.0 3.0 x Water weight / weight% 17 17 17 17 x Phosphate weight / weight% 0.3 0.3 0.3 0.3 x Emulsifier weight / weight% 0.016 0.016 0.016 0.016 Pressure plate temp. C 171 171 171 171 Formatting time, minutes 1.5 2.0 2.5 3.0 Physical properties Density, g / cm ^{2 3} 0.64 0.656 0.656 0.64 ⁴ Bending strength: atm 252.3 244.8 292.4 303.96 ⁴ Flexibility coefficient atm 10 ³ 34.13 23.09 36.72 26.92 ⁴ Dry inside bond: atm 6.93 7.07 7.61 6.12 ⁵ Wet inner bond: atm 1.56 1.63 1.63 1.56

Footnotes to Table ¹ Polymethylene Polyphenyl Polyisocyanate: Equivalent Weight = 133; value 2.8; content about 50% methylene bis (phenyl isocyanate) ^{2 A} mixture of phosphoric acid lauryl ester and phosphoric acid dilauryl ester; Hooker Chemical Company ³ Ethoxylated propoxylated butanol: Witconol APEB: Witco Chemical Company ⁴ Tests performed according to ASTM-1037-72 ⁵ Tests performed according to German V-100 Specifications x Dry weight of wood

Example 2

Chipboard samples were prepared as described in Example 1 and from the components listed in Table 2. The formatting time according to the table

Table 2

Particleboard

E F G Used materials wood chips 644 644 644 The weight of the water in the shavings 56 56 56 Polyisocyanate (Example 1-1) 21 42 21 Water in emulsion 56 56 56 ¹ Lauryl pyrophosphate 2.1 4.2 2.1 Emulsifier (Example 1.1) 0.1 0.1 0.1 x Polyisocyanate% w / w 3.3 6.6 3.3 x Water weight / weight% 17.4 17.4 17.4 x Pyrophosphate 0.33 0.65 0:33 x Emulsifier 0.016 0.016 0016 Pressure plate temp. C 179.4 179.4 179.4 Formatting time, minutes 2 2 2 Physical properties Density: g / cm ³ 0.65 0.65 0.67 ² Bending strength, atm 348 346 361.76 ² Flexibility Module, atm · 10 ³ 34.3 34.88 35.4 ² Dry inside bond, atm 8.7 9.58 8.97 ³ Wet inner bond, atm 2.17 2.58 2.1

Footnotes to Table 2 ¹ Prepared according to Production Example 1 ² Tests performed according to ASTM 1037-72 ³ Tests performed according to German V-100 Specifications x Based on dry weight of wood particles

Example 3

A series of chipboard specimens were prepared from the components and ratios of Example 1, except that the press was heated to 204.4 ° C and maintained at this value for various molding times, see Table 3. The physical properties of the samples thus prepared are shown in Table 3, which shows that the samples exhibit excellent structural strength properties. None of the samples showed any tendency during adherence to adhere to the forming plates while being removed from the mold.

183,031

Table 3

Particleboard

H I J K L Formatting time. minute 1.0 1.5 2.0 2.5 3.0 Physical properties Density, g / cm ³ 0.64 0.64 0.65 0.64 0.64 'Flexural strength. atm 187.68 240 214.2 218.2 229.1 'Flexibility Module, atm KP 27.8 32.1 29.98 29.78 30.8 ¹ Dry inside bond, atm 6:39 6.93 5.98 7.27 7.27 ² Wet inner bandage, atm 1:56 1.63 1.56 1.7 1.63

Footnotes to Table 3 ¹ Tests performed according to ASTM 1037-72 ² Tests performed according to German V-100

Example 4

The chipboard sample series was prepared as described in Example 1, but the polyisocyanate was changed and pyrophosphate obtained from the phosphoric acid oleyl ester obtained in Preparation Example 3 was used instead of the phosphoric acid lauryl ester. The various components and their proportions by weight are shown in Table 4, together with the physical properties of the samples obtained. The chipboard thickness in each case was 9.52 mm (spacing barriers of appropriate thickness were used). None of the samples showed a tendency to stick while being removed from the mold. The physical properties of the different samples indicate that they all have excellent structural strength.

Footnotes to Table 4 ¹ Liquid prepolymer of methylene bis (phenyl isocyanate): equivalent weight = 181 ² Polymethylene polyphenyl polyisocyanate containing 65% methylene bis (phenyl isocyanate):

Equivalent weight = 133 ³ Polymethylene polyphenyl polyisocyanate containing 45% methylene bis (phenyl isocyanate): Equivalent weight = 133.5 ⁴ Liquid methylene bis (phenyl isocyanate) according to U.S. Pat. No. 3,384,653. produced as described: equivalent weight = 143

Table 4

Wood chipboard

Materials MNOPQRSTU

wood chips 644 644 644 644 644 644 644 644 644 Weight of water in wood shavings Polyisocyanate 56 56 56 56 56 56 56 56 56 A ^{* 1} 21 B ² 21 C ³ 21 D ⁴ 21 E ⁵ 21 F ⁶ 21 G ⁷ 21 H ⁸ 21 I ⁹ 21 Water in emulsion 47 47 47 47 47 47 47 47 47 pyrophosphate 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Emulsifier (Example 1.1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 x Isocyanate% w / w 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 x Water weight / weight% 16 16 16 16 16 16 16 16 16 x Pyrophosphate% w / w 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 x Emulsifier weight / weight% 0,016 0,016 0,016 0,016 0,016 0,016 0,016 0,016 0,016 Pressure plate temp. C 171.1 171.1 171.1 171.1 171.1 171.1 171.1 171.1 171.1 Formatting time, minutes (x per kiln dry) 4 4 4 4 4 4 4 4 4 Physical properties Density, g / cm ³ 0.65 0.64 0.67 0.65 0.65 0.67 0.64 0.65 0.65 ¹⁰ Bending strength, atm IO ³ 274 346.8 371.9 299.88 365.84 424.3 403.9 418.8 201.2: ¹⁰ Flexibility Module, atm 31.62 36.8 37.6 29.3 33.5 35.9 39.6 40.9 33.7 ¹⁰ Dry Inside Bond, atm 5.16 8.56 9.24 5.64 5.64 6.39 11.42 11.22 3.19 ¹¹ Wet inner bandage, atm 1,224 1.83 2.17 1.42 1.42 1.49 2.45 2.244 1,088

183 03 i ⁵ Polymethylene Polyphenyl Polyisocyanate Containing 35% Methylene Bis (Phenyl Isocyanate): Equivalent Weight = 140 ⁶ Polymethylene Polyphenyl Poly Phenyl Polyisocyanate Containing 35% Methylene Bis (Phenyl Isocyanate): Equivalent Weight = 140 ⁷ 70% Polymethylene Polyphenyl Polyisocyanate Containing Methylene Bis (Phenyl Isocyanate): Equivalent Weight = 133 ⁸ Same as Example 1 ⁹ Toluene Diisocyanate ¹⁰ Tests according to ASTM 1037-72 ¹¹ Tests according to German V-100 done properly; it is a method for determining the structural strength of the finished sheet after immersion in water for a specified period of time.

Example 5

This example illustrates that the particle board is made with a binder composition according to the invention in which no external emulsifier is present and the polyisocyanate is used purely, i.e. not in the form of an aqueous emulsion.

A series of chipboard samples were prepared from the various components and amounts listed in Table 5. The procedure of Example 1 was followed except that the wood portions were first sprayed with a given amount of water and then with a mixture of polyisocyanate and phosphate lubricant. The physical properties of the finished particle board were determined according to Table 5 and it is clear from the table that all samples have excellent structural strength. The samples were easily removed from the mold and showed no tendency to adhere to the steel sheets used in the production.

Table 5

Particleboard

Materials X X Y Z ZZ wood chips 644 644 644 644 644 Weight of water in the shavings 56 56 56 56 56 Polyisocyanate (Example I.1) 38.6 38.6 38.6 38.6 38.6 Water 56 56 56 56 56 Lauryl pyrophosphate (Example 1 2) 3.9 3.9 3.9 3.9 3.9 x Polyisocyanate % W / w 6 6 6 6 6 x Divide water weight / weight% 17.4 17.4 17.4 17.4 17.4 x Pyrophosphate% w / w 0.6 0.6 0.6 0.6 0.6 Formatting time (minutes) 2 2.5 3.0 2 2.5 Plate thickness (mm) 9.52 9:52 9.52 12.7 12.7 Physical properties Density, g / cm ³ 0.67 0.66 0.67 0.64 0.66 ¹ Bending strength, atm 361.76 352.6 503 294.1 327 ¹ Flexibility module. atm 34 34.68 38.35 25.63 24.8 ¹ Dry inside bond, atm 9.18 9.04 9.58 12.44 12.1 ² Wet inner bandage, atm 2.92 2.85 3.12 3.4 3.33

Table 5 footnotes of x calculated from the dry weight of the wood parts ¹ according to ASTM tests Tests according 1037-72 German ² V-100 standards

Example 6

This example illustrates the production of three chipboards using the process of the present invention from wafer shavings (Welwood of Canada, Ltd.) of various dimensions, i.e., 5 x 5 x 0.079 cm. Flat, 0.08 cm thick wood shavings. No external water or emulsifier was used and the polyisocyanate and phosphate lubricant were used neat.

From the wafers, a series of chipboard samples were prepared from the components and amounts listed in Table 6 using the procedure described in Example 1, except that the chipboard sheets were sprayed with a mixture of polyisocyanate and phosphate lubricant and non-aqueous emulsion as in Example 1 and aluminum. We were used. All samples were easily removed from the mold and showed no tendency to adhere to aluminum sheets. Chipboards exhibited excellent structural strength properties, as shown in Table 6 by their high bending strength.

This value is advantageously compared to the corresponding low level of 170 atm of a commercially available plate made from the same wafer shavings but using phenol-formaldehyde resin as a binder.

Table 6

Forgácslemcz

AA BB cc shavings 955 955 955 The weight of the water in the shavings 45 45 45 ¹ Polyisocyanate 19.1 50 50 Lauryl Pyrophosphate (Example 1 2) 2.5 6.5 6.5 x Polyisocyanate juice /% juice 2 5.2 5.2 x Total water weight / weight% 4.7 4.7 4.7 x Pyrophosphate w / w% 0:26 0.68 0.68 Formatting time (minutes) 4.5 4 4.5 Plate thickness (mm) 1/2 1/2 1/2 Density, g / cm 0.73 0.68 0.72 Bending strength, atm 497.5 540.3 738.48

Footnote x Based on the dry weight of the particle board 'Polymethylene polyphenyl polyisocyanate: equivalent weight = 139; value 3; viscosity at 25 ° C

700 cps; Contains 35% methylene bis (phenyl isocyanate)

Example 7

This example illustrates the use of polyisocyanate binders in combination with commercially available phosphates and 0.7

183,031

Table 7

Particleboard

DD EE FF GG HH II JJ KK Wood chips (Example 1. 1) 1440 1440 1440 1440 1440 1440 1440 1440 Weight of water in the shavings 60 60 60 60 60 60 60 60 Polyisocyanate (Example 1-1) 86.4 86.4 86.4 86.4 86.4 86.4 86.4 86.4 Water added 120 120 120 120 120 120 120 120 Phosphoric trideciléter 8.33 ¹ Fosterge A2523 11.66 ² Tryfac 5573 8.64 ³ Tryfac 325A 12.96 ⁴ Tryfac 610A 17.28 ⁵ Fosterge R 5.75 ⁶ Tryfach 525A 16.4 ⁷ Lauryl pyrophosphate 8.6 x Polyisocyanate% w / w 6 6 6 6 6 6 6 6 x total water weight / weight% 12 12 12 12 12 12 12 12 Formatting time (minutes) 4 4 4 4 4 4 4 4 Plate thickness (cm) 1.27 1.27 1.27 1.27 1.27 1.27 1.27 1.27

weight / weight% phosphorus is used in the binding resin combination.

Samples of wood shavings made from different components and quantities are shown in Table 7; The procedure described in Example 1 is followed except that no emulsifier is used and water is first sprayed onto the chip and then the isocyanate is mixed with the lubricant. The samples were easily removed from the mold and showed no tendency to adhere to the steel sheets used. In contrast, in control wood shavings produced in the same way but with a binder without phosphate lubricant, the sheet adhered to the steel sheets and could not be removed from the mold.

Footnotes to Table 7 ¹ Phosphoric acid lauryl ester prepared from lauryl alcohol, pre-reacted with 3 molar amounts of ethylene oxide, Textilana Givision of Henkel, Inc., Hawthorne, Califomia ² ; Emery Industries Inc., Mauldin, South Carolina ³ Phosphoric acid alkyl ester from ethoxylated lauryl alcohol; Emery Industries Inc.

⁴ Phosphoric acid alkyl ester of ethoxylated medium branched aliphatic alcohol; Emery Industries, Inc.

⁵ Phosphoric acid alkyl ester from N-octyl alcohol; Textilana, see above ^{25 6} Phosphoric acid alkyl ester obtained from ethoxylated lauryl alcohol; Emery Industries Inc.

⁷ According to Production Example 5 x Based on the dry weight of the wood fiber

Example 8

Using the phosphate separator and procedure used in Example 7, a further ³⁵ batches of chipboard samples were prepared. However, the binding resin combination was used at lower concentrations. Table 8 shows the components and ratios as well as the physical properties of each sample. All could be removed from the for40 without the chipboard being damaged or significantly adhering to the molding boards. Samples made with a higher concentration of phosphate release agent slipped out of the forming plates when removed from the mold, but at lower concentrations (OO, QQ, and UU), help was needed to knock the release. The thickness of the samples in the particleboard was 12.7 mm.

Footnotes ¹ P% in Polyisocyanate and Phosphate Combinations ² Tests according to ASTM 1037-72

N. T. = untested substance

-101

183,031

Table 8

Particleboard

Used material LL MM NN OO PP QQ RR SS TT UU W WW wood chips 920 920 920 920 920 920 920 920 920 920 920 920 Water weight in wood shavings 80 80 80 80 80 80 80 80 80 80 80 80 Polyisocyanate (Example 1-1) 46 46 46 46 46 46 46 46 46 46 46 46 Water added 58 58 58 58 58 58 58 58 58 58 58 58 Tryfac 525A (Example 7) - - - - 4.83 2.3 - - - - - - Fosterge R (Example 7) - - 1.6 0.78 - - - - - - - - Fosterge A2523 (Example 7) 3.36 1.62 Tryfac 610A (Example 7) 5.11 2.42 Phosphoric tridedlészter (Example 7) - - - - - - - - 2.33 1.136 - - Tryfac 325A (Example 7) - - - - - - 3.67 1.77 - - - - P% in binder 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 Formatting time (minutes) 4 4 4 4 4 4 4 4 4 4 4 4 Physical properties Density (g / cm ³ ) 0.69 N.T. 0.73 N.T. 0.73 N.T. 0.69 N.T. 0.74 N.T. 0.71 Ν. T. ² Bending strength (atm) 442 Ν. T. 402.5 Ν. T. 431.5 N.T. 410.7 N.T. 422.9 Ν. T. 447.4 Ν. T. ² Flexibility Module (atm · 10 ³ ) 29.5 Ν. T. 28 Ν. T. 28.3 N.T. 28.3 Ν. T. 28.96 Ν. T. 29.2 Ν. T. ² Dry internal bonding (atm) 12.8 N. T. 14 Ν. T. 13.2 N.T. 11.28 N.T. 14.48 N.T. 12.17 Ν. T.

Table 9

Particleboard

Materials XX YY ZZ AAA BBB wood chips 1920 1920 1920 1920 1920 Weight of water in the shavings 80 80 80 80 80 ¹ Phenol-formaldehyde resin - 96 96 96 192 Polyisocyanate (Example 1-1) 96 48 48 48 - Water added 208 160 160 160 112 ² Emulsifier 2.4 2.4 2.4 - - ³ Lauryl pyrophosphate 9.6 - 4.8 - - x Resin weight / weight% 5 5 5 5 5 x Water weight / weight% 15 15 15 15 15 x Phosphate weight / weight% 0.5 - 0.25 - - Pressure plate temperature, ° C 176.6 176.6 176.6 176.6 176.6 Formatting time (minutes) 5.5 5.5 5.5 5.5 5.5 Physical properties Density (g / cm ³ ) 0.67 0.68 0.71 0.71 0.66 ⁴ Bending strength (atm) 248.2 204 225.76 221 188.36 ⁴ Flexibility Module (atm 10 ³ ) 21 20.4 24.24 21.69 20.4 ⁴ Dry bonding (atm) 11.56 10.74 10.33 11.42 6.8 ⁵ Wet internal bonding (atm) 5.3 4.35 4.14 3.4 1,496

Example 9

The example illustrates that the binding resin combination of the present invention can be used in combination with phenol-formaldehyde resin 60 known in the art.

Samples of 1.27 cm in thickness were prepared as described in Example 1 with some differences given below and with the reagents and weights listed in Table 9. For the YY and ZZ plates 65, the phenol-formaldehyde resin was incorporated into the isocyanate emulsion, while for the AAA plate, the chips were first sprayed with the indicated amount of water and then with the phenol-formaldehyde resin and finally with the polyisocyanate. For the control BBB plate, the chips were sprayed with water followed by phenol-formaldehyde resin. Plates XX and ZZ showed no significant adhesion to the compression11

-111

183,031 disks after molding, while YY, AAA and BBB disks experienced serious adhesion problems. Table 9 shows the physical properties of the various disks, showing that the properties of the XX and ZZ discs are superior to those of the YY, AAA, and BBB discs, which are not included in the invention.

Footnotes ¹ PB-65: aqueous suspension, 50% product ² Aqueous solution: styrene-maleic anhydride sodium salt copolymer; 30% solids: Monsanto ³ According to Production Example ^{4 4} Tests performed according to ASTM 1037-72 ⁵ Tests performed according to German V-100 specification ⁶ Based on dry weight of wood

Example 10

A panel of chipboard samples was prepared using a combination of polymethylene polyphenyl polyisocyanate and phosphoric acid alkyl ester or optionally substituted phenyl ester as binder. The polyisocyanate used was about 48% by weight of a methylene bis (phenyl isocyanate) -methylene-polyphenyl-polyisocyanate having an isocyanate equivalent.

134.5 and a viscosity of 173 cps at 25 ° C. The phosphoric ester was different in each case, but the phosphoric acid ester used was a mixture of the phosphoric acid ester of formula I and the phosphoric acid diester of formula Π, where R is shown in Table 10 below. A mixture of phosphoric acid esters was prepared as described in Preparation Example 6.

The disc sample is prepared in each case as follows:

2500 g of Douglas pine chipboard is sprayed with 112 g of polyisocyanate as described in Example 1 and equipment. When the spraying and polyisocyanate treatment is complete, the treated shavings are sprayed with the same method and apparatus in an amount of a mixture of phosphoric acid ester so that the total amount of phosphorus present in the combination of the phosphoric acid ester and the polyisocyanate is about 1% by weight. The amount of phosphoric acid ester used in each case is precisely shown in Table 10. The phosphoric acid ester mixture was diluted with 40-50 g Freon R 11 (trichlorofluoromethane) or water (diluent occasionally shown in Table 10) to facilitate spraying. An aliquot of 2156 g of treated shavings is then used to make a 9.5 mm thick sheet as described in Example 1, but using 60x90cm cold rolled steel sheets and a 46x75cm internal forming frame. The individual steel plates and le10. spreadsheet

R is phosphoric acid- % W / w % W / w Diluent- The detachment ester P is the knitter- acid phosphate agent seal material in the binder ¹

C3H7-C3H6-

C ₄ H ₉ O-C ₆ HSO ₃ HffC-C 4 H ^7-CH2CH2- C3H6- nonylphenyl O-CH2CH2-, C4H9- (OCH2CH2) 2 C6H13- (OCH2CH2) 2- tridecilfenil- (OCH2CH2) 2-C4H9- (OCH2CH2 ) ⁸ 3x di (nonylphenyl) phenyl _(OCH2CH2); x ₁₃ H ₂ C 7 (OCH ₂ CH ₂₎ x ^ ⁹ nonilfenil- _(OCH2 CH2) ₉ - CH3, X is (OCH2 CH ₂₎ x 12- C12H25- _{(OCH2 CH2) 12} - x CHj- (OCHzCHz ) ,, -

Cl 2 H ₂₅ (OCH ₂ CH 2) 2 ₃ -

A mixture of C ₄ H ₉ - c ₆ H ₅ CH ₃ - and C ₁₂ H ₂ 5 - is nonylphenyl

Footnotes to Table 10

1.1 8.6 freon good 1.0 8.7 freon excellent 1.0 9.7 freon relatively 1.0 12.4 WATER good 0.9 14.4 freon excellent 1.0 10.2 freon excellent 1.0 11.9 freon excellent 0.8 16.8 freon excellent 1.0 12.1 freon excellent 0.9 28.9 freon excellent 0.8 25.1 freon excellent 0.8 30.1 freon excellent 1.2 24.3 freon excellent 0.8 29.4 freon excellent 1.2 30.0 freon excellent 0.7 42.2 freon relatively good 1.0 6.2 freon relatively good 1.5 10 freon relatively good 0.9 7.1 freon excellent 0.6 7.4 freon excellent ⁸ Tryfac 5555: Emery Industries

⁹ Tryfac 5556: Emery Industries x All phosphoric ester mixtures with isocyanate, when extracted with water, form a good emulsion.

¹ Binder = Polyisocyanate + Phosphoric Acid Ester ⁷ Diethylamine Salt: Virco Pet 30: Mobil Corporation 65

-121

An aluminum foil sheet is placed between the joined surface of the 183,031 jersey. The plate temperature is 177 ° C and the pressing time is 2.5 minutes at a minimum pressure of 34 atm. After removing the sheet in contact with the aluminum sheet from the press, it is determined how easily the aluminum sheet is removed from the sheet. The evaluation is considered excellent if there is no obstacle to removal; good when peeling is easy or relatively good if some resistance is encountered, but you can peel the disc without tearing or damaging the film.

Example 11

In the same manner as in Example 10, the only difference was that the polyisocyanate was sprayed onto the wood chips in the first spraying operation and then the treated chip was sprayed in a separate operation to 15.27 g? T (RO-Ρ-Ο-P-OR; R = 2-ethylhexyl) ι I

Bis-2-ethylhexylpyrophosphoric acid OH in 50 g of Freon R 11. The resulting sheet easily separates from the aluminum foil and is therefore considered excellent.

Example 12

However, using the procedure of Example 10, using 12% (w / w) dibutylpyrophosphoric acid relative to pyrophosphoric acid and polyisocyanate, relatively good plates are obtained.

Example 13

Additional wood shavings were made at

As described in Example 10, except that the acid phosphates were mixed with the polyisocyanate and diluted with 40-50 g of Freon R 11 before being sprayed onto the chipboard. The polyisocyanate used in the series was the same as in Example 10. In each case, different phosphoric acid esters were used, but they consisted of a mixture of the phosphoric acid esters of formula II and the phosphoric acid diesters of formula II, wherein R is all. table. The mixture of phosphoric esters was obtained as described in Preparation Example 6 and the degree of separation of the aluminum foil was

It was evaluated as described in Example 10. The results are all. Table.

As mentioned in the example above and in Example 10, many of the acid phosphates used have an emulsifying property, i.e. they form emulsions by shaking or mixing with water without the addition of a surfactant. This is particularly advantageous when using a polyisocyanate binder containing an acid phosphate lubricant in the form of an aqueous emulsion, since the above acid phosphates do not require the addition of an emulsifier, they also act as an acid phosphate lubricant and emulsifier. It has now been found that in the case of the phosphoric acid esters of the formulas I and II, wherein R is

R '- (O-CH-CH,

I I

A

R ', A and B are as defined above and n is from 1 to 25, having good self-emulsifying properties.

Table 11

R is in the phosphoric acid ester Weight/ weight% P is the binder in Weight/ weight% acid- phosphate in the binder forking degree x ^J C, ₂ H _{2 S} (OCH ₂ CH) ₃ - 0.6 9.7 excellent x ° C, ₂ H, _{second (OCH2 CH2)} i- 0.6 10.6 excellent x "C ₁₂ H" (OCH ₂ CH ₂ ) _b - 0.6 13.6 excellent x ^B C ₁₃ H ₂ 7 (OCH 3 CHa) e— 0.6 14.3 excellent C3H7- 1.0 5.0 relatively good C "H, - 1.7 10.0 excellent C7H15 1.3 10.0 excellent c, h, ₇ 0.5 4.6 excellent • 2-ethylhexyl- 1.2 10.0 good ⁷ tridecil 0.8 10.0 excellent

Table 11 Footnotes x Phosphoric acid esters and isocyanate mixtures in each case an emulsion formed upon extraction with water, ¹ Binder = polyisocyanate + phosphoric acid ester ² Fosterge A2523: Textilana ³ Tryfac 325A Emery Industries ⁴ Tryfac 525A Emery Industries ⁵ Tryfac 610A : Emery Industries ⁶ Mobil Corporation ⁷ Mobil Corporation

Claims (17)

Patent claims 1. A process for preparing a pressable fiberboard composition comprising cellulosic particles, preferably wood chips, and a polyisocyanate binder, preferably 25-90% by weight, especially 35-65% by weight of polymethylene-polyphenyl-polyisocyanate containing methylene bis (phenylisocyanate). by mixing a mixture of oligomeric polymethylene polyphenyl polyisocyanates containing more than one functional group, optionally in the form of an aqueous emulsion or dispersion, optionally with 40-70% by weight of formaldehyde condensation resin, and then converting the impregnated particles to a pressure of 20-40 atm. 160-190 ° C -131 183 031, characterized in that the cellulose particles, preferably wood chips, are co-treated with the polyisocyanate composition or, optionally after emulsification in water, with from 0.1 to 20 parts by weight of organic phosphate per 100 parts by weight of polyisocyanate, a) (I) or general formula _and phosphoric acid mono-ester or -diester, or an equimolar mixture of (II) (b) pyrophosphate of formula (III) or (IV), or c) a) and b) a mixture of esters wherein R is C8-10 alkyl, C8-20 alkenyl, 8-15 carbon atoms (OCN ₂ CH _{2) n,} where n = 1-5 treated (Priority : May 3, 1979) 2. A process for the preparation of a fiberboard pressable composition comprising polymethylene polyphenyl polyisocyanate containing cellulose particles, preferably wood chips, and a polyisocyanate binder, preferably 25-90% by weight, particularly 35-65% by weight of methylene bis (phenylisocyanate). by mixing a mixture of oligomeric polymethylene polyphenyl polyisocyanates containing more than one unit, optionally in the form of an aqueous emulsion or dispersion, optionally together with 40-70% by weight of formaldehyde condensation resin, and then converting the treated particles to a plate at 2050 atm and At 195 ° C, characterized in that the cellulose particles, preferably wood chips, are co-treated with the polyisocyanate composition or, optionally after emulsification in water, optionally with from 0.1 to 20 parts by weight of organic phosphate per 100 parts of polyisocyanate, (a) a mono-ester or di-ester of phosphoric acid of the formulas I and II, or an equimolar mixture thereof; (b) pyrophosphate of formula (III) or (IV), c) a mixture of esters a) and b), wherein R is a C 12 -C 15 alkyl group or a C 12 -C 20 alkenyl group. (Priority: September 29, 1978) 3. A process for the preparation of a fiberboard pressable composition comprising polymethylene polyphenyl polyisocyanate containing cellulosic particles, preferably wood chips, and a polyisocyanate binder, preferably 29-90% by weight, especially 35-65% by weight, of methylene bis (phenylisocyanate). by mixing a mixture of oligomeric polymethylene polyphenyl polyisocyanates containing more than one functional group, optionally in the form of an aqueous emulsion or dispersion, optionally with 40-70% by weight of formaldehyde condensation resin, and then bleaching the treated particles at a pressure of 20-50 atm. and at 160-195 ° C, characterized in that the cellulose particles, preferably wood chips, are co-treated with the polyisocyanate composition or separately, optionally after emulsification in water, with from 0.1 to 20 parts by weight of organic phosphate per 100 parts polyisocyanate, (a) a mono-ester or di-ester of phosphoric acid of formula (I) or (II) or an equimolar mixture thereof; b) pyrophosphate of formulas III and IV, c) a mixture of esters a) and b) wherein R is C3-C15 alkenyl, C3-C15 alkyl, or phenyl, or phenyl substituted with 1-2 C8-C13 alkyl, or R'1-C15 alkyl; alkyl, or phenyl optionally substituted with 1-2 C 1 -C 15 alkyl, n = 1-25. (Priority of Amendment: November 9, 1980) 4. The process of claim 2 wherein the phosphate is a mixture of phosphoric acid lauryl ester and phosphoric acid dilauryl ester. (Priority: September 29, 1978) 5. A process according to claim 2 wherein the phosphate is pyrophosphate obtained from a mixture of phosphoric acid dilauryl ester and phosphoric acid lauryl ester. (Priority: September 29, 1978) 6. A process according to claim 2 wherein the phosphate is a mixture of phosphoric acid dioleyl ester and phosphoric acid oleyl ester. (Priority: September 29, 1978) 7. A process according to claim 2 wherein the phosphate is pyrophosphate obtained from a mixture of a phosphoric acid oleyl ester and a phosphoric acid dioleyl ester. (Priority: September 29, 1978) 8. The process of claim 2, wherein the cellulose particle is wood chips. (Priority: September 29, 1978) 9. A process according to claim 2, wherein the particles are co-administered in the form of an aqueous phosphate emulsion. (Priority: September 29, 1978) 10. The process of claim 1, wherein the particles are separately treated with the polyisocyanate and the phosphate. (Priority: May 3, 1979) 12. A process according to claim 1 wherein the polyisocyanate and the phosphate are in the form of an aqueous dispersion. (Priority: May 3, 1979) 13. The method of claim 11, which is an embodiment -14183 03; characterized in that the particles are first treated with water followed by polyisocyanate and phosphate. (Priority: May 3, 1979) 14. Composition with long-term storage cellulose particles, pressed into a fibreboard, consisting of 5 to 25% to 90% by weight of polymers of methylene bis (phenyl isocyanate) and 10 to 75% by weight of oligomeric polymethylene polyphenyl polyisocyanates having more than 2 functional groups polyphenyl polyisocyanate - characterized in that 0.1 to 100 parts by weight of polyisocyanate per additional component 20 parts by weight (a) a monoester or diester of phosphoric acid of formula I or II, or an equimolar mixture thereof; or 15 b) pyrophosphate of formula III or IV; obsession c) a mixture of esters a) and b) wherein R is a C8-C15 alkyl group, C 8-20 alkenyl, or C 8-20 C 20 alkyl (OCH ₂ CH ₂ ) _n , where n = 1-5 and optionally 0.1-20% by weight of emulsifier. (Priority: May 3, 1979) 25 15. A durable cellulosic particle-pressed composition comprising from 25 to 90% by weight of an oligomeric polymethylene polyphenyl polyisocyanate having from 25 to 90% by weight of methylene bis (phenylisocyanate) and from 10 to 75% by weight of functional groups. containing polymethylene-polyphenyl-polyisocyanate - characterized in that 0.120 parts by weight, based on 100 parts by weight of polyisocyanate, (a) a monoester or diester of phosphoric acid of formula I or II, or an equimolar mixture thereof; obsession b) pyrophosphate of formula III or IV; obsession c) a mixture of esters a) and b), wherein R is a C 12 -C 15 alkyl group or a C 12 -C 20 alkenyl group, optionally containing from 0.1 to 20% by weight of an emulsifier. (Priority: September 29, 1978) 16. The composition of claim 15 wherein the pyrophosphate is pyrophosphate derived from a mixture of a phosphoric acid lauryl ester and a phosphoric acid dilauryl ester. (Priority: September 29, 1978) 17. The composition of claim 15 wherein the pyrophosphate is pyrophosphate derived from a mixture of phosphoric acid oleyl ester and phosphoric acid dioleyl ester. (Priority: September 29, 1978) 18. The composition of claim 15, further comprising an emulsifier.