CS228940B2 - Bonding composition for boards made of farticles - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a binder composition for particle boards made of materials capable of pressing and forming under heat and pressure, based on polymethylene polyphenyl polyisocyanate and organic phosphate.

The use of organic polyisocyanates, especially toluene diisocyanate, methylene bis (phenylisocyanate and polymethylene polyphenyl polyisocyanates) as binders or as part of binder mixtures used in the preparation of particle boards is well known in the art, see for example U.S. Pat. (+420) 428 592, 3 440 189, 3 557 263, 3 636 199, 3 870 665,

919 017 and number 3 930 110.

In the conventional process for preparing sheets of gelatin material, binder mixtures are used, either in the form of a solution or an aqueous emulsion or suspension, and the binder mixtures are applied to particles of cellulosic material or particles of other types of materials suitable for producing particle boards, or are mixed with these particles in a drum mixer or other suitable mixer. The mixture of particles and binder mixture is then formed into a strand and subjected to heat and pressure using heated plates. The process may be carried out continuously or discontinuously. Sticking of the thus formed plates to the heated mold plates must be avoided by inserting isocyanate-impermeable films between the plate surface and the mold plate surface during the manufacturing process of the particulate sheets, or by covering the mold plates with a suitable release agent before each hot pressing or covering the surface itself. particles with a material that does not stick to the boards. All of these modifications, particularly in the case of continuous manufacturing, are very cumbersome and present a considerable drawback in the otherwise very efficient process for producing particle boards with very advantageous strength characteristics.

The disadvantages of the prior art resulting from the use of organic isocyanates as binder for particulate boards can be overcome by using the binder compositions of the present invention in which certain well-defined phosphorus compounds are added to the isocyanate binder compositions that act as an internal separation agent for the compositions. However, the present invention relates to other types of organic phosphorus compounds added to the polyisocyanate binder compositions than U.S. Pat. No. 4,024,088.

The essence of the particle board binder composition made of materials capable of pressing and forming under heat and pressure is that it consists of a polymethylene polyphenyl polyisocyanate component containing from 25 to 90% by weight of methylene bis (phenyl isocyanate) and the remainder being oligomeric polymethylene polyphenyl polyisocyanates having a bond strength greater than 2.0, and a phosphate component in an amount of from 0.1 to 20 parts by weight per 100 parts by weight of said polyisocyanate component, said phosphate having the general formulas:

O

T (R-O), -P- ^(R V - (1)) in which is

R is a member selected from the group consisting of an alkyl group of 3 to 35 carbon atoms, an alkenyl group of 3 to 35 carbon atoms, an aryl group of 6 to 18 carbon atoms, substituted with at least one alkyl group of 3 to 35 carbon atoms, or an alkyl group of 1 up to 6 carbon atoms substituted by at least one or two acyloxy groups containing 2 to 33 carbon atoms,

R 1 is a member selected from the group consisting of chlorine, C 1 -C 6 alkoxy, C 1 -C 6 di / alkyl / amino, C 1 -C 6 hydroxy / alkylene, and n is an integer of either 1 or 2, wherein in the case where η - 1, one of the two R groups may be a methyl group or an ethyl group, and in the case where n = 1, the two RO groups together with the phosphorus atom to which they are attached, to form a residue of a heterocyclic ring containing 5 to 6 ring atoms.

The advantage of the binder compositions of the present invention is that when used in the manufacture of particle boards in a continuous or batch manner, the particle boards are immediately released from the metal plates of the press in which they are produced and show no tendency to stick or adhere to metal plates. This is a completely unexpected finding, given the previous experience of using polyisocyanates alone as binder resins, as mentioned above.

Any phosphate release agent, either alone or in combination, can be used to prepare the binder composition of the present invention, but compounds of the type:

O t

^{IR 0,} 3- _n - ^P - ^1R '' in which is

R is an alkyl group or an aryl group substituted with an alkyl group, as specified above,

R 1 is chloro, a lower alkoxy group or a di (lower alkyl jamino group as specified above, and n is either 1 or 2.

It is believed that the phosphate compounds of the above formula function as release agents due to the immediate hydrolysis of the compounds under the conditions used in the manufacture of the particle board to give the corresponding hydrogen phosphates of the formula:

O r

(RO) -P - (OH) ’

3-n ⁿ in which they have

R, and n are as defined above.

The latter compounds are already used as internal release agents in polyisocyanate binder mixtures for particle boards. The results of research in this field are set forth to explain the mechanism of action of phosphate release agents in a non-limiting manner.

The compounds of the above general formula which are used as the phosphate component for the binder mixtures according to the invention. may be prepared by conventional methods known in the art. For example, a suitable alcohol of formula:

The corner he has

R, as defined above, reacts with the corresponding phosphoryl halide of the formula:

You drove in

Hal represents chlorine or bromine to give a compound of the formula:

t (RO) ^ - P - Hal in which they have

Hal and R as defined above as the main reaction product. A small amount of a compound of the formula:

O

AND

ROP —- Hab in which they have

Hal and R are as defined above.

These compounds correspond to compounds of formula (I) wherein R 1 is chlorine or bromine and n is 1 or 2. If desired, the two compounds can be separated and converted to compounds of formula (1j) in a conventional manner. however, the mixture of the above compounds can be used without separation as a release agent or as an intermediate for the preparation of other compounds of formula (I) as described below.

Alternatively, the reaction of a suitable alcohol of formula:

The ROH in which R is as hereinbefore defined is carried out with a suitable phosphoryl halide in the presence of a polymethylene polyphenyl polyisocyanate which is one of the components of the binder mixture according to the invention, the resulting product being a polyisocyanate in admixture with an in situ release agent.

Individual compounds of the general formula:

O t

(ROJ _Z P - Hal a

O t

ROP

Hal and R as defined above, or a mixture of the two, are reacted with a suitable lower alkanol, lower alkanol substituted with one or two acyloxy groups, phenol, arylamine, di (lower alkyl) amine or lower alkylene glycol, to form The corresponding compounds of formula (I) in which η 1 or 2. All the above reactions can be carried out by conventional methods, preferably in the presence of inert solvents. Usually the halophosphate of the general formula:

0 't

(RO) _Z P-Hal or

O t

ROP-Hal _r in which they have

Hal and R, as defined above, add dropwise to a solution of other reactants in an inert solvent such as benzene, toluene, xylene and the like. In the case of alkanol, the reaction is usually exothermic and requires external cooling, while in other cases heating to about 100 ° C is sometimes required to complete the reaction. Furthermore, it is also possible to add a tertiary amine, such as triethylamine, pyridine and the like, since it facilitates the reaction by binding the hydrogen halide released in the reaction. The resulting product is isolated by conventional means, for example, the tertiary amine hydrochloride is removed by filtration, followed by evaporation of the inert solvent.

If a mixture of mono- and dihalophosphate is used as the starting material for the reaction, the reaction product will be a mixture of the corresponding compounds of the general formula (1j in which η is 1 or 2. This mixture can be separated into individual components, such as chromatographic separation, or the mixture can be advantageously used without further separation and treatment as a separating agent, which is also within the scope of the present invention.

The binder composition of the present invention consisting of a polyisocyanate component and a release agent can be used in combination with thermosetting resins heretofore used as binders in the art, such as phenol formaldehyde, resorcinol formaldehyde, melamine formaldehyde, ureidoformaldehyde fural, urea formaldehyde, fureuride formaldehyde, fureuride formaldehyde, fureuride formaldehyde furfuride. The application of a combination of these components eliminates the problems of adhesion of the surface treated particle boards to the press plates previously encountered with mixtures of isocyanates and the aforementioned types of thermosetting resin binders, and secondly the physical properties of the particle boards so produced when applying said combinations.

The individual substituents in the compounds used are precisely defined hereinabove, and for the sake of clarity the meaning of these substituents will be further elaborated.

The term "C 3 -C 35 alkyl" means a straight or branched chain saturated monovalent aliphatic. Examples of such groups are propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl a group, eicosyl group, heneicosyl group, docosyl group, pentacoxy group, octacosyl group, nonacosyl group, triacontyl group, pentatriacontyl group and the like, and isomers are included within this range.

The term "C 3 -C 35 alkenyl" refers to a monovalent straight or branched aliphatic radical containing at least one double bond. Examples of such groups are alkyl, butenyl, pentenyl, hexenyl, heptenyl, heptenyl, octenyl, nonenyl, ideceinyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl group, nonadecenyl, elcosenyl, heneicosenyl, docosenyl, tricosenyl, pentacosenyl, triacontenyl, and the like, including isomeric forms thereof.

The term "aryl of 6 to 18 carbon atoms" means a residue obtained by removal of a hydrogen atom attached to a carbon atom in the aromatic hydrocarbon core. Exemplary aryl groups include phenyl, naphthyl, biphenylyl, triphenyl, and the like. The term "C 6 -C 18 aryl substituted with at least one C 3 -C 35 alkyl" refers to an aryl group, as defined above, to which at least one alkyl group, as exemplified above, is attached. Examples of such groups are tolyl, m-xylyl, p-ethylphenyl, m-butylphenyl, p-isohexylphenyl, m-octylphenyl, p-inonylphenyl, o-nonylphenyl, 2-methyl-a a naphthyl group, a 3-ethyl-naphthylQU group, and the like.

The term " acyloxy group having from 2 to 33 atoms. my carbon 'means a residue derived from a saturated and unsaturated aliphatic carboxylic acid such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosainic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, heptriacontanoic acid, dotriacontanoic acid, octenic acid, docenic acid, undecenic acid, tetradecene acid, , tricosic acid, tetracosic acid, pentacosic acid, octacosic acid, triacontenic acid, dotriacontenic acid and the like.

The term "five to six ring heterocyclic nucleus" means a group of the formula:

in which

C _n H 2 _n is alkylene with two to three carbon atoms in the ring member, which may have up to 18 carbon atoms in total in the remainder. Examples of such alkylene groups include ethylene,

1,3-propylene, 1,2-butylene, 1,2-hexylene, 2-methyl-1,3-octylan, 2,5-diethyl-1,3-hexylene, 2,4-hexyl-1,3-pentylene and alike.

The application of the binder mixtures according to the invention can be carried out in the same manner as in the prior art processes in which organic polyisocyanates are used as binder resins or are used as part of binder mixtures (see, for example, DOS 2,610,552 or U.S. Pat. No. 3,428,592, except that in this case, a combination of the phosphate of the above formula (I) and an isocyanate mixture is used as the binder mixture applied to the particles to be bonded to the particle board.

The particle board is produced according to this process by combining particles of wood, or other cellulosic or organic or inorganic materials capable of being compressed using heat and pressure, in the presence of a binder composition of the present invention comprising a mixture of organic polyisocyanates and phosphate of the formula (I), which will also be referred to as "phosphate separating agent".

The polyisocyanate and the phosphate release agents can be contacted with the particles as separate components, or in a particularly preferred embodiment by contacting the polyisocyanate and the phosphates either simultaneously or after pre-mixing. If the polyisocyanate and the phosphate are used separately or in a mixture, they may be used separately, i. without diluents or solvents, or both or both may be used in the form of aqueous dispersions or emulsions.

The polyisocyanate component of the binder composition of the present invention may be any organic polyisocyanate containing at least two isocyanate groups per molecule. Examples of organic polyisocyanates are, for example, diphenylmethane diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, α, n-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, and mixtures of these isomers, which are commercially available, triphenylmethane triisocyanate. 4'-diisocyanate diphenyl ether and polymethylene polyphenyl polyisocyanate. The latter polyisocyanates are mixtures containing about 25 to 90% by weight of phenyl isocyanate and the remainder of the mixture is polymethylene polyphenyl polyisocyanates with a bond strength greater than 2.0. Such polyisocyanates and methods for their preparation are well known, see, for example, U.S. Patent Nos. 2,668,330, 2,950,263, 3,012,008 and 3,097,191. These polyisocyanates are also available in various modified forms. One of these forms is the above-described heat-treated polymethylene polyphenyl polyisocyanate, typically from about 150 ° C to about 300 ° C, until the viscosity at 25 ° C rises to a value in the range of about 0.8 to 1.5 Pa. Another modified polymethylene polyphenyl polyisocyanate is a substance to which a small amount of epoxide has been added to reduce its acidity according to U.S. Patent No. 3,793,362.

A polymethylene polyphenyl polyisocyanate component is present in the binder composition of the present invention, preferably polymethylene polyphenyl isocyanates containing from about 35 to about 65% by weight of phenyl isocyanate are used.

When an organic polyisocyanate in the form of an aqueous emulsion or dispersion is used in the binder composition of the present invention, any of the commonly known preparation of aqueous emulsions or dispersions may be used prior to use of the binder composition. For example, the polyisocyanate is dispersed in water in the presence of an emulsifying agent. The emulsifying agent may be any known emulsifying agent, including anionic and nonionic agents. Examples of non-ionic emulsifying agents include polyoxyethylene and polyoxypropylene alcohols and block copolymers of two or more ethylene oxides, propylene oxides and styrene, alkoxylated alkylphenols such as nonylphenoxypolylethyleneoxy jethanols, alkoxylated aliphatic alcohols of about 4 to 18 carbon atoms, e.g. glycerides of saturated and unsaturated fatty acids such as stearic acid, oleic acid and ricinic acid and the like; polyoxyalkylene esters of fatty acids such as stearic acid, lauric acid, oleic acid and the like; and fatty acid amides such as stearic acid amides, acids lauric acid, oleic acid and the like. A detailed listing of these compounds can be found in: Encyclopedia of Chemical Technology, Second Edition, Vol. 19, pp. 531-554, 1969, Interscience Publishers, New York.

The emulsion or dispersion may be formed at any time prior to use of the binder composition, preferably within about three hours prior to use. Any conventional method for preparing aqueous emulsions can be used to prepare the polyisocyanate emulsions in water used in the binder compositions of the invention. For example, the emulsion may be prepared by mixing the polyisocyanate, the emulsifying agent, and the water under pressure using a conventional spray gun in which water and polyisocyanate jets collide and mix under turbulent conditions in the mixing chamber of the spray gun. The emulsion thus formed is discharged in the form of an atomized liquid and applied to the particles further formed into plates.

As mentioned above, the phosphate separating agent can be contacted with the particles as a separate component, in which case it can be used in pure form, i. without solvents, or as an aqueous solution or dispersion. Most often, the release agent, either pure or in dissolved form, when used alone, i.e. without polyisocyanates, is applied to the particles in the form of a spray. In a preferred embodiment, however, the release agent and the polyisocyanate are used together in a simple mixture. This can be done in several ways. When the polyisocyanate is used as a binder component without diluents, such as water, then the release agent can be added to the polyisocyanates by simple admixture. If the polyisocyanate is used as a binder component in the form of an aqueous emulsion, then the release agent may be added as a separate component during or after emulsion formation, or in a particularly preferred embodiment, the release agent may be premixed with the organic polyisocyanate prior to emulsification. The organic polyisocyanate and the release agent can thus be premixed and stored for any length of time prior to emulsion preparation. Further, if an emulsifier is used to prepare the emulsion, the emulsifier may also be added to the mixture of organic polyisocyanate and release agent, and the resulting storage-capable mixture may be used at any time to prepare an aqueous emulsion by simply mixing with water and the above aqueous emulsion used as binder component.

When the polyisocyanate is used as a binder component in the form of an aqueous emulsion, the proportion of organic polyisocyanate present in said aqueous emulsion is preferably in the range of about 0.1 to about 99% by weight, particularly in the range of about 25 to about 75% by weight.

When the release agent is introduced as a separate component or in combination with a polyisocyanate, the proportion of the release agent used is in the range of about 0.1 to about 20 parts by weight per 100 parts by weight of the polyisocyanate, most preferably in the range of about 2 to about 10 parts by weight. per 100 parts of polyisocyanate. The amount of emulsifier needed to prepare the aqueous emulsion is not critical and varies with the particular emulsifier used, typically from about 0.1 to 20% by weight of the polyisocyanate.

As a starting material for the production of particle boards, cellulosic material and the like can be used which are capable of pressing and joining into a plate shape. Typical materials are wood chips obtained from woodworking wastes such as wood shavings, veneer chips and the like. Also particles of other cellulosic materials such as shredded paper, cellulose or vegetable fibers such as cereal blades, straw, bagasse may also be used. and the like, and non-cellulosic materials such as crushed waste rubber, polyurethane, polyisocyanurate, and similar foam and non-foam polymers. Inorganic materials, such as hydrated alumina, chopped mineral fibers and the like, either alone or in admixture with any of the aforementioned cellulosic or non-cellulosic materials, can also be used to produce particle board.

The particle board is produced by spraying the components of the binder mixture onto the particles by spraying either the components themselves or the mixture, wherein the particles are mixed in a suitable mixer. For example, a total of about 1 to 8% by weight of the binder mixture (in addition to any water present), based on the dry weight of the particles, is added, but both higher and lower amounts of binder mixture may be used.

After sufficient mixing of the particles with the binder mixture, this material is formed into a mat. The mat is then placed in a heated press between the mats. bed sheets and are pressed to form particle boards. The pressing times, temperatures and pressures can vary greatly depending on the thickness of the sheets produced, the desired board density, the particle size used, and other known factors. Typical pressures range is about 2.1 to 4.8 MPa and temperatures about 165 to 185 ° C. The pressing times usually range from 2 to 5 minutes. Since the moisture content present in the chip carpet reacts with the polyisocyanate to form the polyurea as mentioned, the moisture content of the isocyanate binders is not as important as with other binder systems.

The particle board manufacturing process can be carried out batchwise, i. the individual sheets of the particle board may be formed by treating a corresponding amount of chips with a binder mixture by heating and pressing. It is also possible to carry out the process continuously by feeding the treated particles in the form of a continuous particle belt or carpet to the heating and pressing zones defined by the upper and lower pressing bands through which the material to be treated is subjected to the required pressure and heat.

The following exemplary embodiments illustrate the binder composition of the present invention: as well as the methods of preparing the compositions, the compositions and the possibilities of using the binder compositions; according to the invention without limiting the scope of the invention in any way. : · ·.

Example 1.

Dilaurylchlorophosphate A ^:

A solution of 559 grams (3 moles) of lauryl alcohol in 500 ml of toluene under a nitrogen atmosphere was mixed with a total of 203.25 grams (1.5 moles) of phosphorus oxychloride, which was added dropwise over one hour. ^mixtures; during the addition was maintained at a temperature · / from 10 to 14 ° C by external cooling. After dosing the temperature · mixtures cope with ambient temperature (about 20 ° Celsius), and the mixture was allowed to stand overnight. Thereafter, the mixture was heated to 8.8 ° C over a period of two hours while the solvent was distilled off. The last traces of solvent were removed by heating the mixture to 75 ° C under high vacuum to obtain 685.7 grams. a clear colorless liquid in the form of a residue in which the hydrolysable chlorine content was determined to be 7.2% (theoretically 7.83%).

Example 1 a d 2

Methyldilauryl phosphate

A solution of 5 grams (0.15 mol) of methanol and 12.12 grams (0.12 mol) of trlethylamine in 200 ml of toluene was stirred at ambient temperature (22 ° C), adding a total of 45.25 grams to the solution. (0.1 mol) of dilauryl chlorophosphate, prepared according to Example 1, was added dropwise over 13 minutes. After addition, the reaction mixture was stirred further

After 1.5 hours at ambient temperature, triethylamine hydrochloride (7.85 g) was removed by filtration. The filtrate was heated to 95 ° C for several minutes, then cooled to 5 ° C and filtered. The solid thus isolated was analyzed as triethylamine hydrochloride in an amount of 2.82 g. The filtrate was evaporated to dryness and the residue was triturated with 150 ml of ether. The insoluble residue (triethylamine hydrochloride 0.33 g), triethylamine hydrochloride in a total amount of 11 grams, i.e. 80% of the theoretical content, was removed by filtration and the filtrate was evaporated to dryness. The yield was 44 grams of methyldilauryl phosphate, in which 0.09% hydrolysable chlorine was determined corresponding to 1.15% starting material (dilauryl chlorophosphate).

Example 3 n-Butyldilauryl phosphate

A solution of 8.14 g (0.11 mol) of n-butyl alcohol and 12.12 g (0.12 mol) of triethylamine in 200 ml of toluene was stirred at ambient temperature (22 ° C) dropwise. a total of 45.25 g (0.1 mol) of dilauryl chlorophosphate (prepared according to Example 1) was added over seven minutes. The resulting mixture was heated to 100 ° C and left under stirring at this temperature for 30 minutes. After this time, the reaction mixture was cooled to 5 ° C and filtered to remove triethylamine hydrochloride (6.11 g). Low triethylamine hydrochloride content indicates incomplete reaction. Accordingly, an additional 8 grams of triethylamine was added to the filtrate, and the filtrate was heated at 93-101 ° C for an additional 1 hour. After this time, the mixture was cooled to 5 ° C and filtered. An additional 3.5 g of triethylamine hydrochloride was thus obtained. The filtrate was evaporated to dryness and the residue was triturated with 150 ml of ether. The suspension was filtered and an additional 0.18 g of triethylamine hydrochloride was collected and the residue was evaporated to dryness under reduced pressure to give 43.9 g of n-butyldilauryl phosphate.

Example 4 n-octyldilauryl phosphate

In this example, the same procedure as in Example 3 was followed except that n-butyl alcohol was replaced by 13 grams (0.1 mol) of n-octanol to give n-octyldilauryl phosphate as a colorless liquid with a hydrolyzable chlorine content of 0.04 % by weight representing 0.51% by weight of the starting dilauryl chlorophosphate.

Example 5

Dilauryl-N, N-diethylphosphoramide

A solution (7.3 grams (0.1 mol) of diethylamine and 12.12 grams (0.12 mol) of triethylamine in 200 ml of toluene was stirred at ambient temperature (23 ° C), dropwise added over a period of 25 minutes. minutes, a total of 45.2 grams (0.1 mole) of dilauryl chlorophosphate (prepared as described in Example 1) The resulting mixture was stirred for an additional hour at ambient temperature, then cooled to 10 and filtered The isolated solid was triethylamine hydrochloride The filtrate was evaporated to dryness and the residue was triturated with 150 ml of ether.The solid was collected by filtration (0.38 g of triethylamine hydrochloride) and the filtrate was evaporated to dryness with the last traces of volatiles removed. 48.67 g of dilauryl-N, N-diethylphosphoramide were obtained.

Example 6

Dilauryl chlorophosphate prepared in the presence of polyisocyanate

According to this embodiment, to 91 grams (0.68 equivalents) of polymethylene polyphenyl polyisocyanate (equimolar weight 133, average binding 2.8, about 50% methylene bis (phenyl isocyanate) content) was added 3.05 grams (0.02 mole) of phosphoryl chloride and the mixture was stirred under a nitrogen atmosphere until a total of 7.1 grams (0.04 mol) of lauryl alcohol was added in seven portions. The course of the reaction was slightly exothermic (maximum temperature 38 ° C). The resulting mixture was cooled to ambient temperature (about 20 ° C) and allowed to stand until the evolution of hydrogen chloride ceased. The resulting solution of dilauryl chlorophosphate in polymethylene polyphenyl polyisocyanate was then used without further treatment to prepare the particle boards, as will be shown in Example 18.

Example 7

Lauryl dichlorophosphate in the presence of polyisocyanate

In this example, the same procedure was used as in Example 6 except that 184.4 grams (1.38 equivalents) of polymethylene polyphenyl polyisocyanate was used,

7.79 grams (0.052 mol) of phosphoryl chloride and 9.67 grams (0.052 mol) of lauryl alcohol to give a solution of predominantly lauryl dichlorophosphate in polymethylene polyphenyl polyisocyanate, which was used without further processing to prepare the particle boards as described in Example 11 below.

Example 8

A mixture of hydroxypropyldioleyl phosphate and difhydroxypropyl) oleyl phosphate

A total of 10 grams (0.17 mol) of propylene oxide was quickly added dropwise to a stirred solution of 50 grams (approximately 0.1 mol) of acid oleyl phosphate (a mixture of acid mono- and dioleyl phosphates) in 50 mL of methylene chloride. 22 ° C and rapidly rose to 41 ° C, at which temperature heating was started at reflux, after the addition was stirred for an additional hour, during which time the temperature dropped to 25 ° C, after which the volatiles were evaporated.

CHOH t-POCl, i 3

C ₅₀ W ₃₅ COO-CH ₂ using a 50 ° C water bath and the remainder was 60 grams of a colorless oil. This oil was a mixture of hydroxypropyldioleyl phosphate and di (hydroxypropyl) oleyl phosphate.

Example 9

A solution of di (nonylphenyl) chlorophosphate in polyisocyanate

According to this embodiment, to a mixture of 2.9 grams (0.19 mol) of phosphorus oxychloride in 89 grams of polymeithylenepolyphenyl polyisocyanate [equimolar weight 133, containing about 50% methyleinbis (phenylisocyanate), average binding 2.8] was added 8.3 grams with stirring (0.038 mol) nonylphenol. The course of the reaction was slightly exothermic and the temperature of the reaction mixture reached 29 ° C approximately 20 minutes after the end of dosing. The mixture was then slowly warmed to 100 ° C and held at 100 to 115 ° C for one hour. During this time, the weight of the reaction mixture was reduced by 1.2 grams (87% of theoretical loss), the residue was cooled to room temperature to give a solution of dl (nonylphenyl) chlorophosphate in polymethylene polyenyl polyisocyanate.

Example 10

Bis (dioleylglyceryl) chlorophosphate cw-o I c ^ h ₃₅ cooch _z o

and

- P-Ct * 2HCl

The above equation illustrates the use

1,3-dioleylglycerol as starting material, while the reaction described below uses a mixture of 1,2- and 1,3-dioleylglycerol as starting material.

To a solution of 62 grams (0.104 mol) of diolein, a mixture of 1,2- and 1,3-dioleylglycerol in 100 ml of toluene maintained at 20 ° C under a nitrogen atmosphere, a solution of 7.7 grams ( 0.05 mol) of phosphorus oxychloride in 50 ml of toluene. The mixture was stirred during the addition. At the end of the dosing, the mixture was heated under reflux for 5 hours, during which time a light sticky resin formed on the walls of the vessel. After heating, most of the reaction mixture was decanted from the solid residue and excess phosphorus oxychloride and toluene were removed by distillation. The distillation residue consists of bis (dioleylglyceryl) chlorophosphate, which is then used without further preparation to prepare particle plates, as will be shown in Example 20.

Example 11

In this example, a chipboard sample was prepared as follows:

A batch of 1000 grams of Pohderosa pine chips, ground on a hammer mill of 10 millimeters, with a water content of 3.4%, was placed in a rotary drum mixer and the hub rotated, while the chips were sprinkled with an aqueous emulsion prepared by mixing 48.3 grams of lauryldichlorophosphate solution obtained according to Example 8), 96.6 grams of water and 0.75 grams of emulsifying agent (aqueous solution of sodium styrene-maleic anhydride copolymers, 30% solids.) The resulting emulsion was sprayed onto wood chips from a paint spray gun, with the chips mixed for about two minutes In addition, 525 grams of the treated particles were spread into a 30 x 30 om particle board carpet with a plywood molding frame After removing the plywood molding frame, two steel sheets were placed along two opposite sides of the steel plate. steel rods of 10 mm, which corresponds to the desired thickness of the particle board and the second steel plate of 30 x 30 cm is placed from above onto the mat. The whole assembly was then placed on the lower press plate of the press with a capacity of 444.82 kN. Both press plates were preheated to 171 ° C. The press plates were then pressurized. When the pressure reached 3.45 MPa, the pressure was maintained for four minutes. The chipboard thus formed was then de-molded and it was found that no board showed any tendency to adhere to or adhere to the molding boards. This is in direct contrast to the particle board prepared in exactly the same way, but using the same polymethylene polyphenyl polyisocyanate without lauryl dichlorophosphate or any other additives.

The following physical properties were found in the particle board prepared as described above:

density 672.4 kg. m ~ ³ modulus of flexural strength ¹ 12.07 MPa dry internal bond ¹ 1.17 MPa (Restrictions made according to ASTM-1037-72). Example 12

A chipboard sample was prepared in the same manner as in Example 11 with the following changes.

The wood chips used were pine chips with a water content of 10% by weight. A batch of 600 grams of these chips was sprayed in the same manner as in Example 11, using 30 grams of a mixture obtained by mixing 91 grams of polymethylene polyphenyl polyisocyanate (equivalent weight 133, average binding 2.6) and 9 grams methyldilauryl phosphate prepared according to Example 2. 525 grams were then compressed to give a 10 mm particle board in the same manner as in Example 11, using 171.1 ° C press plates and a press pressure of 3.45 MPa, which was applied for four minutes. The board exhibited the following characteristics:

density 689.21 kg. m ³ flexural modulus ¹ 16.06 MPa modulus of elasticity ¹ 2013.34 MPa dry internal bond ¹ 1.13 MPa (Restrictions performed according to ASTM-1037-72 j. Example 13

According to this example, a chipboard sample was prepared in the same manner as in Example 11, with shading changes. Western cedar wood chips with a water content of 4% by weight were used in this embodiment. A batch of 700 grams of these chips was sprayed in the same manner as in Example 11. A preformed mixture was used for the feed.

23.1 g of polymethylene polyphenyl polyisocyanate (as in Example 2) and 2.3 g of a mixture of hydroxypropyldioleyl phosphate and di (hydroxypropyl) oleyl phosphate, prepared according to Example 8.

525 grams of chips were compressed in a sprayed state onto a 10 mm thick chipboard using the procedure of Example 11, the press plate temperature being 171 ° C and the applied pressure was

3.45 MPa, and this pressure was maintained for four minutes. The particle board thus formed was mold-free and showed no tendency to adhere to or adhere to the molding plates.

Example 14 i

According to this embodiment, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. The wood particles used were ponderosa pine chips (as in Example 12) with a water content of 10% by weight. A batch of 1000 grams of these chips was sprayed in the same manner as in Example 11. A preformed mixture of 45 grams of polymethylene polyphenyl polyisocyanate (see Example 11 and 5 grams of n-butyldilauryl phosphate (prepared according to Example 3) was used). a 10 mm thick board in the same manner as in Example 11, using a press plate heated to 177 ° C and a pressurized pressure of 3.45 MPa was maintained for four minutes. mold release properties, without any sign of sticking to the molding plates The board of this example exhibited the following physical properties:

density flexural modulus ¹ modulus of elasticity ¹ dry internal bond ¹ (Resty according to ASTM-1037-72).

672,4 kg.rn “ ³

15,10 MPa

1792.7 MPa

1.24 MPa

Example 15

According to this embodiment, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. The wood particles used were ponderosa pine chips (as in Example 12 with a water content of 10% by weight. A batch of 600 grams of these chips was sprayed using the method of Example 11 using 30 grams of a solution of di (nonylphenyl) chlorophosphate in polymethylene polyphenyl polyisocyanate prepared. according to Example 9. A portion of 525 grams of the sprayed chips was then compressed onto a 10 mm thick chipboard using the procedure of Example 11, the temperature of the press plates being 171 ° C and the pressing pressure being 3.45 MPa for four The particle board thus formed was freed from the mold and very freely released from the molding boards and the following physical properties were found:

density 672.4 kg. m ^-3. flexural strength modulus ¹ 11.51 MPa modulus of elasticity ¹ 1599.6 MPa dry internal cohesion ¹ 1.10 MPa (Cities according to ASTM-1037-72).

Example 16

According to this embodiment, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. The chips used were ponderosa pine chips (as in Example 12 with a water content of 10% by weight. A batch of 525 grams was sprayed in the same manner as in Example 11 using 30 grams of a mixture obtained by mixing 91 parts by weight of polymethylene polyphenyl polyisocyanate and 9 parts by weight of dilauryl). The N, N-diethylphosphoramide (prepared according to Example 5) was then pressed onto a 10 mm thick chipboard in the same manner as in Example 11, at a press plate temperature of 171 ° C and a pressurizing pressure of 3.45 MPa. The pressure was applied for four minutes, and the particle board thus produced was de-molded and released well from the molding plates.

density 689.2 kg. m ~ ³ modulus of flexural strength ¹ 15.72 MPa modulus of elasticity ¹ 1882.3 MPa dry internal cohesion ¹ 1.38 MPa (Cities made according to ASTM-1037-72). Example 17

A chipboard sample was prepared in the same manner as in Example 11 with the following differences. The wood particles used were ponderosa pine chips (as in Example 12) with a water content of 10% by weight. A batch of 525 grams of these chips was sprayed in the same manner as in Example 11, using 30 grams of the mixture obtained by mixing 91 parts by weight of polymethylene polyphenyl polyisocyanate and 9 parts by weight of dilouryl chlorophosphate (prepared as described in Example 1). The injected chips were then compressed to form a 10 mm chipboard in the same manner as in Example 11, using a press plate temperature of 171 ° C and a pressure of 3.45 MPa, which was applied for four minutes. The particle board thus produced was mold-free, showing excellent removal properties and no sticking to the molding plates. This plate had the following physical characteristics:

density 706.0 kg. m ~ ³ flexural modulus ¹ 15.7 MPa elastic modulus ¹ 2144.3 MPa dry internal cohesion ¹ 1.17 MPa (Cities made according to ASTM-1037-72). Example 18

In this example, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. The wood particles used were ponderosa pine chips (as in Example 12) with a water content of 10% by weight. A batch of 600 grams of these chips was sprayed using the procedure of Example 11 using 30 grams of a solution of dilauryl chlorophosphate in polymethylene polyphenyl polyisocyanate (prepared according to Example 6). Next, 525 grams of the plates were compressed onto a 10 mm thick particle board using the procedure of Example 11 at a temperature of 171 ° C, a pressure of 3.45 MPa and a pressure of four minutes. The plate thus produced was mold-free and showed excellent release from the molding plates. The board thus produced exhibited the following characteristics:

flexural modulus of ¹ MPa modulus 10.07 ¹ 1661.7 MPa internal cohesion dry ¹ 1.24 MPa (cities according to ASTM-1037-72).

Example 19

According to this embodiment, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. The wood particles used were ponderosa pine chips (as in Example 12) with a water content of 10% by weight. A batch of 1000 grams of these chips was sprayed in the same manner as in Example 11 using a mixture of 40.5 grams of polymethylene polyphenyl polyisocyanate (as in Example 11) and 4.5 grams of the dilauryl octyl phosphate prepared according to Example 4. Next, 525 grams of sprayed chips were compressed. to a chipboard having a thickness of 10 mm, using the same procedure as in Example 11. The temperature of the press plates was 177 ° C and the press pressure was 3.45 MPa for four minutes. The chipboard thus formed was then mold-free, freeing itself from the forming plates without any sticking. The plate thus produced had the following physical characteristics:

density 672.4 kg. m ^-3 flexural modulus ¹ 16.2 MPa modulus of elasticity ¹ 1841 MPa dry internal cohesion ¹ 1.52 MPa (tests performed according to ASTM-1037-72). Example 20

In this example, a chipboard sample was prepared in the same manner as in Example 11 with the following changes. A batch of 1000 grams of the same chips as in Example 11 was sprayed in the same manner as in Example 11 using an emulsion of 38.64 grams of polymethylene polyphenyl polyisocyanate (as in Example 11), 9.66 grams of bis (dioleylglyceryl) chlorophosphate prepared according to Example 10. , and 1.4 grams of an emulsifying agent as in Example 11 in 96.6 grams of water. Next, 525 grams of the injection chips were compressed onto a 10 mm thick chipboard using the procedure of Example 11. The temperature of the press plates was 177 ° C and the press pressure was 3.45 MPa, and this pressure was applied for four minutes. The plate thus produced was mold-free, freeing itself from the mold plates.

example 21

This example illustrates the preparation of a sheath plate of cellulosic animal waste using the procedure of Example 1. A batch of 1000 grams of air-dried horse droppings was shredded in a mixer using the same procedure and apparatus as in Example 11, and this material was then sprayed with an emulsion of 45 grams of polymethylene polyphenyl polyisocyanate (as in Example 11), 5 grams of dilauryl chlorophosphate (prepared according to Example 6), and 0.8 grams of an emulsifying agent as in Example 11 in 45 grams of water. Next, 525 grams of the injected material was then compressed onto a 12.7 mm thick plate using the procedure of Example 11. The temperature of the press plates was 177 ° C and the press pressure was 3.45 MPa, which was applied for four minutes. The plate thus produced was mold-free and showed good release from the press plates without sticking. This plate had a flexural strength of 4.83 MPa and an internal dry bond strength of 0.16 MPa, according to ASTM-1037-72.

Example 22

The procedure of this example illustrates the preparation of the sheath plate from inorganic particles. Hydrated alumina particles were used in this procedure. A batch of 650 grams of hydrated alumina was mixed by hand with a solution of 120 grams of polymethylene polyphenyl polyisocyanate (as in Example 11) and 10 grams of dilauryl chlorophosphate (prepared according to Example 6) in 50 ml of acetone. After mixing, acetone was evaporated in a circulating air oven and the remaining particles were then compressed to form a 10 mm plate using the same procedure as in Example 11. The press plate temperature was 210 ° C and the press pressure

3.45 MPa, which was applied for four minutes. The solid sheet thus produced showed a weight gain of 0.43% by weight after 24 hours storage in water at ambient temperature. No signs of crumbling or loss of strength were observed.

Claims (1)

Binder mixture for particle boards of materials capable of pressing and forming under heat and pressure, characterized in that it consists of a polymethylene polyphenyl polyisocyanate component containing from 25 to 90% by weight of methylene bis (phenyl isocyanate) and the remainder OF THE INVENTION consists of oligomeric polymethylene polyphenyl polyisocyanates having a bond strength greater than 2.0, and a phosphate component in an amount of from 0.1 to 20 parts by weight per 100 parts by weight of said polyisocyanate, said phosphate having the general formulas O t ( ^r ~ °> ₃ —p— ^(R 1> 1 in which denotes R is selected from the group consisting of an alkyl group of 3 to 35 carbon atoms, an alkenyl group of 3 to 35 carbon atoms, an aryl group of 6 to 18 carbon atoms, substituted with at least one alkyl group of 3 to 35 carbon atoms, or an alkyl group of 1 up to 6 carbon atoms substituted by at least one or two acyloxy groups containing 2 to 33 carbon atoms, R 1 is a member selected from the group consisting of chlorine, C 1 -C 6 alkoxy, di / alkyl, C 1 -C 6 amino, amino / C 1 -C 6 alkylene / oxy, and n is an integer of either 1 or 2, wherein in the case where n = 1, then one of the two R groups may be a methyl group or an ethyl group, and further in the case where in is equal to 1, then the two RO groups together with the phosphorus atom to which they are attached to form a residue of a heterocyclic ring containing 5 to 6 ring atoms.