JPH0118068B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyisocyanate-phosphate ester composition, and more particularly, particles of a storage-stable and compressible organic material are treated with the composition and formed by applying heat and pressure using a heating plate. The present invention relates to a composition that imparts internal mold releasability to a molded article. There is now widespread recognition of the use of organic polyisocyanates, particularly toluene diisocyanate, methylene vinyl (phenyl isocyanate), and polymethylene polyphenyl polyisocyanate, as binders or as a component of binders for the production of particle board. However, for example, U.S. Pat.
No. 3636199, No. 3870665, No. 3919017, and No. 3930110
Please refer to the issue. In one exemplary method, the binder resin, optionally in solution or aqueous suspension or emulsion, is tumbled into particles of cellulosic material or other material capable of forming particle board. It is applied or mixed using a device or a blender or other form of agitator. The mixture of particles and binder is then formed into a mat and subjected to heat and pressure using a heating plate. The process can be carried out batchwise or continuously. To avoid boards formed in this way from sticking to the heating platen, an isocyanate-impermeable sheet may be inserted between the board surface and the platen during the forming process, or the platen may be removed before each forming operation. It has been necessary to coat the surface with a suitable mold release agent, or coat the surface of the particles themselves with a material that will not stick to the disc. Each of these methods, especially those that are being operated continuously, is cumbersome and represents a drawback to the very satisfactory production of particleboard with very attractive structural strength. It's summery. The above deficiencies of using organic isocyanates as particulate board binders can be very satisfactorily overcome by incorporating certain phosphorus-containing compounds as internal mold release agents into the isocyanate compositions utilized. Here we have discovered that it can be minimized. We describe the incorporation of phosphorus-containing compounds as internal mold release agents in the production of polyether polyurethanes, US Pat.
I know number 4024088. Since the phosphorus compound disclosed in this document is an internal mold release agent for foams and elastomers obtained by mixing and casting a liquid polyisocyanate and a liquid polyether polyol, it is not suitable for the purpose of the present invention. do not have. The present invention provides storage that imparts internal mold release properties to the molded body when molded into a board by contacting particles of compressible organic material with a polyisocyanate and then applying heat and pressure to the treated particles. A stable composition, which has the formula (a)

[Formula] and

Phosphate esters of [formula] and ammonium salts, alkali metal salts and alkaline earth metal salts thereof; (b) Acid phosphate esters () and () and ()
Pyrophosphate esters represented by those derived from a mixture of and (c)

[Formula] and

[Formula] Acid phosphate ester () and () o-
Monoacyl derivative; (d) formula

[Formula] A carbamoyl phosphate ester having the formula and ammonium salts, alkali metal salts, and alkaline earth metal salts of the compound of the formula (); (e)

[Formula] and

【formula】 branched polyphosphoric acid ester; (f) General formula

100 parts by weight of a polyisocyanate of a phosphate selected from the following: a polyphosphoric acid ester corresponding to the formula containing (n=3) cyclometaphosphoric acid ester; and (g) a mixture of two or more of the above compounds; 0.1 to 20 parts by weight per R;
is alkyl having 8 to 35 carbon atoms, 8 to 35 carbon atoms;
alkenyl with 35 carbon atoms, and

[Formula] (wherein R' is alkyl having 8 to 35 carbon atoms, one of A and B is hydrogen and the other is selected from the group consisting of hydrogen and methyl, and n is 1 to 5. R 1 is a number with an average value); R ₁ is 1
is a hydrocarbyl having from 1 to 12 carbon atoms; R ₂ is a hydrocarbyl having from 1 to 12 carbon atoms and at least one additional

and n is an integer. "Alkyl having 8 to 35 carbon atoms" means a saturated monovalent aliphatic group having this number of carbon atoms in the molecule, and may be straight chain or branched. Examples of such groups include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,
Eicosyl, heneicosyl, docosyl, tricosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, pentatriacontyl, etc., and also include isomers thereof. "Alkenyl having 8 to 35 carbon atoms" means a monovalent straight-chain or branched aliphatic group containing at least one double bond in the molecule and having the above number of carbon atoms. do. Examples of such groups include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, pentacocenyl, triacontenyl,
pentatriacontenyl, etc., including isomers thereof. "Pyrophosphate ester derived from acid phosphate esters () and () and mixtures of () and ()" has the following meanings. Acid phosphates ( ) and ( ) are generally prepared in the form of mixtures of monoacid phosphates ( ) and diacid phosphates ( (as defined) with phosphorus pentoxide, according to methods well known in the art for the production of acid phosphate esters; see, for example, "Organophosphorus Compound",
See pages 220-221. The mixture of monoacid and diacid phosphoric esters thus obtained can be separated, if necessary, by fractional crystallization of salts such as barium, for example as described in the above-mentioned references. Individual acid phosphate esters or mixtures of the two can be used in the process of the invention. Pyrophosphate esters () and () are derived from the corresponding acid phosphate esters () and (), respectively, with the latter, carbonyl chloride, aryl or alkyl monoisocyanate and polyisocyanate, N-N'-dihydrocarbyl-carbodiimide, etc. easily obtained according to methods well known in the art by reaction with a dehydrating agent such as, for example, F. Kramer and M. Winter, Chem. Ber. 94 , 989.
(1961); 92 , 2761 (1959); M. Smith, JG Mofuat and HG Khorana, J.Am.Chem.Soc. 80 ,
6204 (1958). The individual acid phosphates () and () can be converted separately into the corresponding pyrophosphate esters, or the mixture of the two types of acid phosphates () and () can be converted into equivalent mixtures of pyrophosphates. can do. In the case of the acid phosphate ester of the above formula (), the corresponding pyrophosphate ester is of the formula where R has the meaning as defined above. In the case of the acid phosphate ester of the above formula (), the corresponding pyrophosphate ester has an average composition of the formula is a complex mixture represented by, where X
is a value having an average value of 1 or more than 1, and R has the meaning as defined above. "Hydrocarbyl of 1 to 12 carbon atoms"
means a monovalent group obtained by removing one hydrogen atom from a parent hydrocarbon containing these numbers of carbon atoms. Examples of such groups include alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, etc. and isomers thereof; alkenyl such as vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl. , decenyl, dodecenyl, etc. and their isomers; aralkyls such as benzyl, phenylpropyl, phenethyl, naphthylmethyl, etc.; aryls such as phenyl, tolyl, xylyl, naphthyl, biphenylyl, etc.; cycloalkyls such as cyclobutyl, cyclopentyl, cyclohexyl, cyclo heptyl, cyclooctyl, etc. and isomers thereof; and cycloalkenyls such as cyclopentenyl, cyclohexenyl, cycloheptenyl,
cyclooctenyl, etc. and their isomers,
It is. "Alkali metals" are lithium, sodium,
It is in its well-recognized sense to include potassium, rubidium and cesium.
"Alkaline earth metal" is also of a well-recognized meaning to include calcium, strontium, magnesium and barium. The process of the present invention is carried out substantially according to said processes in the art in which organic polyisocyanates are used as binder resins or as components thereof (for example, DE 2610552
and U.S. Pat. No. 3,428,592), the main exception is that the phosphoric esters as defined above are used in combination with particle treatment isocyanate compositions to be combined to form particle board together. . Particleboard is therefore made by bonding particles of compressible wood or other cellulosic or organic material together using heat and pressure in the presence of a binder system. The binder system consists of a combination of an organic polyisocyanate and a phosphate ester as defined above (hereinafter referred to as phosphate ester mold release agent). The polyisocyanate and phosphate ester mold release agent can be contacted with the particles as separate, separate components, or, in one preferred embodiment,
The polyisocyanate and phosphoric ester are contacted with the particles either simultaneously or after mixing. Whether the polyisocyanate and the phosphoric ester are introduced separately or in a mixture, they can be used as such, i.e. without diluent or solvent, or one or both can be incorporated into an aqueous suspension or emulsion. It can be used in the form. The polyisocyanate component of the binder system can be any organic polyisocyanate containing at least two isocyanate groups per molecule. Examples of organic polyisocyanates include diphenylmethane diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, α,α′-xylene diisocyanate, 2,4
- and 2,6-toluene diisocyanate, and mixtures of both these isomers (both commercially available),
triphenylmethane triisocyanate, 4,
4′-diisocyanate diphenyl ether, and polymethylene polyphenyl polyisocyanate,
It is. The latter polyisocyanate has a content of about 25 to ca.
A mixture containing 90% by weight of methylene bis(phenylisocyanate), the remainder of the mixture being
Polymethylene polyphenyl polyisocyanate with functionality greater than 2.0. Such polyisocyanates and methods of making them are well known in the art and are described, for example, in U.S. Pat. No. 2,683,730;
See No. 2950263, No. 3012008, and No. 3097191. These polyisocyanates are also available in various modified forms. One such form is the above-mentioned material which is subjected to heating, generally at a temperature of about 150°C to about 300°C, until the viscosity (at 25°C) increases to a value in the range of about 800 to 1500 centipoise. Contains polymethylene polyphenyl polyisocyanate. Another modified polymethylene polyphenyl polyisocyanate was treated with a small amount of epoxide to reduce its acidity according to US Pat. No. 3,793,362. Polymethylene polyphenyl polyisocyanate is a preferred polyisocyanate for use in the binder of the present invention. Particularly preferred polymethylene polyphenyl polyisocyanates are those containing from about 35 to about 65 weight percent methylene bis(phenyl isocyanate). When the organic polyisocyanate is to be used as a binder in accordance with the present invention in the form of an aqueous emulsion or suspension, the aqueous emulsion or suspension is removed from the aqueous emulsion or suspension before using the composition as a binder. It can be made by any of the techniques known in the art for the production of suspensions. Illustratively, a polyisocyanate is dispersed in water in the presence of an emulsifier. The emulsifier can be any emulsifier known in the art, including anionic and nonionic emulsifiers. Examples of nonionic emulsifiers include:
Alcohols of polyoxyethylene and polyoxypropylene and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene; alkoxylated alkylphenols such as nonylphenoxy poly(ethyleneoxy)ethanol; approx. Alkoxylated fatty alcohols such as ethoxylated and propoxylated fatty alcohols containing 4 to 18 carbon atoms; glycerides of saturated and unsaturated fatty acids such as stearic acid, oleic acid, ricinoleic acid, etc.; stearin acid,,
polyoxyalkylene esters of fatty acids such as lauric acid, oleic acid, etc.; fatty acid amides such as dialkanolamides of fatty acids such as stearic acid, lauric acid, oleic acid, etc. A detailed invention of such materials can be found in the Encyclopedia of Chemical Technology, 2nd Edition, Volume 19, pages 531-554, published by Interscience Publishers, Inc., New York. Formation of the emulsion or suspension can be carried out at any time prior to use as a binder composition, but is preferably carried out within about 3 hours prior to use. Any method conventional in the art for making aqueous emulsions can be used to make the aqueous polyisocyanate emulsions used in the process of the invention. Illustratively, an emulsion is formed by combining polyisocyanate, emulsifier, and water under pressure using a conventional spray gun, in which a flow of water and a flow of polyisocyanate are combined. collide and mix under turbulent conditions in the mixing chamber of the spray gun. The emulsion thus formed is discharged in the form of a spray, which spray is applied to the cellulosic particles formed in the board in the manner discussed below. As discussed above, the phosphate mold release agent can be contacted with the particles as one separate component, in which case it is used in neat form, i.e. without diluent, or in an aqueous solution or Used as a suspension. Preferably the phosphoric ester is provided to the particles in the form of a spray when used alone, either neat or in diluted form, ie when used separately from the polyisocyanate. However, in a preferred embodiment of the invention, the phosphate ester mold release agent and polyisocyanate are used together as a single composition. This can be achieved in several ways. Thus, when the polyisocyanate is used as the binder resin without a diluent such as water, the phosphate mold release agent can be incorporated into the polyisocyanate by simple mixing. When the polyisocyanate is used as the binder resin in the form of an aqueous emulsion, the phosphoric ester mold release agent can be added as a separate component during or after the formation of the emulsion, or can be added as a particularly advantageous embodiment. In the process, the phosphoric ester is premixed with the organic polyisocyanate prior to its emulsification. As described later, the phosphoric ester according to the present invention does not have a P-OH bond in its structure, so it does not react with the polyisocyanate at room temperature. and can be stored for any desired period of time prior to emulsion formation. Additionally, when an emulsifier is used in emulsion production, the emulsifier can be incorporated into the mixture of organic polyisocyanate and phosphate ester mold release agent to form a storage-stable composition; It can be converted into an aqueous emulsion at any desired time for use as a binder resin by simple mixing with water. When a polyisocyanate is used as a binder in the form of an aqueous emulsion, the proportion of organic polyisocyanate present in the aqueous emulsion advantageously ranges from about 0.1 to about 99% by weight, and from about 25 to about 99% by weight. Preferably it is in the range of 75% by weight. Whether the phosphate ester mold release agent is introduced as a separate component or in combination with the polyisocyanate, the proportion of phosphate ester mold release agent used is approximately 0.1 per 100 parts by weight of polyisocyanate. from about 2 to about 20 parts by weight, preferably from about 2 to about 10 parts by weight per 100 parts by weight of polyisocyanate. The proportion of emulsifier required for making aqueous emulsions is not critical and will vary depending on the particular emulsifier used;
Generally, based on polyisocyanate, approximately
It is in the range of 0.1 to 20% by weight. The starting materials for particle board include particles of cellulosic and similar materials that are compressible and capable of being bonded into the form of a board. Typical materials of this type are wood particles derived from timber industry waste such as planing shavings, veneer shavings, and the like.
Other cellulosic materials such as shredded paper pulp or vegetable fibers such as corn stalks, wheat straw, millet hulls, etc., as well as particles of polymeric foams such as polyurethane waste, polyisocyanates, etc., may also be used. Methods for producing suitable particles are well known and conventional. Mixtures of cellulosic particles may also be used if desired. Particleboard, for example, has been successfully made from wood particle mixtures containing up to about 30% bark. The moisture content of the particles may suitably range from about 0 to about 24% by weight. Typically,
Particles made from wood chips contain about 10-20% moisture and may be used without first drying. Particleboard is made by spraying the particles with the components of the binder composition, either separately or in combination, while the particles are rolled or agitated in a blender or similar mixing device. . Illustratively, a total of about 2 to 8% by weight of the binder system (excluding any water contained therein) is added based on the dry weight of the particles, although greater or lesser amounts of binder may be added. Agent resins may be used for any application. If desired, other substances such as wax sizes, flame retardants, pigments, etc. can also be added to the particles during the compounding stage. After effective mixing to create a homogeneous mixture,
The coated particles are formed into a loose mat or felt and preferably contain a moisture content of about 4 to about 18 percent by weight. This mat is then attached to a mesh board (caul).
The particles are placed in a heated press between the plates and compressed to integrate the particles into a single board. Pressing times, temperatures, and pressures will vary widely depending on the thickness of the board being made, the desired density of the board, the size of the particles used, and other factors well known in the art. To illustrate, for medium density 1/2 inch thick particle board, pressures of about 300 to 700 psi and temperatures of about 325-375 degrees are typical. Pressing times are typically about 2-5 minutes. Since some of the moisture present in the mat reacts with the polyisocyanate to form polyurea as previously described, the level of moisture present in the mat is less likely to occur for isocyanate binders than for other binder systems. Not critical. The above method can be carried out in batches,
That is, individual sheets of particle board can be formed by treating the appropriate amount of particles with a binder resin combination and heating and pressing the treated material. Alternatively, the process may be carried out continuously by feeding the treated particles in the form of a continuous web or mat into a heating and pressing zone defined by upper and lower continuous steel belts. The steel belt is subjected to the necessary heat and pressure. Whether the process of the present invention is carried out batchwise or continuously, the particle board produced using the polyisocyanate and phosphate mold release agent combination of the present invention will not be affected by the presses used to form it. It releases easily from the metal plate and shows no tendency to stick to it. This is in direct contrast to prior experience when using polyisocyanates alone as binders as discussed above. Any of the phosphoric ester mold release agents defined above can be used alone or in combination in the process of the invention, including pyrophosphoric esters () and () or mixed pyrophosphoric esters derived from mixtures of acid phosphoric esters () and (). Preference is given to using esters.
For example, any free hydroxyl groups present in the pyrophosphate or in the form of the unconverted acid phosphate starting material will generally be present in the vicinity of the polyisocyanate used in the process of the invention. Well-masked to be non-reactive at temperatures, the pyrophosphate esters can be stored in combination with the polyisocyanates for long periods of time without exhibiting any signs of deterioration. However, when the mixture of pyrophosphate and polyisocyanate is emulsified and used in the process of the invention,
The process temperature and generated steam during particle board formation involve the hydrolysis of pyrophosphate esters and regenerate the corresponding acid phosphate esters, which then play a role in helping release the particle board from the press plate. It is believed that it is working. It should be understood that the above theory is presented merely for illustration and is not intended to limit the scope of the invention in any way. As mentioned above, the monoacid phosphate esters () and diacid phosphate esters () and their esters used in the process of the present invention are the corresponding alcohols ROH (wherein R is as defined above). and phosphorus pentoxide (Kosolapov, supra). As is clear to those skilled in the art, it is possible to obtain corresponding mixtures of acid phosphate esters () and (or) () by using mixtures of two or more different alcohols during the above reaction. , in which the various components of the mixture have different values of the radical R. Also, as mentioned above,
The monoacid and diacid phosphates obtained in the above reaction can be fractionated into their individual components by conventional methods such as fractional crystallization, and the individual compounds thus obtained can be used in the method of the invention. Alternatively and preferably, the mixture of mono- and di-acid phosphates obtained in the above reaction can be used as a component in the process of the invention without separation, or can be converted to the corresponding mixture of pyrophosphate esters using the steps discussed above, which can then be used in the process of the invention. Examples of acid phosphate esters of the above formula () which can be used individually or in combination with other acid phosphate esters in the process of the invention include mono-O
-Octyl, mono-O-nonyl, mono-O-decyl, mono-O-undecyl, mono-O-dodecyl, mono-O-tridecyl, mono-O-tetradecyl, mono-O-pentadecyl, mono-O-hexadecyl , mono-O-peptadecyl, mono-O-
octadecyl, mono-O-nonadecyl, mono-O
-Eicosyl, mono-O-heneicosyl, mono-
O-docosyl, mono-O-tricosyl, mono-O
-Pentacyl, mono-O-hexacosyl, 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-heneicosenyl, mono-O-docosenyl, mono-O-tricosenyl,
Diacid phosphate esters of mono-O-pentacocenyl, mono-O-triacontenyl, and mono-O-pentatriacosenyl, and the esterifying group is capped with about 1 to 5 moles of ethylene oxide. It is a diacid phosphate derived from a monohydric alcohol such as lauryl. Examples of acid phosphate esters of the above formula () which can be used individually or in combination with other acid phosphate esters in the process of the invention are O,O-di(octyl), O,O-di(octyl), (nonyl), O,O-di(decyl), O,O-di(undecyl), O,O-di(dodecyl), O,O-di(tridecyl), O,O
-di(tetradecyl), O,O-di(pentadecyl), O,O-di(hexadecyl), O,O-di(heptadecyl), O,O-di(octadecyl),
O,O-di(nonadecyl), O,O-di(eicosyl), O,O-di(heneicosyl), O,O-di(docosyl), O,O-di(tricosyl), O,O
-di(pentacosyl), O,O-di(hexacosyl), O,O-di(heptacosyl), O,O-di(octacosyl), O,O-di(nonacosyl), O,
O-di(triacontyl), O,O-di(pentatriacontyl), O,O-di(dodecenyl),
O,O-di(tridecenyl), O,O-di(tetradecenyl), O,O-di(pentadecenyl),
O,O-di(hexadecenyl), O,O-di(heptadecenyl), O,O-di(octadecenyl),
O,O-di(nonadecenyl), O,O-di(eicosenyl), O,O-di(heneicosenyl), O,
One of O-di(docosenyl), O,O-di(tricosenyl), O,O-di(pentacocenyl), O,O-di(triacontenyl), and O,O-di(pentatriacosenyl) Acid phosphate esters, as well as diesterized monoacid phosphate esters, which are derived from monohydric alcohols such as lauryl in which the esterifying group is capped with about 1 to 5 moles of ethylene oxide. An example of a phosphate ester of the latter type which is available in admixture with the corresponding diacid phosphate ester is the material sold by Emery Industries under the trademark Trifuac. Examples of pyrophosphates of the above formula () which can be used individually or in combination with other pyrophosphates in the process of the invention include tetraoctyl, tetranonyl, tetradecyl, tetraundecyl, tetradodecyl, Tetra (tridecyl), Tetra (tetradecyl), Tetra (pentadecyl), Tetra (hexadecyl), Tetra (heptadecyl), Tetra (octadecyl), Tetra (nonadecyl), Tetra (eicosyl) Tetra (heneicosyl), Tetra (docosyl), Tetra (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 (heneicosenyl), Tetra (docosenyl), Tetra (tricocenyl) ), tetra(pentacocenyl), tetra(triacontenyl) and tetra(pentatriacocenyl) pyrophosphate esters. The above formula () which can be used individually or in combination with other pyrophosphate esters in the process of the invention
Examples of pyrophosphate esters 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(heneicosyl), di(docosyl), di(tricosyl), di(pentacosyl), di(hexacosyl), di(heptacyl), Di (octacosyl), di (nonacosyl),
Di(triacontyl), di(pentatriacontyl), di(dodecenyl), di(tridecenyl), di(tetradecenyl), di(pentadecenyl), di(hexadecenyl), di(heptadecenyl), di(octadecenyl), di( They are pyrophosphate esters of nonadecenyl), di(eicosenyl), di(heneicosenyl), di(docosenyl), di(tricosenyl), di(pentacocenyl), di(triacontenyl), and di(pentatriacosenyl). The above formula () which can be used in the method of the present invention
and acid phosphate esters () denoted as ()
O-monoacyl derivatives of and () are easily prepared by methods well known in the art. Illustratively, using the corresponding acid phosphate ester () or () in the form of silver or other metal salts and the method described by Kosolapov, supra, p. 334,
Reaction with a suitable acyl halide R ₁ COHal, where Hal represents chlorine or bromine and R ₁ is as defined above. Examples of the O-monoacyl derivatives of acid phosphate esters () and () include the O-monoacyl derivatives of the various acid phosphate esters () and
It is a derivative of acetyl, O-propionyl, O-octanoyl, O-decanoyl, O-dodecanoyl, O-benzoyl, O-toluoyl, and O-phenacetyl. The carbamoyl phosphates with () used in the process of the invention are described, for example, in F. Kramer and M. Winter, Chem. Ber. 92 , 2761 (1959).
are easily prepared by reaction of the appropriate acid phosphate ester () or () with the appropriate hydrocarbyl mono- or poly-isocyanate using the method described in . Examples of such carbamoyl phosphates include methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, hexylcarbamoyl, decylcarbamoyl of the monoacid phosphates exemplified above (stabilized in the form of their ammonium or alkali metal salts). , dodecylcarbamoyl, allylcarbamoyl, hexenylcarbamoyl, octenylcarbamoyl, decenylcarbamoyl, dodecenylcarbamoyl, phenylcarbamoyl, tolylcarbamoyl, diphenylcarbamoyl, benzylcarbamoyl, phenylpropylcarbamoyl, and similar hydrocarbamoyl derivatives. be. The carbamoyl phosphate ester () may contain free OH groups due to incomplete conversion of the acid phosphate upon reaction with a suitable hydrocarbyl isocyanate. This is because the OH group has low reactivity with respect to isocyanate. Such compounds containing free OH groups can be used without undesirable side effects due to the low reactivity of the OH groups with isocyanates. The polyphosphoric acid ester corresponding to formula () used in the process of the present invention is a suitable trialkyl phosphoric acid ester (RO) ₃ PO (wherein R is as defined above).
is readily prepared by reacting with phosphorus pentoxide using the method described in Kosolopov, supra, p. 341. Generally, the composition of polyphosphoric acid ester is generally expressed by the formula (), and includes a cyclic compound (n=3) having a six-membered ring consisting of another phosphorus atom and an oxygen atom. The polyphosphoric acid esters corresponding to formulas () and () used in the process of the present invention are suitable di-
or tri-alkyl phosphates and appropriate halophosphates.

It can be easily prepared by reaction with [Formula] (wherein Hal is chlorine or bromine) using, for example, the method described on page 338 of Kosolopov, supra. The method also includes the removal of alkyl halides. In another embodiment of the present invention, the combination of polyisocyanate and phosphoric ester mold release agent used as a binder in the present invention may be a thermosetting material conventionally employed in the art. It can be used with resin binders such as the phenol-formaldehyde, resorcinol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, urea-furfural and condensed furfuryl alcohol series. The use of such a combination not only avoids the problem of adhesion of the finished particleboard to the press, which is a problem hitherto encountered with mixtures of isocyanates and thermosetting resin binders of the type mentioned above. , the physical properties of the particle board thus obtained are significantly improved by the use of this combination. The following Preparation and Examples describe the manner and process of making and using the invention and represent the best mode contemplated by the inventors of carrying out the invention, but are not intended to be limiting. It's not a thing. Production method 1 Production of pyrophosphate ester from lauric acid phosphate 70 g of lauric acid phosphate (a mixture of O, O-dilauryl-acid phosphate and O-lauryl dioic acid phosphate; Futskerkerkar) and 60 g of lauric acid phosphate ester
g of phenyl isocyanate is charged into a dry flask equipped with a stirrer, condenser, and drying tube, the flask is immersed in an oil bath preheated to 80°C, and the contents of the flask are poured into an oil bath. Bath temperature is 115
Stir while gradually increasing to °C. Carbon dioxide evolved over about an hour. After the evolution of carbon dioxide had ceased, the reaction mixture was cooled to room temperature and diluted with 100 ml of chloroform. The resulting mixture was filtered and the solid thus collected (24.8 g of N-N'-diphenylurea) was washed with chloroform. The combined liquid and washing liquid was concentrated on a rotary dryer with a bath temperature of 50°C. Once most of the solvent had evaporated, crystals of N,N'',N''-triphenyl biuret separated, evaporation was stopped and this solid material (6.6 g) was separated. The liquid was evaporated to dryness and finally the excess phenyl isocyanate was removed under reduced pressure at 50°C. The residue (70 g) was the desired pyrophosphate ester in the form of a colorless to pale yellow liquid. The infrared spectrum of the product (in _CHCl3 ) does not show any band characteristics of P--OH bonds, and P
It had a strong band at 940 cm ^-1 , which is characteristic of the -O-P bond. Production method 2 Production of pyrophosphate ester from lauric acid phosphate A total of 70 g of lauric acid phosphate (same starting material as used in production method 1) was charged into a flask equipped with a stirrer, reflux condenser and gas inlet, 65
Heat to melt at -75°C under nitrogen. Stir the melt while adding a slow stream of phosgene
Allowed to pass for 2.5 hours. The temperature was maintained within the above range throughout this addition. Gas evolution from the reaction mixture was intense during the first hour of phosgene addition, gradually subsided, and was very slow at the end of the phosgene addition period. After the addition was complete, the mixture was purged with nitrogen for 15 hours, during which time the temperature was maintained within the above range. At the end of this time, the pressure inside the reaction flask gradually decreases to about mercury.
Gaseous hydrogen chloride and carbon dioxide were removed by vacuuming to 1.0 mm. The viscous residue thus obtained solidified completely when left overnight. Thus, about 60
66 g of pyrophosphate were obtained as a solid which slowly melted at .degree. Process 3 Production of pyrophosphate from oleyl phosphate ester A mixture of 200 g of oleyl phosphate (O, O-, supplied by Futsker Chemical Company)
(consisting of a mixture of dioleyl acid phosphate ester and O-monooleyl acid phosphate ester) was prepared at 160° C. for 5.5 hours at a temperature of 85-90° C. using the method described in Process 1.
g of phenyl isocyanate. The N,N'-diphenylurea (68 g) was removed by filtration after diluting the reaction mixture with 200 ml of chloroform. The liquid was concentrated on a rotary evaporator and excess unreacted phenyl isocyanate was removed by distillation at reduced pressure. N,N',N''-triphenyl biuret crystallized from an oily residue when left at room temperature. After removing the crystals by filtration, 196 g
A liquid product is formed whose infrared spectrum is P-
It showed a band at 940 cm ^-1 characteristic of O--P bond, but no characteristic band of P--OH. Preparation 4 Preparation of Pyrophosphate from Lauric Acid Phosphate A solution of 30.4 parts by weight of lauric acid phosphate (same starting material as in Preparation 1) in 21 parts by weight of toluene was charged into a dry reactor that had been previously purged with nitrogen. The solution was heated to 40° C. with stirring, at which point 7.6 parts by weight of polymethylene polyphenyl polyisocyanate [equivalent weight =
133; functionality 2.8; containing approximately 50% methylene bis(phenylisocyanate)] was added.
The resulting mixture was stirred while a flow of phosgene was introduced (approximately 0.1 parts by weight/min) and the temperature was slowly increased.
The temperature was raised to 80℃. The temperature was maintained at this level while phosgene was introduced continuously until a total of 20 parts by weight of phosgene had been introduced. The total time of phosgene addition was 5 hours and 50 minutes. The reaction mixture was heated at the same temperature for an additional 40 minutes before the phosgene addition was complete and heated to 90-95°C and purged with nitrogen for 2 hours to remove excess phosgene. The pressure in the reactor was reduced until toluene reflux began, and purging with nitrogen was continued for an additional 2 hours. The toluene was then removed by vacuum distillation and the last traces were removed in vacuo. The residue was cooled to room temperature, treated with diatomaceous material (Celite 545) and filtered after stirring for 30 minutes. Thus, a mixture of lauryl pyrophosphate ester and polymethylene polyphenyl polyisocyanate which was found to contain 6.08% by weight of phosphorus was 23.7
Parts by weight were obtained. Production method 5 Another production of pyrophosphate ester from lauric acid phosphate ester The method described in Production method 4 is used, but the polymethylene polyphenyl polyisocyanate used therein is replaced with an equivalent amount (6.8 parts by weight) of phenyl isocyanate to produce lauryl pyrophosphate. Another batch of phosphoric ester was obtained. Example 1 A series of wood particle board samples were made by the following method with the component amounts (all parts by weight) shown in Table 1 below. Wood chips (wheel shavings) were placed in a rotating mixing drum and the drum was rotated while the particles were sprayed with an aqueous emulsion of polyisocyanate, water, phosphate ester, and emulsifier.
The emulsion was made by mixing the ingredients using a Turrex mixer prior to use. The resulting emulsion was sprayed onto the wood particles using a paint spray gun with rotation for 45-120 seconds to obtain homogeneity. The coated particles were formed into a felt mat on a 12 inch by 12 inch cold rolled steel plate with the aid of a plywood forming frame. After removing the forming frame, a steel bar with a thickness corresponding to the desired thickness of the finished particle board (1/4 inch) is placed along the two opposing edges of the steel plate and the second A 12 inch by 12 inch cold rolled steel plate was placed on top of this pine. This finished assembly was then placed on the lower plate of a Dake press capable of 100,000 pounds of force. Both plates of the press were preheated to the selected temperatures shown in Table 1. Pressure was then applied and the molding times shown in Table 1 were calculated from the point at which the pressure on the mat reached 500 psi. After the molding time shown in Table 1,
The pressure was released and the particle board was demolded.
In all cases, demolding was easily carried out without any tendency for the board to stick to the plates it was in contact with. This is in contrast to the behavior of boards made under the same conditions and without the presence of lauric acid phosphate in the emulsion used as a binder during board manufacture. Various samples of particle board thus produced were then subjected to a series of physical tests and the properties thus determined are recorded in Table 1. These properties indicate the excellent structural strength properties of these boards.

【table】

Table: Example 2 A series of wood particle board samples were made using the method described in Example 1 using the various ingredients and amounts (all weight percent) shown in Table 2 below. The molding times shown in the table for samples E and F are based on the molding time when the pine is heated to its internal temperature (measured by an inserted thermocouple).
This is the time it was held under pressure (500psi) after reaching 130㎓. Sample G was a comparative sample molded as described in Example 1. The physical properties measured for each of the final particle boards are also shown in Table 2 and demonstrate the excellent structural strength of each sample. All samples demolded easily and showed no signs of adhesion to the steel plates used for their manufacture.

【table】

EXAMPLE 3 A series of samples of wood particle board were made using exactly the same reactants and proportions as shown in Example 1 and using exactly the method described in that example. However, the press plate was preheated to 400℃ and held at that temperature for various molding times shown in Table 3 below. The physical properties of the samples thus prepared are also recorded in Table 3 and show that all of these samples have excellent structural strength. None of these samples showed any tendency to stick to the mold plate during demolding.

[Table] Example 4 A series of samples of wood particle board were prepared using the method described in Example 1, but changing the nature of the polyisocyanate and substituting lauric acid phosphate as described in Process 3. It was produced using a pyrophosphate derived from oleyl acid phosphate. The various ingredients and their proportions (all parts by weight) are shown in Table 4 below, along with the physical properties measured on the final samples. The thickness of the board samples was 3/8 inch in all cases (spacer rods of approximately the same thickness were used). None of the samples showed any tendency to stick to the mold plate during demolding. The physical properties of the various samples show that they all have excellent structural strength.

【table】

EXAMPLE 5 This example illustrates the production of particle board according to the invention using a binder composition in the absence of any external emulsifier, the polyisocyanate being present as is, i.e. in the form of an aqueous emulsion. It was applied without any problems. A series of samples of wood particle board were prepared using the various ingredients and amounts (all parts by weight) shown in Table 5 below and using the method described in Example 1, except that the wood particles were first of water and then with a mixture of polyisocyanate and phosphate mold release agent. The physical properties measured for each of the finished particleboards are also shown in Table 5 and indicate excellent structural strength for each sample. All samples demolded easily and showed no signs of adhesion to the steel plates used during their manufacture.

【table】

[Table] Example 6 In this example, three particle boards were made according to the method of the present invention from "wafer" chips approximately 2 inches by 2 inches by 1/32 inch in size and supplied by Weldwood of Canada. It explains things. No external water or emulsifier was used, and the polyisocyanate and phosphate mold release agents were applied as is. A series of samples of particle board from this wafer chip were made using the various components and amounts (all parts by weight) shown in Table 6 below and using the method of Example 1, except that the wood wafers were It was sprayed with a mixture of isocyanate and phosphate ester mold release agent, the same aqueous emulsion as in Example 1 was not sprayed, and an aluminum mold plate was used. All samples demolded easily and showed no signs of adhesion to the aluminum plates used for fabrication. The superior structural strength of the resulting particle board, as evidenced by the height of the modulus of failure shown in Table 6, is due to the superior structural strength of the resulting particle board, which can be obtained from similar wafer chips using a commercially available phenol-formaldehyde resin binder. This compares very well with the lower numbers (2500psi) measured on Tsukutsuta boards.

【table】

EXAMPLE 7 This example describes a series of particulate polymers using a polyisocyanate binder in combination with various commercially available phosphoric esters in an amount equivalent to about 0.7% by weight of phosphorus in the binder-resin combination. It explains how to manufacture a kuru board. These various samples were made using the various ingredients and amounts (all parts by weight) shown in Table 7 and using the method of Example 1, except that no emulsifier was used and water was first sprayed onto the chips. This was followed by spraying an isocyanate mixed with a mold release agent. All samples were easily demolded and showed no signs of adhesion to the steel plates used for manufacture.
In contrast, a comparison board made in exactly the same manner but omitting the use of a phosphate ester mold release agent adhered to the steel plate used in its manufacture and could not be demolded without damaging the board surface.

【table】

Table: Example 8 A further series of particleboard samples were prepared using the same phosphate ester mold release agent and method used in Example 7, but at a lower concentration in the binder resin combination. Manufactured by The various components and their proportions (all parts by weight) are shown in Table 8 below, along with the physical properties measured on several samples. All samples could be demolded without damage to the board or significant adhesion to the mold plate. Samples made with a high concentration of phosphate ester mold release agent slide out between the mold plates during demolding, whereas samples made with a low concentration of phosphate ester mold release agent (OO, QQ, and UU) successfully release from the mold. needed help, namely, tapping the molded plate. All samples are 1/1 on the finished board.
It was 2 inches thick.

【table】

EXAMPLE 9 This example illustrates the use of a binder resin combination according to the present invention with a prior art phenol-formaldehyde resin binder. All samples (1/2 inch thick) were prepared using the method described in Example 1, with the exceptions detailed below, and using the reactants and proportions (all parts by weight) shown in Table 9. . For boards YY and ZZ,
The phenol-formaldehyde resin is mixed into the isocyanate emulsion while the board
In the case of AAA, the chips were first sprayed with the indicated amount of added water, then with phenol-formaldehyde resin, and finally with polyisocyanate. comparison board
In case of BBB, the chips are sprayed with water and
It was then sprayed with phenol-formaldehyde resin. Boards XX and ZZ did not show significant adhesion to the molded plate after molding, but boards YY,
Severe adhesion problems were encountered in the case of AAA and BBB. The physical properties of these various boards are also shown in Table 9, from which it can be seen that the properties of boards XX and ZZ, which are both within the scope of the present invention, as well as those of boards YY, AAA, which are outside the scope of the present invention, It can be seen that the properties are clearly superior to those of BBB.

【table】

Claims (1)

[Claims] 1. (a) A polyester comprising from about 25 to about 95% by weight methylene bis(phenyl isocyanate), with the remainder of the mixture being an oligomeric polymethylene polyphenyl polyisocyanate having a functional group greater than 2.0. methylene polyphenyl polyisocyanate, and (b) approximately per 100 parts by weight of the above polyisocyanate.
from 0.1 to about 20 parts by weight of the formulas independently selected from the types consisting of R' from 8 to
alkyl having 35 carbon atoms, one of A and B representing hydrogen and the other consisting of hydrogen and methyl, and n having an average value of 1 to 5) A storage-stable polyisocyanate-phosphate ester composition comprising a mixture of at least one acid phosphate ester and a pyrophosphate ester derived by removal of water of condensation from a mixture of two or more of the acid phosphate esters. 2. A composition according to claim 1, wherein the pyrophosphate is derived from a mixture of lauryl diacid phosphate and dilauryl monoacid phosphate. 3. A composition according to claim 1, wherein the pyrophosphate is derived from a mixture of oleyl diacid phosphate and dioleyl monoacid phosphate. 4. A composition according to claim 1, further comprising an emulsifier.