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    • 专利摘要:

    公开号:SU849990A3
    申请号:SU792818201
    申请日:1979-09-28
    公开日:1981-07-23
    发明作者:Мэклавлин Александр；Ханс Рихтер Райхард；Юджин Реймор Младший Хэролд
    申请人:Дзе Апджон Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF MANUFACTURING PLATES FROM PARTICLES OF ORGANIC MATERIALS The invention relates to the woodworking industry, and more specifically to the production of wood boards. There are known methods for producing plies from particles of an organic material, including treating particles of an organic material with a polyisocyanate. composition followed by hot pressing r. and r. A disadvantage of the known methods is the adhesion of the plates to the pressing surface. . The purpose of the invention is to reduce the adhesion of the plates to the pressing surface. I The goal is achieved by the fact that before pressing the particles of organic material are further processed by phosphate or a mixture of phosphato from the group of the acidic salt of phosphoric acid О RO-Р-ОН 1 (YAO) ОР-ОИ
    and their salts of ammonium, alkali and alkaline earth metals, or pyrophosphates, obtained from acidic salts of phosphoric 30
    where, in formulas, VIII R is selected from the group of shkil with the number of carbon-acid atoms 1 and II and their ammonium salts, alkali and alkaline-earth metals, or o-monoacyl derivatives of acid salts of phosphoric acid I c II O «RO-P-OCOR ( RO) xP-OCOR or carbamoyl phosphates R NHGP-OP-ORV and their ammonium, alkali and alkali-alkaline metals, or branched polyphosphates RO-P-0-P (OR) a 1. 0-P (OWa. 0-P (OY) g or polyphosphates (P0-p-o; i,
    yes from 8 to 35; alkenyl with the number of carbon atoms from 8 to 35,
    or P.- (0-CH-CH),
    A B
    containing as R alkyl with a carbon number of from 8 to 35, one of the Ive is hydrogen, and the other is selected from the group consisting of hydrogen and methyl;
    Cz - hydrocarbyl with the number of atoms
    carbon from 1 to 12; R is selected from the group of hydrocarbyl with the number of carbon atoms from 1 to 12 / hydrocarbyl, substituted by at least one
    ABOUT
    additional -NHCOO-P (OR),
    a group where R is as indicated above; .
    n is an integer
    moreover, the amount of phosphate or mixture of phosphates is from 0.1 to 20 parts by weight, per 100 parts by weight. polyisocyanate composition.
    . As a polyisocyanate composition, polymethylene polyphenyl polyisocyanate containing from 25 to 90 wt.% Methylenebis (phenyl isocyanate) and oligomeric polymethylene polyphenyl polyisocyanates with a functionality higher than 2. are used. - the rest.
    Polymethylene polyphenyl polyisocyanate contains from 35 to 65% by weight of methylene oxide (phenyl isocyanate).
    As a mixture of phosphates, a mixture of phosphoric acid lauric acidic salt and dilauric acidic acid phosphate salt is used.
    as a pyrophosphate, use is made of a product obtained by removing condensation water from a mixture of phosphoric acid lauric acid salt and dilauric secondary acidic phosphoric acid salt.
    As a mixture of phosphates, a mixture of oleic primary acidic salt of phosphoric acid and dirleic acid of the secondary acidic salt of PHOSPHORIC acid is used.
    as a pyrophosphate, use is made of a product obtained by removing condensation water from a mixture of oleic primary acid salt of phosphoric acid and dioleinic secondary acid salt of phosphoric acid.
    wood particles are used as particles of organic material.
    The treatment with the polyisocyanate composition and the treatment with phosphate or a mixture of phosphates are carried out simultaneously in the form of an aqueous emulsion.
    The aqueous emulsion of the polyisocyanate composition contains an emulsifier.
    The treatment with the polyisocyanate composition and the treatment with phosphate or a mixture of phosphates are carried out separately.
    The polyisocyanate composition and the phosphate or phosphate mixture are used in the form of an aqueous dispersion.
    Alkyl with the number of C atoms from 8 to 35 denotes a saturated monovalent aliphatic residue with a linear or branched chain, containing the specified number of carbon atoms in
    0 molecule. Examples of these groups are octyl, nonyl, decyl, undecyl ,. dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecens, eicosyl, geneicosyl ,.
    5 docosyl, tricosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontil, pentatriaconyl, etc., including their isomeric forms.
    Alkenyl with the number of C atoms from 8 to 35 denotes a monovalent linear or branched aliphatic residue containing at least one double bond and the indicated number of carbon atoms in the molecule. Examples of such groups include okte5 nil, nonenyl, as a lecturer, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadetsenil, Eiko-zenil, genzykozenil, dokozeNil, tri0 Kozeny, pentakozenil, triakon ± enyl, pentatriakontenil etc. ., and their isomeric forms.
    Pyrophosphates ... derived from the acid salts of phosphoric acid 1 and II
    and mixtures I and II, denotes the following. .
    Acid salts of phosphoric acid I and II are usually obtained as mixtures of the secondary acid salt of phosphoric acid II and the primary acid salt of phosphoric acid I, mixtures of which are obtained by reacting the corresponding alcohol ROH, where R is as described above, with the phosphoric anhydride according to the known method for the preparation of acid salts of phosphoric acid acid. .
    Thus, the resulting secondary and primary acidic salts of phosphoric acid are isolated, for example, by fractional crystallization of barium or Q-like salts. Separate acidic salts of phosphoric acid or mixtures thereof can be used according to the proposed method.
    Pyrophosphates II and IV are easily obtained from the corresponding acid salts of phosphate acid II and I by the interaction; the latter with a dehydrating agent, for example, carbon dioxide, aryl, or alkyl monoisocyanates and polyisocyanates, N, N-digidrocarbylcarbo-diimides, and the like. according to known methods.
    Separate acidic salts of phosphoric acid} and II can be converted into the corresponding pyrophosphates, or mixtures of 5 of these two types of acidic salts of phosphoric acid I and II can be converted into an appropriate mixture of pyrophosphates. As for the acidic salts of phosphoric acid of formula II, the corresponding phosphoric acid pyrophosphates are expressed by the formula III {YAO) 2.P-0-P (OO2, where R is indicated above ... What is the acid salts of phosphoric acid of formula I, TSE, the corresponding pyrophosphates are complex mixture, the average composition of which is expressed by formula IV where X is the number with an average value of 1 or higher, and R is indicated. Hydrocarbyl with the number of C atoms from 1 to 12 inclusively means one valence residue obtained by removing one hydrogen atom from the main hydrocarbon with the specified G atom content. Examples of such Groups are alkyl, for example, methyl, ethyl propyl, butyl, pentyl, hexyl, octyl decyl, dodecyl, etc., as well as their isomeric forms, alkenyl, for example vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, undecenyl, dodecenyl, : etc., as well as their isomeric forms; aralkyl, for example benzyl, phenylpropyl phenethyl naphthylmethyl, and the like; aryl, for example, phenyl, tolyl / xylyl, naphthyl, biphenyl, etc. J cycloalkyl, for example cyclobutyl, cyclopentyl cyclohexyl, cycloheptyl, cyclooctyl, etc., as well as their isomeric forms; cycloalkenyl, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctyl, and the like. and their isomeric forms. ... Alkaline means lithium, sodium, potassium, rubidium and cesium. Alkaline earth metal means calcium, strontium, magnesium and barium. The proposed method is carried out co. According to these well-known techniques, organic polyisocyanate is used as the binding resin or its component, except that a certain phosphate is used here in combination with the isocyanate composition used to treat the particles combined to form plywood. Thus, the slab is produced by combining particles of wood or another cellulosic or organic material that is suitable for pressing, using heat and pressure in the presence of a system of a binding substance containing a combination of organic polyisocyanate and phosphate which is hereinafter referred to as a phosphate all-phosphating agent. A portion of the organic material can be treated with a polyisocyanate and phosphate or a mixture of phosphates, as separate components, either simultaneously or after mixing. The polyisocyanate and phosphate can be used in its pure form, i.e., without diluents or solvents, one or both of them can be introduced in the form of aqueous dispersions or emulsions. Each organic polyisocyanate containing at least two isocyanate groups per molecule, for example, diphenylmethane diisocyanate j m- and p-phenylene diisocyanate, chlorphenylene diisocyanate, ct sbxylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, anhydroxy acid, can be a pisiocyanate composition; , 4,4-diisocyanate diphenyl ether and polymethyl polyphenyl polyisocyanates. The latter polyisocyanates are mixtures containing about 25 to 90% by weight of methylene bis (phenyl isocyanate), with the remainder of the mixture being prlmethylene polyphenyl polyisocyanates with a number of functional groups higher than 2.0. Such pris-isocyanates and methods for their preparation are known, and they are also available in various modified species. One of these species contains this polymethylene polyphenyl polyisocyanate, which is heated at 150 - until the viscosity (at) rises to 800 - 1500 cP. Another modified polymethylene polyphenyl polyisocyanate is such that it is treated with a small amount of epoxide to reduce its acidity. . . Polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the binding system of the substance according to the invention. Particularly preferred polymethylene polyphenyl polyisocyanates are those which contain from about 35 to 65% by weight of methylene bis (phenyl isocyanate). If an organic polyisocyanate is used as a system of a substance binder, in the form of an aqueous emulsion or dispersion according to the invention, the aqueous emulsion or dispersion is prepared using any techniques known for preparing aqueous emulsions or dispersions before using the composition as a binding agent. substances, and the polyisocyanate is dispersed in water in the presence of an emulsifier. The latter is any known emulsifier, including anionic and non-ionic agents.
    The non-ionic emulsifier emmers are polyoxyethylene and polyoxypropylene. containing from about 4 to about 18 C atoms; glycerides of saturated and unsaturated fatty acids, for example stearic, oleic and ricinolic acids, and the like; polyoxyalkylene fatty acid esters of, for example, stearic, lauric, oleic, and similar acids; amides of fatty acids, for example dialkanolam ides of fatty acids (stearic, lauric, oleic, etc.),
    The preparation of the emulsion or dispersion can be carried out before their use. In the composition of the binder, but preferably they are prepared within 3 hours before use. The aqueous polyisocyanate emulsion used according to the inventive method is formed, for example, by mixing the polyisocyanate, emulsifier and pressurized water using a known sprayer in which water jets and the polyisocyanate collide and mix in the mixing chamber of the sprayer under stormy conditions. The emulsion thus obtained is discharged in the form of an aerosol, which is applied to the cellulosic particles intended to form a mass of boards in this manner.
    As already described, the phosphate release agent can contact the particles as a separate component in its pure form, i.e. without diluents or as an aqueous solution or as an aqueous dispersion. If phosphate is used separately, i.e. without a polyisocyanate, in pure or diluted form, it is applied to the particles as an aerosol. But according to the proposed method, it is preferable to use a phosphate release agent together with polyeocyanate in one composition.
    When a polyisocyanate is used as a polymer binding agent without diluents, a phosphate release agent is introduced into the polyisocyanate by simple mixing. In the case of the use of a polyisocyanate as a binding srla in the form of an aqueous emulsion, the phosphate surfactant is added as a separate component during or after the formation of the emulsion, or, as a rule,. phosphate is pre-mixed with organic polyisocyanato before emulsification of the latter.
    Thus, the organic polyisocyanate and the phosphate release agent can be premixed and stored during a specific period before the formation of the emulsion.
    If an emulsifier is used in the preparation of an emulsion, it can also be used in a mixture of organic polyisocyanate and a phosphate release agent: to form a storage-stable composition that can be converted into an aqueous emulsion at any time for use as a working solution by simple mixing with water.
    When using a polyisocyanate
    5, as a binder in the form of an aqueous emulsion, the content of organic polyisocyanate in said aqueous emulsion is preferably in the range of 0.1-99% by weight, preferably in the range of 25-75% by weight.
    0
    If the phosphate release agent is administered as a separate component or in combination with a polyisocyanate, then the ratio of the phosphate release agent used is in the range of from about 0.1 to about 20 parts by weight. per 100 weight parts polyisocyanate, preferably in the range of 2 to 10 weight.h. per 100 weight parts polyisocyanate. The content of the emulsifier required for the preparation of the aqueous emulsion is not critical and varies depending on the emulsifier used, but is usually in the range of 0.1 - 20 wt.% In terms of
    5 per polyisocyan.
    The raw material for the manufacture of plates consists of particles of cellulose and similar material suitable for pressing and joining
    0 into slabs, for example, from wood particles obtained from wood waste. work, such as chips. Other particles of cellulosic material, such as ground paper, wood or wood, can also be used.
    5 vegetable fiber (corn stalks, straw, pressed sugar cane .n.), Or non-cellulosic material, such as polyurethane waste, polyisocyanate and the like
    0 polymer foams. Methods for the preparation of suitable particles are known and conventional. You can also use a mixture of cellulose particles. The slab is successfully obtained
    5 for example, from mixtures of wood particles, containing up to about 30%. bark.
    The moisture content of the particles is in the range of approximately from 0 to 24 wt.%. Particles obtained from wood waste, as a rule, contain. 10-20% moisture and can be used without prior
    5 drying. Plywood is obtained by treating particles of an organic material with a polyisocyanate composition and phosphate or a mixture of phosphates, separately or in combination. In a mixer or similar devices. After processing, a loose mat or felt is formed from the homogeneous mixture, preferably containing 4-18 wt. Then the mat is placed in a hot press and compacted until the particles solidify in the plate. The pressing time, temperature and pressure vary greatly depending on the thickness of the board obtained, the desired density of the board, the size of the particles used and other factors. For example, a pressure of about 300 to 700 US pounds per square inch (amf / inch) (/ "21-49.2 kg / cm) is used to make a medium density plate of 0.5 inch (1.27 cm) thick. and a temperature of about 325-375 ° F (VlGB 190,). The duration of the press is about 2-5 minutes. Since part of the moisture in the mat interacts with the polyisocyanate to form a polyurea, the amount of moisture in the mat is not so critical in the case of isocyanat based binders, as. in the case of others. This method is carried out intermittently, i.e., individual plates are pressed by treating a suitable number of particles with a combination of resin bonding, heating and pressing the treated material. Alternatively, the method is carried out in an intermittent manner. as a continuous mat to the heating and pressing zone, bounded by the upper and lower permanent metal braces that are used for hot pressing. The plate is easy to remove from the metal plates of the press, and it it does not tend to adhere to these plates. This is exactly the opposite of the previous experience in which only one polysocyanate is used as a binding resin. While each of these phosphate. Selection agents can be used either separately. Or According to the proposed method, preferably pyrophosphates III and IV or mixed pyrophosphates obtained from mixtures of acid salts of phosphoric acid I and M are used. The free hydroxy groups present in the pyrophosphates, or the free hydroxy groups present in the unconverted starting acid salts of phosphoric acid, are sufficiently inert at room temperature with respect to the used erythrocyanate, i.e. Phosphates can be stored in combination with the indicated polycyrene cyanate for a long time without any deterioration in quality. If the mixture of glyphosphate and polyisocyanate is emulsified and used by the proposed method, the steam produced during the formation of the plate leads to hydrolysis of the pyrphosphate with the reduction of the corresponding acidic salts of phosphoric acid, which facilitate the removal of the plate from the press. Examples of acidic salts of phosphoric acid of formula I, which can be used alone or in combination, c. other acid salts of phosphoric acid according to the proposed method can be mono-o-octyl, mono-nonyl, mono-o-decyl, mono-o-undecyl, mono-o-dodecyl, mono-o-tridecyl, mr-o tetradecyl, mono-o-pentadecyl, mono-o-hexadecyl, mono-o-heptadecyl, mono-o-octadecyl, mono-o-nonadecyl mono-o-eicoside, mono-o-geneicosyl, mono-o-docosyl mono o-tricosyl, mono-0-pentacosyl, mono-o-hexacosyl, mono-o-heptacosyl, mono-o-octacosyl,. mono-o-nonacoside, mono-o-triacontil ,. mono-o-pentatriaconethyl, mono-o-dode-tsenil, mono-o-tridecenyl, mono-o-tetradecenyl, mono-o-pentadacenyl, monog-o-hexadecenyl, mono-o-heptadecenyl l, mono-o-octadecenyl , mono-o-nonadecenyl, mono-o-eicocenyl mono-o-heicoicenyl, mono-o-doporzenyl, mono-o-crosenoyl, mono-o-pentacosenyl, mono-otriacontenyl and. mono-p-pent. a triacozenyl primary acidic salts of phosphoric acid and primary acidic salts of phosphoric acid, where the esterifying residue is obtained from lauric and similar monohydric alcohols bound (blocked) using about 1-5 mol of ethylene oxide. Examples of acidic salts of phosphoric acid of formula II, used or in combination with other acidic salts of phosphoric acid according to the proposed method, can be o, o-di (rktil), o, o-di (nrnyl), 0,0-di (decyl ), 0,0-di (undecyl), o, o-di (dodecyl), o, o-di (tridecyl) 1, o, p -... di (tetradecyl), o, o-di (pentadecyl) , o, o-di (hexadecyl), o, o-di (heptadecyl), (octadecyl), P, R-DI (nonadecyl), o, o-di (eikrzil), p, r-di (geneacryl) , o, o-di (docrzil), ogr-di (tricosyl), o, o-diC (pentacosyl), o, di , o, r-di (nonakozil) / o, o-di (triacontil), o, r- di (pentatyryne), b, o-di (dodetsen.il), o, rd di tridetseiil), o, o -: - di1tetradecenyl) o, R-di (pentadecenyl), o, heptadecenyl), o, o- di octadecenyl), P, o-di (nonadecenyl), o, o-di (eik6zenil) o, o-di (geneicocenyl), o, o-di (docosenyl), - o, Pr-di (tricrsenyl) V , P-da (pentacryl), o, o-di {triacontenyl) and
    o, o-di (pentatriacoeenyl) secondary acidic phosphoric acid esters, and diaterified secondary acidic salts of phosphoric acid, where the esterifying residue is obtained from lauric and similar monohydric alcohols blocked using about 1-5 mol of ethylene oxide.
    Examples pirofos Fatov which are used alone or in combination with other pyrophosphates, according to the proposed method can be tetrabktil, tetranonil, tetradecyl., TetraUNDetsil, tetradodetsil, tatra (tridecyl) tetra (tetradecyl) tvtra (pentadecyl) tetra {hexadecyl) tetra (heptadecyl), tetra (octadecyl), tetra. (noia 1 cil), tetra (eicosyl) / tetra-. (genonecosyl), tetra (docosyl), tetra (triCodl), tetra (pentacosyl), (dodedenyl), tetra (tridelenil), tetra (tetradedenyl), tetra (pentadecenyl), tetra (hexadedenyl), tetry (hepts1decenyl}, tetra (octadecenyl), tetra (nonadecenyl), tetra (eicosyl)), tetra (hecadecenyl), tetra (docosenyl) tetra (tricozenyl), tetra (pentacosenyl), tetra (triacontenyl) and tetra (penta triacosenyl) pyrophosphates; di (octyl), di (nonyl), di (decyl), di (undecyl), di Dod cycl), di (tridecyl), di (tetradecyl), di (pentadecyl), di (hexadecium), di (hexptadecyl), di (octadecyl, di (nonadecyl), di (eicosyl), di (genzyCosyl), di ( docosyl), dy (tricosyl), di (pentacosyl), di (hexacosyl), di (heptacosyl),. di (octacosyl), di (nonacosyl), di trijacontil), di (pentatriacontil), di (dodecenyl), di ( tridecenyl), di (tetradecenyl), di (pentadecenyl), di (hexadecenyl), di (heptadecenyl), di (octadecenyl), di (nonadecenyl), d (eicosenyl), di (geneoicosenyl), di (docosenyl), di ( tricozenyl), di (pentacosenyl), di (triacontenyl) and di (penta triacosenyl) pyrophosphates,
    o-Monoacyl-derivatives of acid salts of phosphoric acid I and II are obtained by known methods. For example, the corresponding acidic salts of phosphoric acid G or f (in the form of their salts of silver or other metals are reacted with a suitable acyl halide K COH 1, where Hat is chlorine or bromine, and R is above.
    Examples of o-monoacyl derivatives of acidic salts of phosphoric acid I and I are o-acetyl, o-propionyl, o-octanoyl, o-decanoyl, o-dodecanoyl, o-benzoyl, o-toluene, p-phenacetyl derivatives of various acid salts phosphoric acid I and I.
    Carbamoyl phosphates, which are used according to the proposed method, are obtained by the interaction of suitable
    acid salts of phosphoric acid I or II with a suitable hydrocarbyl mono or polyisocyanate. Examples of such carbamoyl phosphates are methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, gbxylcarbamoyl, decyl of rba-. moyl, dodecylcarbamol, allylcarbamoyl; hexenylcarbamyl, octenylcarbamoyl, decenylcarbamoyl, dodecenylcarbamoyl, phenylcarbamoyl, tolylcarbamoyl, diphenylylcarbamoyl,
    O benzylcarbamoyl, phenylpropylcarbamoyl and the like hydrocarbamoyl derivatives of secondary acid salts of phosphoric acid, stabilized in the form of their ammonium or alkali metal salts.
    Carbamoyl phosphates i may contain free OH groups, which are formed by the incomplete conversion of the acidic salts of phosphoric acid in reaction with a suitable hydrocarbyl isocyanate due to the poor reactivity of these OH groups with isocyanate.
    The polyphosphates used according to the inventive method are easily obtained by reacting a suitable trialkyl phosphate (RO) .jPO, where R is indicated above, with phosphorus pentoxide. Typically, polyphosphates are. complex mixtures that include cyclic compounds () containing a ring with 6 elements of alternative phosphorus and oxygen atoms.
    Polyphosphates corresponding to the formula V and VH are easily obtained by reacting a suitable di- or triskylphosphate with an appropriate O / f halophosphate.
    (R0) 2. P-Na1, where Na is chlorine or bromine, using, for example, a known method that involves the isolation of alkyl halide.
    1. Preparation of pyrophosphates from lauri-. new acid salt of phosphoric acid.
    A mixture containing 70 g of lauric acid salt of phosphoric acid (a mixture of p, o-; dilauric secondary acid salt of phosphoric acid and o-lauric primary acid salt of phosphoric acid) and 60 g of phenyl isocyanate are loaded into a dry flask equipped with a stirrer, condenser and drying tube. The flask is loaded into an oil bath, preheated before. The contents of the flask are enticed, and the temperature of the oil bath is slowly raised to. Carbon dioxide is released for approximately 1 hour,,
    After the evolution of carbon dioxide has ended, the reaction mixture is cooled to room temperature i is diluted. 100 ml of chloroform. The resulting mixture was filtered and the solid thus collected (24.8 g m, M-diphenylurea) was washed with chloroform.
    The combined filtrates and washes are concentrated on a rotary evaporator at bath temperature. After evaporation of most of the solvent, N, N, N -triphenylburet crystals are isolated, and evaporation is interrupted to filter out the solid (6.6 g). The filtrate is evaporated to dryness and treated with reduced pressure to remove excess phenyl isocyanate. The residue (70 g) is the desired pyrophosphate as a colorless, slightly yellow liquid.
    The infrared spectrum of the product (in CHCr.) ® shows no bandwidth typical of P-OH-CI, but shows a sharp band at 940 typical of P-O-P-bonds.
    2. Preparation of pyrophosphate from the phosphoric acid lauric acid salt.
    A total amount of 70 g of phosphoric acid lauric acid salt (starting material is the same as in Preparation 1) is loaded into a flask equipped with a mixer, a reflux condenser, and a gas inlet and heated under nitrogen at 65-75 ° C until melted. The molten substance is stirred, and a stream of phosgene is slowly let in for 2.5 hours. The temperature during the addition is kept within the specified limits. The gas evolution from the reaction mixture proceeds strongly only during the first hour of the addition of phosgene, then it slowly subsides and by the end of the addition of phosgene is very slow. After the addition is complete, the mixture is purged with nitrogen for 15 hours, and the temperature is maintained in the specified range. After
    this pressure in the reaction flask is slowly reduced to about
    1.6 N No. 4 Hg to remove hydrochloride and carbon dioxide. In this way, the viscous residue solidifies completely into the shadow of the night. Get 66 g of pyrophosphate in the form
    solid, which gradually melts at.
    3. Preparation of pyrophosphate from oleic acid phosphoric acid.
    A mixture containing 200 g of oleic acid salt of phosphoric acid (paluchein from a mixture of o, o-dioleic acid, the phosphoric acid salt and o-rtoHolenic acid salt of phosphoric acid) is reacted with 160 g of feyly isocyanate at 85-90 C for 5, 5 h using the method that was obtained in preparation 1.
    N, H-Difensh1 Urea (68 g) was removed by filtration after diluting the reaction mixture with 200 ml of chloroform. The filtrate is concentrated on a rotary evaporator and the excess of the non-regenerated phenyl isocyanate is removed by distillation under reduced pressure. The N, s, H-Triphenylbioure crystallizes out of the oil residue by exposure at room temperature. The yield after removal of the crystals by filtration is 196 g of the liquid product, the infrared spectrum of which shows a band at 940 cm typical of the P-O-f band, but does not show any bands typical of the P-OH bands.
    4. Preparation of pyrophosphate from the phosphoric acid lauric acid salt. A solution consisting of E0.4 wt.h. lauric acid salt of phosphoric acid (the same as in Preparation 1) at 21 weight parts. toluene, loaded into a dry reactor, pre-cleaned with nitrogen. The solution is heated to stirring, and 7.6 parts by weight is added. polymethylene polyphenyl polyphosocyanate (equivalent weight 133, functional capacity 2.8), containing approximately 50% methylene bis (phenyl isocyanate) per 5 parts by weight toluene.
    I mix the mixture;
    and a stream of phosgene is introduced (about 0.1 weight.h / min) and the temperature is slowly raised to (Us, is maintained at this level, and phosgene is constantly injected until
    introduced 20 weight.h. last one. The total phosgene addition time is 5 hours and 50 minutes. The reaction mixture is heated at the same temperature for another 40 min after the completion of the addition of phosgene and
    before heating "(up to 90-95 ° C and purifying nitrogen cm for 2 h to remove excess phosgene. Then reduce the pressure in the reactor before starting treatment of toluene with reverse
    refrigerating and purging with nitrogen for 2 hours. Toluene is then removed by distillation at. reduced pressure, its last traces in the ugisum. . The residue is cooled to room temperature, treated with diatomaceous
    ground and filtered after stirring for 30 minutes. Thus, 23.7 parts by weight are obtained. mixtures of lauryl pyrophosphate and popimethylene polyphenyl poly-iso-anate, which contains
    6.08 wt.% Phosphorus.
    5. Preparation (further) of pyrophosphate from phosphorus lauric acid salt. fororic acid. .
     By applying the method described in Preparation 4, but replacing the poly No. thylene-polk-phenyl-polio-eo-Hio used there with an equivalent amount (6.8 sec., P.) Of phenylisocyanate, one more batch of pyrillates are obtained.
    Example 1. Wood chips (Turner's BARS) are placed into a mixing drum and rotate it; spray it with a water emulsion of polyisocyanate, water, phosphate
    and emulsifier. Emulsion get eme-;
    shivan their components using Türreks mixer. The resulting emulsion is sprayed with wood spray particles, cleaning them for 45-120 seconds to obtain homogeneity. Coated particles are formed into a felt mat on a 12x12 inch (1 inch 2.54 cm) cold rolled steel plate. With a molding frame.
    After removing the molding frame, steel bars with a thickness corresponding to the desired thickness (1/4 inch) of the final plywood; placed along the two opposite ends of the specified steel plate, and another 12x12 inch W929 cm steel plate laid on the side of the mat. Then the entire xylplect is placed on the bottom plate of the Dake press with a capacity of 100 thousand amf. Both press plates are preheated to the temperature specified in
    Table 1. Then it is treated with pressure for the time specified in Table 1, counting from the point when the pressure on the mat reaches 500 A / inch (L 35.1 kg / cm. After the pressing time specified in Table 1, the pressure is released and plywood is removed from the mold.
    In all cases, removing the plate from the mold is easy. The tendency of the slab to adhere to the plates with which it was in contact was absent, which was not observed under identical conditions, but without the use of the lauric acid phosphoric acid salt in the emulsion used in preparing the slab .:
    Thus obtained various samples of the plate are subjected to a series of tests that show the Excellent structural properties of the strength of the 0 plates (Table 1) ..
    , l and 1
    Polymethylene polyphenyl polyisocyanate
    p and m echenie. with an equivalent weight of 133 and a functional capacity of 2.8, containing approximately 50% methylenebene (vinyl isocyanate).
     A mixture of lauric primary acid salt of phosphoric acid and dilurinic secondary acid salt of β-phosphoric acid.
    5 Ethoxylated propoxylated butanol.
     In terms of dry weight of wood particles.
    Example 2. The plate is obtained using the method described in example 1, using the components and their quantities (by weight), in the aeano table. 2. pressing time
    for samples E and F, the mat is held at the pressure (500 am.C./inch) after
    .in the mat temperature reached, by definition, contained inside
    Plate temperature, ° С
    Pressing time, min
    Density, kg / m
    Break modulus, kg / cm
    Longitudinal moduleNote.
    frozen The slab is prepared using the method, as well as peareH-iW combs and their amounts specified in Example 1, except that the press plates are preheated to 400 F (204,) and pressed during the time indicated in Table 3. 65
    thermoelement 13 (fF (54.44 ° С). Sample G — control, pressed as described in Example 1. The physical properties of each plywood produced, shown in Table 2, show
    Excellent structural strength of various samples. All samples are easily removed from the mold and show no signs of sticking to the steel plates.
    used to obtain them.
    to
    table 2
    179.44 179.44 179.44
    2
    2
    672.77 672.77
    360.63 314.77 373.99
     Schuch you, to ak ogshsano in obtaining 1..
    jt- In terms of dry weight
    wood particles.
    The physical properties of the samples thus obtained are listed in Table 3, whence it is clear that all the samples have excellent structural strength and none of them adheres to the Plates for Pressing during the removal of the molds.
    19 Extrusion pressure, min. Density, kg / m 640.74 Breaking modulus, kg / cm 194.02 Longitudinal elastic modulus, kg / cmts 10; Dry interconnect, kg / cm Moist internal communication, kg / cm 1, 61 1.68
    PRI me R 4, Ylitu is obtained using the method described in. Example 1, but varying the nature of polyeocyatan, and using instead. laurey of the 4-acid salt of phosphoric acid pyrophosphate, obtained from the oleic acid salt of phosphoric acid, as described in Preparation 3.
    Components, their relationship and the physical properties of the samples
    84999020
    Table 3 1.0, 74 28.66 6.60
    listed in table 4. The thickness of the plywood specimens in all cases is 3/8 inches (using stainless steel rods with a suitable thickness). As can be seen from the table. 4, none of the samples have a tendency to adhere to the plates for the press or during demoulding, and all the samples have excellent structural
    strength. :
    t a l l c a -4 1.5 2.0 2.5 3.0 640.74 656.75 640.74 640.74 640.74 656.75 640.74 640.7-5 258.15 221 , 44 225.66 236.9 33.18 31 30.79 31.91 7.17 6.18 8.52 8.52 1.61 1.73 1.68
    Indicators Density, kg / m yopul, KF / CH Modulus of longitudinal elasticity, kg / cm X and 10 Dry internal communication, kg / cm Moist internal communication, kg / cm P r and the sword and e,. Example 5. According to the proposed use of the composition, which is not an emulsifier and is used in a cat in pure form of an aqueous emulsion. Samples receive items and their amounts are listed in Table 5 of the method described
    Total water
    weight..
    Prodzhekve table. four
    n L sh t and
    17.4 i7.4 17.4 17.4 656.75 640.74 672.77 656.75 656.75672.77 640.74656.75640.74 283.30 358.53 384.59 310.02 378, 21438.67 327.58433.04.0410.08 32.68 38.10 38.94 30.36 X ", bZ37.01 40.9842.3234.86 5.34 8.45 9.56 5.83 5.336.60 12,8111,593,30 1,26 1,89 2.24 1.47 1.471,54 2.532,311Л Liquid pre-polymer methylenebis (phenyl neocyan1 a) with an equivalent weight of 181 .. 3. Polymethylene polyphenyl poly (II) containing about 65% methlen bis (phenyl eocyanate) with an equivalent weight 133.. Polymethylene polyphenyl polyisocyanates containing approximately 45% methylenebis (feklyeocyanate) with; equivalent weight of 133.5. Liquid Methyls equivalent weight is 140. Poly {"ethylene polyphenyl polyesocyanate containing approximately 70% methylenebis (phenyl isocyanate} with an equivalent weight of 133. The same as for example .1, That is the same as in example. On the basis of the arterially dry wood. Litas receive the same quantity from the tree.) the way with and The external rum contains polyisocyanate ide, i.e. not in. from various stones (by weight), using Example 1, for JLEZLL-.LlL.LL L..nZlL31jL, the first particles are given the indicated amount of water, 3S, and then with a mixture of polyisocyanate and phosphate release agent. The physical properties defined for each plywood produced show excellent strength of various samples (Table 5). All samples are easily removed from the form to have no sign of sticking to the steel plates, Use to get them. T-a b litsa 5 h aa and. In terms of dry
    Example b. According to the proposed method, three kinds of wafer chip chips having dimensions of 2x2x1 / 32 inches are obtained, which are produced without the use of water from the outside or an emulsifier, and the polyisocyanate and the phosphate release agent are used in pure form.
    Samples of wafer chips obtained from various components and their amounts (by weight) using the method described in example 1, except that the chips are sprayed with a mixture of polyisocyanate. and phos-Continued table. five
    fathom is not in the form of an aqueous emulsion, and that aluminum molds are used. All samples are easily removed from the mold and show no sign of adhesion to the aluminum plates used to make them. The excellent properties of the product obtained are determined by a high modulus of rupture indicated in Table. b, it is distinguished favorably from those obtained from the same type of wafer chips using a binder from phenol-formaldehyde resin. .
    t and blitz 6. weight of wood particles.
    25
    Note. In terms of dry weight, wood: V Polymethylene polyphenyl polyisocyanate
    Etc. and measure 7. Plate samples are obtained using polyisoyate binder compounds in combination with various phosphates. ,
    Samples obtained from the components and their quantities (by weight) listed in table. 7, using the method.
    Klhnlya sour salt of phosphoric acid
    Laur noaa sour salt ff
    acid. .
    Alkyl sour salt of phosphoric acid
    The same Ms.
    also. . Laurine pyrophosphate
    Popiocyanatos weight.
    Total amount of water, wt.%
    84999026
    Continued table. waffles Q equivalent weight of 139 and a functional ability of 3.0 V hococ at 25 ° C 700 SP. Contains approximately 35% methylene bis (phenyl isocyanate).
    described in example 1, except that no emulsifier and shavings are used, first sprayed with water and then isocyanate, mixed. with phosphate. All Samples are easily removed from the mold and do not show adhesion to the steel plate,
    used for their pressing.
    T ai li aa 7;
    12.96
    17.28
    3.75
    16.4
    bb
    b 12
    6 12
    b
    D 2
    12 fl (.. PRMMMZhSH, E ......., -. 1 ..: tameueovy, mn 444 1.27 1.27 1.27 Toptsit of the board, cm O 0 I m H W and W ..., .
    Example 8. Plate samples are obtained: using phosphate, aaac x. agents according to the method of example 7, but at the level of concentrations indicated in.
    3) Samples are easily removed from the mold without significant sticking to the preform. Using
    Continued table. 7 P 1 I FF
    权利要求:
    Claims (2)
    [1]
    at higher concentrations of phosphate, the samples obtained during excavation are expelled from the mold, while samples obtained with the use of lower concentrations of phosphate 00, QQ, and VV should be removed by special techniques, for example, by tapping. All samples are 1.27 cm thick. It was obtained on lauric alcohol, in principle, a weimode of ice about 3 mol, ethylene oxide .. obtained from a toxilated lauric acid. . Derived from ethoxylated aliphatic alcohol with a branched middle chain. Derived from n-octyl .. Derived from ethoxylated lauric alcohol. Received according to Preparation 5 .. based on dry wood waffles ,. n t and I ---....-..... ".," ", .-" ", 66 IN | M" 4444 "1.27 1.27 1.27 1.27 1.27 Claim 1. Method for manufacturing plates of particles of organic material, including processing particles of organic material with a polyisocyanate composition followed by hot pressing, characterized in that, in order to reduce sticking to the pressing surface, before hot pressing, particles of organic material are additionally treated with phosphate or a mixture of phosphates from the group of acid salts of phosphoric acid OG (RO) 2. RO-P-OH and their salts of ammonium, alkali and alkali earth metals, or pyrophosphates obtained from acidic salts of phosphoric acids I and II and their ammonium salts, alkali metals. And alkaline-earth metals, or o-monoacyl derivatives of acidic salts of phosphoric acid RO-j-OCOR (RO) 2-P-OCOR or carbs1moyl phosphates of R, NHCO-0-P- (OR) V and their ammonium, alkali metal and alkaline-earth metal salts, or branched polyphosphates О О RO-PO- PCORli CROij. Р-Р-Р-о-рСойи О-РСОЯ h. 1 O-p {OR) u NU or polyphosphates. VIII (ROP-OH, where in formulas I-VIII, R is chosen in the group of alkyl with the number of carbon atoms: yes from 8 to 35; alkenyl with the number of carbon atoms from 8 to 35; or R-lo-Ch-CM) i containing R is alkyl with 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; ft | - hydrocarbyl with the number of atoms, carbon from 1 to 12; R is selected from the group of hydrocarbyl with the number of carbon atoms from 1 to 12; hydrocarbyl carbon 1 by at least one additional group. MNSOO-RSOUg where R is as above; n - integer number,. . moreover, the amount of phosphate or mixture of phosphates is from 0.1 to 20 parts by weight. per 100 weight parts polyisocyanate composition. 2. Method POP.1, characterized in that polymethylene polyphenyl polyisocyanate containing from 25 to 90% by weight of methylene bis (phenyl isocanate) i is used as the polyisocyanate composition. and oligomeric polymethylene polyphenyl polyisocyanates with a functional ability of greater than 2 else. 3. Method qon.2, which is related to the fact that polymethylene polyphenyl polyisocyanate contains from 35 to 65 wt.% Methylene bis (phenyl isocyanate). 4. Method of method 1, that is, with the fact that as a mixture of phosphates use a mixture of lauric primary acidic salt of phosphoric acid and dilauric secondary acidic salt of phosphoric acid. 5. Method POP1, characterized in that the product obtained by removing condensation water from the pyro-osphate is used. a mixture of lauric acid salt of phosphoric acid and dilauric secondary acid salt of phosphoric acid. 6. Method POP1, characterized in that a mixture of oleic acidic phosphoric acid salt and a dioleic acidic acidic phosphoric acid salt is used as a mixture of phosphates. 7. The method according to Claim 1, which is based on the fact that the product obtained by removing condensation water from a mixture of oleic acidic phosphoric acid salt and dioleic acidic phosphoric acid salt is used as pyrophosphate. . 8 i The method according to p. 1, characterized in that wood chips are used as particles of organic material. 9. The method according to claim 1, which is also characterized by the fact that the treatment with the polyisocyanatum composition and the treatment with phosphate or a mixture of phosphates are carried out simultaneously in the form of an aqueous emulsion. 10. The method according to claim 9, from l and h and yushchi and the fact that the aqueous emulsion of a polyisocyanate composition contains an emulsifier. l ii. The method according to Claim 1, about tl and h. Aa ya and so that the treatment with the poly-eianed composition and the treatment with phosphate or a mixture of phosphates are carried out separately. , 12. The method according to claim 11, whether it is a polyisocyanL-35 composition And phosphate or a mixture of phosphates is used in the form of an aqueous dispersion. Sources of information, accepted attention in the examination of 84999036 1. US Patent No. 3930110, cl.428-424 1975.
    [2]
    2. US Patent No. 3428592, Ky.260-29.2, 1969.
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    同族专利:
    公开号 | 公开日
    TR21115A|1983-09-30|
    JPS57115416A|1982-07-17|
    JPS5549245A|1980-04-09|
    BE879080A|1980-03-28|
    JPS5722012B2|1982-05-11|
    JPH0118068B2|1989-04-03|
    ZA794752B|1980-08-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2533834C2|2009-06-16|2014-11-20|ХАНТСМЭН ИНТЕРНЭШНЛ ЭлЭлСи|Reaction system and method of obtaining lignocellulose product|JPS6315129B2|1980-07-15|1988-04-04|Nippon Petrochemicals Co Ltd|US4388138A|1980-08-11|1983-06-14|Imperial Chemical Industries Limited|Preparing particleboard utilizing a vegetable wax or derivative and polyisocyanate as a release agent on metal press parts|
    US4352696A|1981-03-30|1982-10-05|The Upjohn Company|Process and composition|
    JPS647842B2|1981-10-14|1989-02-10|Mitsui Toatsu Chemicals|
    JPS5863435A|1981-10-14|1983-04-15|Mitsui Toatsu Chem Inc|Manufacture of particle board|
    JPH072210B2|1985-10-21|1995-01-18|株式会社大川原製作所|Granulation control method for hygroscopic powder|
    JP2015511652A|2012-03-15|2015-04-20|ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ|Modified isocyanate composition and method for producing the modified isocyanate composition|
    WO2018070539A1|2016-10-14|2018-04-19|旭化成株式会社|Isocyanate composition and production method for isocyanate polymer|
    US11118001B2|2016-10-14|2021-09-14|Asahi Kasei Kabushiki Kaisha|Isocyanate composition, method for producing isocyanate composition, and method for producing isocyanate polymer|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US94720978A| true| 1978-09-29|1978-09-29|
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