CN1131958A - Self-releasing binder system for composite products - Google Patents
Self-releasing binder system for composite products Download PDFInfo
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- CN1131958A CN1131958A CN95190739A CN95190739A CN1131958A CN 1131958 A CN1131958 A CN 1131958A CN 95190739 A CN95190739 A CN 95190739A CN 95190739 A CN95190739 A CN 95190739A CN 1131958 A CN1131958 A CN 1131958A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2125/00—Compositions for processes using internal mould release agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A composition is disclosed for a self-releasing binder composition useful for preparing a composite article prepared by contacting at least (1) a polyisocyanate compound; (2) a compound of one of formulae (I), (II), (III); and (3) a polyether containing compound. The components which make up the self-releasing binder composition can be applied to substrate particles, for example, cellulosic, polymeric, inorganic, or similar particles, or combinations thereof. This composition can provide excellent adhesion of the particles while at the same time offering easy and dependable releasability from a wide variety of metal surfaces.
Description
The present invention relates to be used to prepare the tackiness agent of composite prod.More specifically, the present invention relates to the composite prod made by levigated material (preferred lignocellulose).
Adopt organic multiple isocyanate as tackiness agent from levigated timber, comprise that it is well-known that wood chip, wood chip, strand or fiber prepare plate-like product.The reference that this class is used comprises for example United States Patent (USP) 3,428,592; 3,440,180; 3,557,263; 3,636,199; 3,870,665; 3,919,017 and 3,930,110.In a typical method; adopt the agitator of drum device, mixer or other form, adhesive resin (the optional form that is solution or aqeous suspension or emulsion) is added to or mixes with the particle of cellulose materials or the base material that can form composite product of other type.Then, the mixture of this particle and tackiness agent is configured as slab and heat and pressurize with heating platen.This method can take partial or continuous operating method to carry out.
Be bonded on the heating platen for fear of composition board or other product, so far, in forming process, must between the surface of plate and heating platen, insert the thin slice of an impermeable isocyanic ester, or before each molded operation, apply the surface of heating platen with suitable releasing agent.Another kind method is the surface with the coated materials particle of non-caked heating platen itself.Above-mentioned any scheme is a trouble under the situation of operate continuously particularly, in addition, also is a defective for the very satisfied method of very attractive composite product on the preparation structural strength properties.
As United States Patent (USP) 4,257, described in 995, for the purpose that reaches the demoulding has advised phosphate ester acid is added in the isocyanate compound as " inner pattern releasing agent applicable ".Though as if above-mentioned system can be from the demoulding on the aluminium pressuring template,, the performance of the demoulding extreme difference that but seems from the steel.Other demoulding system with similar shortcoming comprises as United States Patent (USP) 4,933,232 disclosed use polymerized fatty acids and/or the multi-carboxy compound that contains the polymerized fatty acid groups that combines with isocyanic ester or as United States Patent (USP) 4,528, the 153 disclosed systems that sulfonic acid and isocyanic ester are combined.Therefore, be sought after developing a kind of adhesive composition, this system can not only be given and be treated that the agglutinating particle provides good adhesive property, also demonstrate simultaneously can be well the performance of the demoulding on the various metal crimp templates.
Therefore, the present invention is a kind of binder composition from the demoulding, its method for making is to be enough to form under the reaction conditions of binder composition contact (1) polyisocyanate compound at least, and (2) content is per 100 parts of (weight) polyisocyanate compound about 1 compounds to one of about 20 parts following formula:
In the formula, X is oxygen or sulphur, and R is alkyl or contains ether or the alkyl of ester group, and can be ring-type, and R ' is R, H or acyl group, formamyl, phosphoryl or alkylsulfonyl; And (3) contain the compound of polyethers, and supplementary condition are as follows: the compound that (i) wherein contains polyethers does not contain active hydrogen, and the content that contains the compound of polyethers is that per 100 parts of (weight) polyisocyanates contain about 1 to about 2000 parts; The compound that (ii) wherein contains polyethers contains at least one active hydrogen, and the content of compound that contains polyethers is for the compound of formula I, and OH: the NCO equivalence ratio was less than about 0.77: 1.00; For the compound of formula II, OH: the NCO equivalence ratio was less than about 0.25: 1.00; And for the compound of formula III, OH: the NCO equivalence ratio was less than about 0.10: 1.00.
Another embodiment of the invention is a kind of method for preparing composite product, be included in following (1) polyisocyanate compound at least that contacts of reaction conditions that is enough to form composite product, (2) content is per 100 parts of (weight) polyisocyanates about 1 compounds to one of about 20 parts following formula:
In the formula, X is oxygen or sulphur, and R is alkyl or contains ether or the alkyl of ester group, and can be ring-type, and R ' is R, H or acyl group, formamyl, phosphoryl or alkylsulfonyl; (3) contain the compound of polyethers, supplementary condition are as follows: the compound that (i) wherein contains polyethers does not contain active hydrogen, and the content that contains the compound of polyethers is that per 100 parts of (weight) polyisocyanates contain about 1 to about 2000 parts; The compound that (ii) wherein contains polyethers contains at least one active hydrogen, and the content of compound that contains polyethers is for the compound of formula I, and OH: the NCO equivalence ratio was less than about 0.77: 1.00; For the compound of formula (II), OH: the NCO equivalence ratio was less than about 0.25: 1.00; And for the compound of formula (III), OH: the NCO equivalence ratio was less than about 0.10: 1.00; And (4) substrate particles.
The binder composition from the demoulding that comprises said components (1), (2) and (3) can be the fabulous condition of bonding creation and can make the substrate particles that is compacted into composite product keep bond strength in it.That these above-mentioned substrate particles can comprise is inorganic, polymeric or other organic particle or particularly cellulosic particle for example wood chip, wood chip, various particle, strand or fiber or other levigated base material.In addition, this adhesive composition can make final composite product be easy to the demoulding on the metal die of aluminium, steel or other type or the pressuring template.Therefore, it is to be applicable to for example to pursue the Perfected process that is easy to the industrial sheet material tinuous production of the demoulding fast.
In enforcement of the present invention, as described in this manual, regulation comprises that at least the component that the adhesive composition from the demoulding of component (1), (2) and (3) at first requires is polyisocyanates (1).Term used herein " polyisocyanates " refers to any, and to have average functionality be 2 or bigger, and promptly per molecule on average has the isocyanic ester of two isocyanate groups at least.Therefore, vulcabond is included in wherein.As the illustration of organic multiple isocyanate be '-diphenylmethane diisocyanate, and PPDI, chlorobenzene vulcabond, α, α-xylylene diisocyanate, 2,4-and 2,6-tolylene diisocyanate and commercially available these two kinds of mixture of isomers, triphenylmethane triisocyanate, 4,4 '-two isocyanide acyl phenyl ether and poly methylene poly phenyl poly isocyanates.A kind of polyisocyanates in back is to contain about 25% mixture to about 90% (weight) two (phenyl isocyanate) methane, and the rest part of this mixture is that functionality is equal to or greater than about 2.0 poly methylene poly phenyl poly isocyanate.This class polyisocyanates and preparation method thereof is being well-known in the art; Can consult for example United States Patent (USP) 2,683,730; 2,950,263; 3,012,008 and 3,097,191.These polyisocyanates also can various modifications form obtain.One of these forms comprise poly methylene poly phenyl poly isocyanate.
Poly methylene poly phenyl poly isocyanate is the polyisocyanates that is preferred for adhesive composition of the present invention.Particularly preferably be and contain about 35% poly methylene poly phenyl poly isocyanate to about 65% (weight) two (phenyl isocyanate) methane.
In one embodiment of the invention, the organic multiple isocyanate that is used for adhesive composition can be the form of water miscible liquid or dispersion liquid.In this case, before being used for tackiness agent, said composition can adopt any relevant technologies known in the art to prepare water miscible liquid or dispersion liquid.Illustrate, polyisocyanates can be dispersed in the water that contains emulsifying agent.Emulsifying agent can be that any is known in the art, comprise negatively charged ion and non-ionic reagent.Illustration as nonionic emulsifying agent is polyoxyethylene and polyoxypropylene alcohol and two or more oxyethane, propylene oxide, butylene oxide ring and cinnamic segmented copolymer; Alkoxylated alkylphenol is poly-(vinyloxy group) ethanol of Nonylphenoxy for example; The alkoxylate fatty alcohol for example contains the ethoxylation and the propoxylation fatty alcohol of about 4 to 18 carbon atoms; Saturated and unsaturated fatty acids is the glyceryl ester of stearic acid, oleic acid and ricinolic acid for example; Lipid acid is stearic acid, lauric acid and oleic polyoxyalkylene ester for example; And fatty acid amide for example comprises two alkanolamides as stearic acid, lauric acid and oleic lipid acid.About the detailed description of this class material referring to Encyclopedia of Chemical Technology, SecondEdition, Vol.19, pp.531-554, Interscience Publishers, NewYork.
The preparation of emulsion or dispersion liquid can be carried out in the arbitrary time before itself and binder composition use.Any ordinary method for preparing water miscible liquid in the art all can be used to prepare the water miscible liquid of polyisocyanates, for example just is prepared applying polyisocyanates employing on-line mixing device before the substrate particles of selecting.
Except polyisocyanates, the present invention also uses the organic acid compound (2) that is selected from following formula: compound
In the formula, X is oxygen or sulphur, and R is alkyl or contains ether or ester group and can be the cyclic alkyl that R ' is R, H or acyl group, formamyl, phosphoryl or alkylsulfonyl; For reference for simplicity, in this article these materials are called " containing the organic acid compound ", but, no matter in the term of routine, whether this compounds is called or contains " organic acid ", included always be attached to above all compounds in various herein.
The aryl that in the structural formula shown in above, R and R ' be selected from the alkyl with at least 3 carbon atoms, the alkenyl with at least 3 carbon atoms, aryl, replaced by at least one alkyl, the alkyl that replaced by 1-2 acyloxy wherein acyl group are the residues with aliphatic monocarboxylic acid of at least 2 carbon atoms.Above-mentioned in various each R and R ' group all can at random promptly not contained active hydrogen atom by one or more inert substituents thereby be that the inert substituting group replaces in the presence of polyisocyanates.Illustration as this class inert substituent is alkoxyl group, alkyl thiol, alkenyl oxy, alkenyl sulfydryl, chlorine, bromine, iodine, fluorine, cyano group etc.
Therefore, above structural formula comprehensive compound comprise for example phosphate ester acid, sulfonic acid and carboxylic acid.Also comprise for example derivative of o-monoacyl, formamyl, phosphoryl and the alkylsulfonyl of arbitrary group of organic acid anhydride or mixed anhydride simultaneously; Polyphosphate comprises the polyphosphate and the ring metaphosphoric ester of branching; And composition thereof.
Term " acid anhydride " comprises that part is by P contained compound (I) or sulfocompound (III) deutero-pyrophosphate and pyrosulfuric acid ester.Pyrophosphate and pyrosulfuric acid ester can be according to method well known in the art from its corresponding phosphate ester acid or acidic sulfate by the latter and dewatering agent for example carbonyl chloride, aryl or single alkyl isocyanate and polyisocyanates, N, the reaction of N '-dihydro carbon back carbodiimide etc. makes; Consult for example F.Cramer and M.Winter, Chem.Ber.94,989 (1961); F.Ramirez, J.F.Marecek and I.Ugi, J.Am.Chem.Soc.97,3809 (1957).
The preferential phosphorous or sulfocompound of selecting is the liquid ester class, comprises monoesters, diester and composition thereof, and these materials are well-known, and are available on market.When needing,, react the phosphate ester acid that can easily prepare the formula (I) that is monoesters and diester form of mixtures with Vanadium Pentoxide in FLAKES or oxysulfide by alcohol roh or mercaptan RSH (wherein the definition of R is the same) according to sophisticated method; For example consult Kosolapoff, Organophosphorus Compounds, pp.220-221, John Wiley andSons, Inc., New York, 1950.Also preferred simultaneously pyrophosphate or by the mixture deutero-mixing pyrophosphate of phosphate ester acid and pyrosulfuric acid ester or by the mixture deutero-mixing pyrosulfuric acid ester of sulfonic acid, they are easy to by method preparation cited above.
The illustration of the P contained compound of the following formula (I) that can use separately in the method for the invention or be used with other phosphate ester acid is the phosphate ester acid phosphate ester acid of list-O-octyl group, list-O-nonyl and list-O-decyl for example of monoesters; The phosphoric acid ester of diester is O for example, O-two (octyl group), O, O-two (nonyl) and O, the phosphate ester acid of O-two (decyl); Pyrophosphate is the pyrophosphate of four octyl groups, four nonyls and tetradecyl and two (octyl group), two (nonyls) and two (decyls) for example; And with list-O-octyl group, list-O-nonyl and list-O-decyl or O, O-two (octyl group), O, O-two (nonyl) and O, O-two (decyl) or blended list-O octyl group, O, the list of O-two (octyl group) or different chain length-O-alkyl and O, the end capped polyphosphate of the composition of O-dialkyl group.Clearly, wherein esterified group is that end capped phosphate ester acid of 1-trichlorine butylene oxide ring and thiophosphatephosphorothioate are particularly advantageous to the present invention by the monohydroxy-alcohol deutero-, with oxyethane, propylene oxide, the epoxy chloropropane or 1,1 of suitable mol ratio.
Other are used for phosphate compound of the present invention and comprise the monoacyl phosphate ester acid for example the derivative of O-decanoyl, O-lauroyl and O-benzoyl can be by Koso-lapoff; ibid; p.334 described method preparation; for example octenyl formamyl, decene base formamyl and dodecenyl succinic formamyl phosphoric acid ester can be by F.Cramer and M.Winter for the carbamyl phosphate ester; Chem.Ber.; pp.92,2761 (1959) described method preparations.
Shown in the formula as mentioned in the above (II), carboxylic acid and poly carboxylic acid also can be used for the present invention.They can comprise many-and list-ethylenic unsaturated acid for example 3-octylenic acid, the 11-laurostearic acid and 1 of for example straight chain and side chain, 12-12 (acid).Poly carboxylic acid that molecular weight is bigger and polyfunctional carboxylic acid can be mixed with low viscous, so that spray on the substrate particles with other component of the present invention.
Suitable especially sulfonic acid shown in the formula above (III) comprises for example aromatics monosulfonic acid of decane sulfonic acid, octadecane sulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, naphthene sulfonic acid, hexanaphthene sulfonic acid and this class, and these reagent can be by known method by for example hexyl benzene, dodecylbenzene, octadecyl benzene or its mixture sulfonation prepare with alkylbenzene.
In enforcement of the present invention, also use the compound (3) that contains polyethers.This compound that contains polyethers can contain active hydrogen, or as its end group or side group, and can have the part that is not active hydrogen and still be non-reacted, be inert to polyisocyanates basically promptly.Therefore, no matter whether this compounds mainly or basically is categorized as polyether compound by standard terminology, " compound that contains polyethers " used herein comprises that any contains the compound of one or more polyether moieties.
In one embodiment, this polyether compound contains active hydrogen.As J.B.Niederl and V.Niederl, p.263 Micromethods of Ouanitative Organic Analvsis can adopt Zerewitinoff Test to measure to have determined whether active hydrogen described in (New York 1946).Usually, active hydrogen in this compounds can generate urethane with the polyisocyanates reaction and comprise the relevant polymkeric substance of polyureas and polyurethane/polyurea, therefore, the product of gained is the polymer binder of urethane, polyureas or polyurethane/polyurea in some embodiments of the present invention.The compound that preferably contains compound bearing active hydrogen and be hydroxy functional groups is polyvalent alcohol or monohydroxy-alcohol for example.Usually, typically be used for preparing any polyether glycol urethane and relevant polymer process, that comprise the so-called polyester polyol that contains polyether moiety (being also referred to as the polyether polyester polyvalent alcohol) and be suit and have a hydroxyl value that can in relative broad range, change, preferably from 10, more preferably 100 to 6,000, optimum chooses 600.
Preferred alcohols comprises and is selected from following a few class separately or the polyvalent alcohol and the monohydroxy-alcohol of blended composition: (a) many-or the alkylene oxide adduct of monohydroxy-alkane or alkene; (b) alkylene oxide adduct of non-reducing sugar and sugar derivatives; (c) alkylene oxide adduct of phosphorus and Tripyrophosphoric acid; And (d) alkylene oxide adduct of polyphenol.Above-mentioned a few class polyvalent alcohol is referred to herein as " basic polyvalent alcohol ".The example that is used for the alkylene oxide adduct of polyhydroxyalkanes of the present invention is ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxyl butane and 1,6-dihydroxy-hexane, glycerine, 1,2,4-trihydroxybutane, 1,2,6-trihydroxy-hexane, 1,1,1-trimethylolethane, 1,1,1-TriMethylolPropane(TMP), tetramethylolmethane, polycaprolactone, Xylitol, arabitol, Sorbitol Powder, N.F,USP MANNITOL, sucrose, various amine, and composition thereof etc. adducts.
Be used for of the present inventionly also having poly-(oxygen propylidene) glycol, trivalent alcohol, tetravalent alcohol and hexanol and with any of this ethylene oxide-capped class alcohol.Above-mentioned these alcohol also comprise poly-(oxypropylene oxygen ethene) polyvalent alcohol.When adopting oxyethane, can for example it be mixed along polymer chain by any mode as interior block, end-blocks or random distribution block or its any combination.In addition, the pure and mild mercaptan compound of polyester polyols that contains polyether moiety can be used for the present invention.
Other compound that the contains polyethers for example compound of polyvalent alcohol, polythiol and other the isocyanate-reactive of polyamine, amine terminal also is applicable to the present invention.Another kind of preferred polyhydric alcohols comprises polymkeric substance " copolymer polyols " of the basic polyvalent alcohol of acrylonitritrile-styrene resin for example that contains stable dispersion.
Other polyether glycol that is used for the inventive method comprises for example United States Patent (USP) 3,325,421; 4,042,537; Disclosed polyurea polylol in 4,089,835; United States Patent (USP) 4,407, disclosed poly-oxamate polyvalent alcohol in 983; And United States Patent (USP) 4,374,209 for example; 4,324,716; 4,310,448; 4,310,449; 4,350,857; With 4,305, disclosed polyisocyanates adduction product in 858.
There is not the compound that contains polyethers of active hydrogen can be in enforcement of the present invention yet.The inert reaction product of previously described polyether glycol, polyamine or polythiol constitutes the important group of this compounds.According to J.B.Niederl and V.Niederl, Micromethods of Ouani-tative Organic Analysis, p.263 (New York 1946) is described, term " inert " refer to this reaction product basically not with the self-releasing binder composition in polyisocyanates reaction.These inert reaction products can add to by the polyether compound that will contain the group of active hydrogen, epoxide or any and isocyanate reaction by being prepared in the excessive polyisocyanates of stoichiometry, generating and contain an active isocyanate functional group at least, are commonly referred to prepolymer.The other parts of not explaining when the prepolymer of Xing Chenging can contain urethane, polyureas, polythiourea or narrate active hydrogen-contg compound in the past like this.
The inert reaction product of the second class polyether glycol is that the esterification by polyether glycol and organic acid or organic acid anhydride generates.Therefore, comprise oxyethane, propylene oxide, butylene oxide ring and tetrahydrofuran (THF) and multipolymer thereof or mixture and have single-or the polyethers of polyhydroxy functional groups can be by known method and common acid or anhydride reaction to prepare the inertia polyether ester.The example of common acid is acetate, propionic acid, lauric acid and toluenesulphonic acids, and diacetyl oxide and Tetra hydro Phthalic anhydride are the illustrations as common acid anhydride.
The compound that the 3rd class contains the inertia polyethers can be prepared by the reaction of polyether glycol and monoisocyanates generation carbamyl derivative.The derivative of urea, thiocarbamide, epoxide and siloxanes equally can be by making with the reaction of the compound of the amine that contains polyethers accordingly, mercaptan, epoxy and siloxanes respectively.The example of the monoisocyanates that can suitably use is a phenylcarbimide.
Other is not the derivative of tresylate, acrylate, aldehyde and the succinimido of polyoxyethylene glycol with the compound that contains polyethers that isocyanate reaction does not promptly contain any active hydrogen.The example of other inert compounds is poly-alkoxyl group ether, poly-alkoxyl group epoxide, poly-oxyalkylsiloxane, poly-alkoxyl group acid amides and poly-ketonic ether, and wherein the active hydrogen of side group or end group or functional group react as mentioned above.Though it is not above cited comprehensive, but those skilled in the art that are apparent, when with organic acid (2) when using, if there are enough content of polyether to realize the demoulding, so, the chemical process by standard just can make and polyisocyanates is inactive various functional group plays a role within the scope of the invention.The compound that contains polyethers of preferably this " inertia " and the weight ratio between the polyisocyanates are per 100 parts of polyisocyanates from 1, more preferably from 4, most preferably from 6 to 2,000, more preferably 20, most preferably 15 parts.
Containing the active hydrogen polyether compound also can use in the present invention with the mixture that contains the inertia polyether compound.
Above-described is the component of self-releasing binder system itself.The parent material that is used for composite product also comprises substrate particles.These particles are cellulosic and can compactings and be bonded to tabular particle in a preferred embodiment.Usually these materials are from the wood-curing waste wood particle that obtains such as plane wood shavings, veneer fragment for example.The particle of other cellulose materials is for example corn stalk, straw and bagasse of paper scrap, paper pulp or vegetable fibre for example, and the material that belongs to non-cellulose is scrap metal for example; Urethane, polyisocyanates, polyethylene and similar polymkeric substance; Glass fibre; And composition also can use.According to the present invention, when forming shaving board or other composite product, inorganic material is hydrated aluminum oxide, gypsum and garrulous mineral fiber for example, can use separately or use with above-mentioned any material-mix cellulosic or non-cellulose.When needing, also can use the mixture of various cellulose grains.If select cellulose grain as base material, usually preferred its initial moisture content is less than about 25% (weight).
In the present invention, can adopt the different methods of some contact parent materials, these parent materials comprise that polyisocyanates (1), organic acid compound (2) contain polyether compound (3) and substrate particles (4).In first kind of implementation method, the component (1), (2) and (3) that separate can be combined simultaneously and are coated on the substrate particles.Term " simultaneously " referred to before being coated on the substrate particles the mode that component (1)-(3) are combined of separating, no matter be (2) and (3) in conjunction with before contact with (1) then and finish or the component (1) of separating, the single current that (2) and (3) infeed are combined the mode of finishing.
In one embodiment, selection contain the organic acid compound in advance with the polyether compound that contains active hydrogen for example polyether glycol mix.Like this, usually, can form the composition that shelf-stable is easy to store and transport.In this case, the weight ratio that contains organic acid compound and contain the active hydrogen polyether compound is preferably from 1: 7600 to 1: 0.10, more preferably from 1: 275 to 1: 0.70, most preferably from 1: 12 to 1: 1.For convenience's sake, preferably under the condition of envrionment temperature and pressure, the method and apparatus that adopts any present technique field personnel to be familiar with simply mixes to guarantee homogeneity; Yet, can adopt freezing point from given component to the very wide condition of the scope of its boiling point, because every kind of component all is preferably liquid.Therefore, preferred temperature range be from 0 ℃, more preferably from 15 ℃ to 70 ℃, more preferably 50 ℃, the preferred pressure scope is about 0 to about 3 normal atmosphere (atm).(1 normal atmosphere equals 101,325 Pascal, or about 0.1MPa.).In one embodiment, can adopt elevated temperature and pressure to improve the flowability in the sticking system of selected materials.The viscosity that contains organic acid compound/contain mixture of active hydrogen polyether compound is preferably from 10, more preferably 50 to 5,000, more preferably 400 centipoises (cps).For the component (2) of some selections, they are solids or at room temperature are insoluble to the compound that contains polyethers, therefore, need be heated its fusing point or dissolved click in order to produce uniform mixture.Usually, the senior monoester form that preferably adopts the liquid phosphate ester acid for example 2-ethylhexyl-or isodecyl-, because they are easier to dispose and are compatible with polyvalent alcohol.
After preparation comprised the mixture that contains polyether compound (3) and organic acid (2), this mixture can contact and be coated on the substrate particles of cellulosic or other type with polyisocyanates.The weight ratio that contains organic acid compound and polyisocyanates is preferably from about 4, preferably from about 6 to about 12 parts, more preferably from about 8 parts contain organic acid compound and about 100 parts of polyisocyanates.Because polyisocyanates produces urethane and/or polyureas with containing the compound bearing active hydrogen reaction, therefore, before being coated to particle, when all mixing, these components must in the mixed short period, apply.In order to mix the compound of polyisocyanates and isocyanate-reactive, can adopt any to be generally urethane and be familiar with personnel in the relevant technical field of polymer or adopt exhausted means, method, device or condition.Above-mentioned these comprise that for example impact is mixed into shower nozzle; The simple mixing; For on a small scale or can adopt manual or mechanical means respectively on a large scale; Or employing cylinder or vibrating machine.Because being reflected between the component of the polyisocyanates of this mixture and isocyanate-reactive is heat release in nature, so, preferably 0 ℃, more preferably 20 ℃ to 50 ℃, more preferably contact under 30 ℃.
In another embodiment of the invention, each component of binder composition can be mixed simultaneously, because for example adopt three streaming mixing heads, and the pre-mixing that need not to carry out organic acid compound (2) Yu contain polyether compound (3).In another embodiment, organic acid compound (2) can with polyisocyanates (1) pre-mixing.In this case, preferably,, therefore may there be enough package stabilities because polyisocyanates and organic acid compound (2) are active under certain conditions just finishing pre-mixing before contacting with containing polyether compound.
In another embodiment, the component of binder composition (1), (2) and (3) are bonded and are processed into shelf-stable and leave material in the independent container in, till needs are used for being coated to substrate particles (4) and go up.Those skilled in the art that be it is evident that can obtain some is used for by containing the method for organic acid compound (2) with the polyisocyanates reaction treatment, and like this, reaction product is inert and polyisocyanates is no longer had activity.This example can be referring to United States Patent (USP) 4,258, and 169, United States Patent (USP) 4,478,738 and United States Patent (USP) 4,772,442.According to the mode that has or do not exist active hydrogen in the compound, the compound (3) that contains polyethers can combine with polyisocyanates (1).In one embodiment, contain the active hydrogen polyethers compound prepolymer for example polyether glycol can produce by sophisticated method in this area.In another embodiment, the compound that contains the inertia polyethers for example the polyethers monohydroxy-alcohol of esterification can mix with polyisocyanates.For containing the compound of polyethers, no matter whether it contains active hydrogen, can with react or mix with the polyisocyanates that contains organic acid compound (2) reaction, or can at first react or mix with polyisocyanates, then with contain organic acid compound reaction, or, it can be added in the polyisocyanates (1) simultaneously containing polyether compound (3) and containing under the very little situation of reactivity between the organic acid compound (2).
Usually, preferably by polyisocyanates (1) is heated the liquid mixture that (1), (2) and (3) is processed into shelf-stable about 60 to about 190 ℃ temperature; Simultaneously or then about 1 combine the formation reaction mixture with each to about 20 parts (2) and (3) by per 100 parts of polyisocyanates; Unlikely being separated when keeping the heating certain hour that this reaction mixture is at room temperature cooled off.In a preferred embodiment, with organic acid and polyisocyanates at about 60 ℃ of chemical combination 2 hours to about 190 ℃ temperature range; Add the compound that contains polyethers that does not contain active hydrogen then.Preferably, organic acid is a phosphate ester acid; Polyisocyanates is the polymeric isocyanic ester, and the compound that contains polyethers is the polyether glycol of esterification.Organic acid is that benchmark is preferably 1-20 part with the consumption that contains the compound of polyethers with 100 parts of polyisocyanates.In a preferred embodiment, be that benchmark preferably adopts 4-12 part phosphate ester acid and 6-20 part to contain the compound of polyethers with 100 parts of polyisocyanates.In this case, the polyethers monohydroxy-alcohol that can add esterification under the temperature that improves reflects the trace impurity that contains active hydrogen that may exist, and preferably adds down at 60-80 ℃, keeps this temperature 0.5-1.5 hour till impurity becomes inertia.Basically be not separated when under any circumstance, all keeping the heating certain hour that this reaction mixture is at room temperature cooled off.If do not contain the impurity of active hydrogen, the polyethers monohydroxy-alcohol of esterification can at room temperature mix with the polyisocyanates of the reaction product that contains phosphate ester acid.Binder composition from the demoulding is the material of liquid, shelf-stable and can stores considerable time till needs are coated on the substrate particles.
In another preferred embodiment, polyether glycol (3) and phosphate ester acid (2) can add to by keeping 2-3 hour down in the excessive polyisocyanates of stoichiometry (1) and at 60-100 ℃.Adopt the ratio of material same as described above.Monomer two (phenyl isocyanate) methane that preferred polyisocyanates has high level, like this, the viscosity of final reacting product preferred 50 is to 1000cps, more preferably 500cps.When needing, product that can viscosity is lower mixes with the high-grade polymeric isocyanate to improve viscosity.On the other hand, the viscosity high product that is generated by senior polymeric isocyanate can be mixed with the polyisocyanates of two (phenyl isocyanate) methane that contains higher proportion to obtain the lower product of viscosity.In both cases all suitably the consumption of conditioned reaction agent so that the finished product belong to preferred weight range.
As illustration be, " oven dry " weight is benchmark with particulate, can add the adhesive composition of total amount (except that any moisture and, total composition weight that can exist in particle) for about 2 to 8 (weight), but more or more a spot of adhesive composition can be used for any specific purposes.As illustration is that for example in twisted wire plate and thin plate, operable amount of binder is that benchmark is less than 1% (weight) with particulate " oven dry " weight in the bigger occasion of particle size.Promptly have bigger surface area/volume ratio (for example under the situation in Powdered inorganic materials) in the very little occasion of particle size, adhesive consumption preferably is about 30% (weight) at the most, preferred about 20% (weight).When needing, also can for example wax sizing agent, fire retardant, pigment and composition thereof add in the particle with other material before adhesive composition is coated to base material or in the coating procedure.
In a preferred embodiment of the invention, the substrate particles after the coating forms loose slab or felt simultaneously or subsequently, preferably contains 4-20% (weight) moisture.Then, be placed in the thermocompressor slab and compression, making the substrate particles compacting is that one becomes closely knit composite product.Press time, temperature and pressure are with the density of the thickness of slab of being produced, required plate, factor that particulate size and other of adopting is well known in the art and in wide variation very.The isopycnic 0.5 inch thick shaving board of centering for example, pressure is about 300 to about 700 pounds/square inch usually, and temperature is about 325 °F to about 400 °F.Press time is about 2 to about 5 minutes usually.
Aforesaid method can carry out in batches, that is, by handling an amount of particle with adhesive resin composition, then, the material after heating and the pressing treatment is molded into shaving board piecewise.On the other hand, this method can take the successive mode to carry out, that is, with the particle after the processing of continuous coiled material or slab form, carry by heating and blanketed zone by continuous belt demarcation up and down, applies essential heat and pressure to it and by it.
No matter method of the present invention is undertaken by mode in batches or continuously, the composite product of having found to adopt self-releasing binder composition as herein described and having produced is easy to the demoulding from the pressed metal plate that is used for making its shaping, in addition when heating platen be formed from steel and by other material situation that for example aluminium, chromium and nickel are made commonly used under still demonstrate and can significantly reduce the trend that adheres to or be bonded on the heating platen.This be with former experience with adopt separately polyisocyanates or polyisocyanates and phosphate ester acid, sulfuric ester or independent carboxylicesters in certain heating platen direct correlated result on the steel particularly.
Following preparation and embodiment are intended to illustrate the present invention and neither also should by any way it not thought limitation of the scope of the invention.
Used in an embodiment term definition is as follows:
DOWANOL
TMThe product that 500 expressions can be bought from Dow Chemical Company, it is that molecular weight that the assorted feed (heterofed) by oxyethane and propylene oxide makes is 500 monohydroxy-alcohol.
P-425, the product that expression can be bought from Dow Chemical Company, it is that molecular weight is the polyether glycol of 425 propylene oxide base.
E-400, the product that expression can be bought from Dow Chemical Company, it is that molecular weight is the polyethers monohydroxy-alcohol of 400 Oxyranyle.
ETHFAC
TMPD-O, expression can be from the product of Ethox Corporation purchase, and it is Gao Dan-ester isodecyl phosphate ester acid.
ETHOX
TM101, expression can be from the product of Ethox Corporation purchase, and it is monoesters/two ester mixtures of isodecyl phosphate ester acid.
BIO-SOFT
TMS-100, expression can be from the product of Stepan Company purchase, and it is the straight chain Witco 1298 Soft Acid.
STEPANTAN
TMH-100, expression can be from the product of Stepan Company purchase, and it is a branched dodecylbenzene sulfonic acid.
PRIPOL
TM1009, expression can be from the product of Unichema International purchase, and it is C
36The carboxylic acid dimerization.
MPEG 350 AC, the product that expression can be bought from Dow Chemical Company, it is that molecular weight is the acetic ester of 350 methoxy poly (ethylene glycol) monohydroxy-alcohol.
GLY PO AC, the product that expression can be bought from Dow Chemical Company, it is that molecular weight is the triacetate of 1800 propoxylated glycerol.
KESSCO
TMPEG 200 DL, expression can be from the product of Stepan Company purchase, and it is the dilaurate that contains 4 moles of ethylene oxide.
PAPI
TM27, expression can be from the product of Dow Chemical Company purchase, and it is the polymerization diphenylmethane diisocyanate with 134 isocyanurate equivalents.
PAPI
TM88, expression can be from the product of Dow Chemical Company purchase, and it is the polymerization diphenylmethane diisocyanate with 136 isocyanurate equivalents.
ISONATE
TM125M, expression can be from the product of Dow Chemical Company purchase, and it is the '-diphenylmethane diisocyanate with 125 isocyanurate equivalents.Embodiment 1-6
Adopt the formulation 6 kinds of different binder compositions of the present invention (embodiment 1-6) shown in the table 1.Also prepare other 3 kinds and do not contained any binder composition that contains polyether compound (3) (in the same old way 1,3 and 4); Therefore, these several embodiment of the present invention and as a comparison case usefulness only do not represented.Every kind of prescription is all by polyisocyanates: polyethers: organic acid is 100 parts: 13.6 parts: the preparation of 9.9 parts weight ratio, and in the same old way 1,3 and 4 by polyisocyanates: the ratio of organic acid is 100 parts: except the situation of 9.9 parts of preparations.To 2 only contain polyisocyanates in the same old way.Be used for each embodiment and be PAPI in the same old way polyisocyanates
TM88.
For the above embodiments,, will contain organic acid compound (2) and at room temperature mix with the compound that contains polyethers (3) with before isocyanic ester (1) contacts.The compound (3) that will contain polyethers weigh and the beaker of packing in, will contain that organic acid compound (2) is weighed and the same beaker of packing in, then, these two kinds of compounds are stirred several minutes together till limpid, uniform mixture produces.With this mixture with several weeks of single-phase maintenance.
For the demolding performace of test recipe, adopt the prescription of explanation in the table 1, by aforementioned ratio, be benchmark with the dry weight of the stranded plate wood chip (being generally 3 inches * 1 inch * 0.05 inch) of standard aspen wood orientation, prepare composition board by 6.2% binder content.The material that is made into is measured together and before just will spraying to wood chip, be transported in the static mixer.The timber particle rolls in rotary drum and by the speed of per second 1-5 gram (g/s) spray is introduced rotary drum by the hole of rotary drum.Spraying continues 1-3 minute, then, this wood chip is rolled 10 minutes again.
After applying the blended component, in the system film frame box that manually wood chip is placed on the billet 2 feet * 2 feet or 10 inches * 10 inches.Utilize the billet of the billet sheet at top and bottom then or directly facing to top heating platen compacting plank base.Adopt typical compacting parameter: 2 minutes time; 190 ℃ of temperature; Pressure 400-500 pound/square inch (2.75MPa-3.44MPa).As long as this surface does not add processing in addition before pressing operation or in the operating process, just should when beginning, the surface of press fully be cleaned.
The part that term used herein " demoulding " is defined as being produced needn't from the surface lever up and can not leave over particle and have to the compacting another part before it is scraped off from the surface.
Table 1
| The embodiment numbering | Contain polyether compound (3) | Organic acid (2) | Heating platen is formed | Demoulding number |
| ????1 | ?DOW?ANOL TM????500 | ??ET?HF?AC TM????PD-O | 316 stainless steel top are at the bottom of the carbon steel | 18+ |
| ????2 | ????P425 | ??ET?HF?AC TM????PD-O | 316 stainless steel top are at the bottom of the carbon steel | 5+ |
| ????3 | ????E400 | ??ET?HF?AC TM????PD-O | 316 stainless steel top are at the bottom of the carbon steel | 5+ |
| ????4 | ?DOW?ANOL TM????500 | ??ET?HF?AC TM????101 | 316 stainless steels | 2+ |
| ????5 | ?DOW?ANOL TM????500 | ?STEPANTAN TM????H-100 | The carbon steel top is at the bottom of 410 stainless steels | 4+ |
| ????6 | ?DOW?ANOL TM????500 | ??PRIPOL TM????1009 | Carbon steel pushes up at the bottom of 410 stainless steels | 4+ |
| To in the same old way 1 | ????-- | ??ET?HF?AC TM????PD-O | 316 stainless steels | 0 |
| To in the same old way 2 | ???-- | ????-- | 316 stainless steels | 0 |
| To in the same old way 3 | ???-- | ?ST?EP?ANT?AN TM????H-100 | The carbon steel top is at the bottom of 410 stainless steels | 0 |
| To in the same old way 4 | -- | ??PRIPOL TM????1009 | The carbon steel top is at the bottom of 410 stainless steels | ????0 |
All tests adopt aspen wood to carry out.
-expression does not exist.
The part that+expression basis has been passed through is easy to the situation of the demoulding, and expectation can realize again
The demoulding; Yet, on these specific aspects, stopped test.
To 1-4 in the same old way only as contrast and do not represent embodiment of the present invention.Embodiment 7
PAPI with a 3000 grams (80.6% (weight))
TM27 pack into is furnished with in many necks reactor of mechanical stirrer and nitrogen purging.Polyisocyanates is heated to 80-85 ℃, subsequently, is guaranteeing under the slight blistered situation, in about 15 minutes, add the ET HF AC of a 300 grams (8.1% (weight))
TM101.After about 30 minutes, in 12 minutes, introduce MPEG 350 AC of 420 grams (11.3% (weight)), and make to be reflected at and kept again under 80-85 ℃ 1.5 hours.Obtain single-phase, uniform liquid.
Handle the pine sheet that water content are 8 kilograms of 8% portions with the aerosol sprays and ozone of the aliquot sample of 300 gram (5%) tackiness agents, and it is pressed into the plate of 10 inches described in the embodiment 1-6 * 10 inches.The demoulding the results are shown in table 2.Embodiment 8
PAPI with a 3000 grams (80.6% (weight))
TM27 are heated to 82 ℃, thereafter, add the ET HF AC of a 300 grams (8.1% (weight)) in 17 minutes under mechanical stirring and nitrogen purging
TM101.Guarantee slight the foaming.Keep reaction 30 minutes down at 82 ℃, then, during 20 minutes, add the GLY-PO AC of 420 grams (11.3% (weight)).After keeping 1.5 hours again under 80-83 ℃,, obtain even, monophasic liquid with the reaction mixture cool to room temperature.
Adopt aforesaid method, it is on 7% the 6957 gram pine sheets that above-mentioned aliquot sample (5.8% resin) tackiness agents of 431 grams are coated to water content.Make the composition board of 10 inches * 10 inches series, its demoulding the results are shown in table 2.Embodiment 9
KESSCO with a 5.7 grams (25% (weight))
TMThe ETHFAC of PEG 200 DL and 1.2 grams (5% (weight))
TMThe PD-O combination.This mixture is added to the PAPI of 16.4 grams (70% (weight))
TMIn 88, and thorough mixing before the aspen wood chip of in being coated to several minutes, making.
The aspen wood chip of a 803 grams is restrained the adhesive treatment described in (2.8% (weight)) embodiment 1-6 with 23.3.The data of the composition board demoulding are listed in table 2.Embodiment 10
With 80 gram (8.6% (weight)) ET HF AC
TM101 and 110 gram (11.8% (weight)) DOW ANOL
TM500 mixture is introduced a 243 grams (26% (weight)) in 85 ℃ of warmed-up ISONATE under nitrogen purging
TMAmong the 125M.In 45 minutes, introduce.Entered addition week after date at about 8 minutes, colourless MDI becomes obvious band foamy golden yellow.This reaction mixture was kept under 81-89 ℃ 1.75 hours again, let alone cooling then, demonstrate muddy yellow, slightly toughness.Then this mixture and 500 is restrained the PAPI of (53.6%)
TM88 at room temperature mix.
Adopting said apparatus and method that the aliquots containigs of this mixture of 340 grams (5.4%) are sprayed to water content is on 15% the 6000 gram pine sheets.Make 20 inches * 20 inches composition board, demoulding data are listed in table 2.
Only be appointed as 5,6 and 7 Comparative Examples in the same old way as contrast and do not represent embodiment of the present invention.Comparative Examples: in the same old way 5
ETHFAC with 15.1 grams (7% (weight))
TM101 add 200 gram PA-PI to
TMIn 88, under nitrogen atmosphere, be heated to 90 ℃ during 10 minutes.Under 90 ℃, continue reaction 2 hours again.
As mentioned above, in the ratio adhesive treatment aspen wood of 164 gram timber and 3.3 gram (2% (weight)) tackiness agents, make 6 inches * 6 inches plate, the demoulding the results are shown in table 2.Comparative Examples: in the same old way 6
PAPI with a 28.7 grams
TM88 and 9.6 restrain (25% (weight)) mpeg 3 50 AC at room temperature combines.This mixture is coated to 1395 grams to be equivalent on the aspen wood chip of 2.7% (weight).The demoulding data of formed composition board are listed in table 2.Comparative Examples: in the same old way 7
KESSCO with 5.7 grams (25.8% (weight))
TMPEG 200 DL and 16.4 gram PAPI
TM88 mix, and are coated on the 1083 Keshan poplar sheets.The demoulding data of composition board are listed in table 2.
Table 2
| The embodiment numbering | Polyether compound | Organic acid | Heating platen is formed | Demoulding number |
| ????7 | ?MPEG?350?AC | ??ET?HF?AC TM????101 | The carbon steel top is at the bottom of 316 stainless steels | ????100+ |
| ????8 | ?GLY-PO?AC | ??ET?HF?AC TM????101 | The carbon steel top is at the bottom of 316 stainless steels | ????12+ |
| ????9 | ??KESSCO TM???200?DL | ??ET?HF?AC TM????PD-O | The carbon steel top is at the bottom of 410 stainless steels | ????4+ |
| 10 | ?DOW?ANOL TM500 (prepolymers) | ??ET?HF?AC TM????101 | Carbon steel pushes up at the bottom of 316 stainless steels | ????3+ |
| To in the same old way 5 | ??----- | ??ET?HF?AC TM????102 | The carbon steel top is at the bottom of 316 stainless steels | ????0 |
| To in the same old way 6 | ?MPEG?350?AC | ??----- | Carbon steel pushes up at the bottom of 316 stainless steels | ????0 |
| To in the same old way 7 | ??KESSCO TM???200?DL | ??----- | The carbon steel top is at the bottom of 410 stainless steels | ????0 |
Embodiment 7,8 and to 5 and 6 adopt pines to carry out in the same old way.
Embodiment 9 and to 7 adopt aspen woods to carry out in the same old way.
-expression does not exist.
The part that+expression basis has been passed through is easy to the situation of the demoulding, and expectation can realize again
The demoulding; Yet, on these specific aspects, stopped test.
To 5-7 in the same old way only as contrast and do not represent embodiment of the present invention.
Claims (10)
1. binder composition from the demoulding, should be to be enough to form under the reaction conditions of binder composition contact (1) polyisocyanate compound at least from method for making of the binder composition of the demoulding, (2) content be per 100 parts of (weight) polyisocyanate compound about 1 compounds to one of about 20 parts following formula:
In the formula, X is oxygen or sulphur, and R is alkyl or contains ether or the alkyl of ester group, and can be ring-type, and R ' is R, H or acyl group, formamyl, phosphoryl or alkylsulfonyl; And (3) contain the compound of polyethers, and supplementary condition are as follows: the compound that (i) wherein contains polyethers does not contain active hydrogen, and the content that contains the compound of polyethers is that per 100 parts of (weight) polyisocyanates contain about 1 to about 2000 parts; The compound that (ii) wherein contains polyethers contains at least one active hydrogen, and the content of compound that contains polyethers is for the compound of formula I, and OH: the NCO equivalence ratio was less than about 0.77: 1.00; For the compound of formula II, OH: the NCO equivalence ratio was less than about 0.25: 1.00; And for the compound of formula III, OH: the NCO equivalence ratio was less than about 0.10: 1.00.
2. method for preparing composite product, this method is included in following (1) polyisocyanate compound at least that contacts of reaction conditions that is enough to form composite product, and (2) content is per 100 parts of (weight) polyisocyanate compound about 1 compounds to one of about 20 parts following formula:
In the formula, X is oxygen or sulphur, and R is alkyl or contains ether or the alkyl of ester group, and can be ring-type, and R ' is R, H or acyl group, formamyl, phosphoryl or alkylsulfonyl; (3) contain the compound of polyethers, supplementary condition are as follows: the compound that (i) wherein contains polyethers does not contain active hydrogen, and the content that contains the compound of polyethers is that per 100 parts of (weight) polyisocyanates contain about 1 to about 2000 parts; The compound that (ii) wherein contains polyethers contains at least one active hydrogen, and the content of compound that contains polyethers is for the compound of formula I, and OH: the NCO equivalence ratio was less than about 0.77: 1.00; For the compound of formula (II), OH: the NCO equivalence ratio was less than about 0.25: 1.00; And for the compound of formula (III), OH: the NCO equivalence ratio was less than about 0.10: 1.00; (4) substrate particles.
3. according to the method for claim 2, wherein (1), (2) at first contact with the formation reaction mixture with (3), then this reaction mixture are contacted with substrate particles (4).
4. according to the method for claim 2, wherein, (1), (2) and (3) are processed into the mixture of liquid, shelf-stable by polyisocyanates (1) is heated to about 190 ℃ temperature at about 60 ℃; Simultaneously or then about 1 combine the formation reaction mixture with each to about 20 parts (2) and (3) by per 100 parts of polyisocyanates; Unlikelyly when keeping the heating certain hour to make this reaction mixture cool to room temperature be separated significantly.
5. according to the method for claim 2, its Chinese style I compound is selected from phosphate ester acid; The acid phosphoric anhydride; The acid polyphosphate; And composition thereof.
6. according to the method for claim 5, wherein the acid phosphoric anhydride is selected from the phosphoryl of o-monoacyl, formamyl, acid anhydrides and the derivative of alkylsulfonyl, and composition thereof; The acid polyphosphate is selected from polyphosphate, ring metaphosphoric ester and composition thereof of side chain.
7. according to the method for claim 2, what the compound that wherein contains polyethers was selected from that (1) be selected from polyether glycol, polyethers mercaptan, polyetheramine, polyether polyester polyvalent alcohol, hydroxy polyethers siloxanes, amino-polyether siloxanes and composition thereof contains the active hydrogen polyether compound; (2) be selected from the compound that contains the inertia polyethers of polyether ester, polyethers ethers, polyethers isocyanate prepolymer, polyetherketone, polyethers acid anhydride, polyether polyester, polyether thiourea alcohol ester, polyetheramides, polyethers epoxide, polyether silicone and composition thereof; (3) and composition thereof.
8. according to the method for claim 2, wherein polyisocyanates be selected from '-diphenylmethane diisocyanate, and PPDI, chlorobenzene vulcabond, α, α-xylylene diisocyanate, 2,4-and 2,6-tolylene diisocyanate and composition thereof, polymeric tolylene diisocyanate, triphenylmethane triisocyanate, 4,4 '-two isocyanide acyl phenyl ether, poly methylene poly phenyl poly isocyanate and composition thereof.
9. according to the method for claim 2, wherein substrate particles is selected from cellulose materials, lignocellulose, polymkeric substance, metal, inorganic materials and composition thereof.
10. according to the method for claim 2, its Chinese style II compound is selected from carboxylic acid, carboxylic acid dimerization, poly carboxylic acid and composition thereof, and the compound of formula III is selected from sulfonic acid, poly-sulfonic acid and composition thereof.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27094494A | 1994-07-05 | 1994-07-05 | |
| US08/270,944 | 1994-07-05 | ||
| US33316694A | 1994-10-02 | 1994-10-02 | |
| US08/333,166 | 1994-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1131958A true CN1131958A (en) | 1996-09-25 |
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ID=26954591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95190739A Pending CN1131958A (en) | 1994-07-05 | 1995-06-30 | Self-releasing binder system for composite products |
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| Country | Link |
|---|---|
| EP (1) | EP0719303A1 (en) |
| JP (1) | JPH09502763A (en) |
| KR (1) | KR960704979A (en) |
| CN (1) | CN1131958A (en) |
| AU (1) | AU679645B2 (en) |
| BR (1) | BR9506013A (en) |
| CA (1) | CA2170397A1 (en) |
| FI (1) | FI960997A0 (en) |
| MY (1) | MY130593A (en) |
| NO (1) | NO960868L (en) |
| WO (1) | WO1996001293A1 (en) |
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| CN113103396A (en) * | 2020-01-13 | 2021-07-13 | 万华化学集团股份有限公司 | Artificial board without aldehyde addition and manufacturing method thereof |
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| DE19724199A1 (en) * | 1997-06-09 | 1998-12-10 | Basf Ag | Emulsifiers |
| JP5634944B2 (en) * | 2011-06-02 | 2014-12-03 | 三井化学株式会社 | Polyurethane adhesive and laminate film |
| US9540513B2 (en) | 2012-11-21 | 2017-01-10 | Basf Se | Lignocellulosic article and method of producing same |
| WO2019068529A1 (en) * | 2017-10-06 | 2019-04-11 | Basf Se | Water-dispersible polyisocyanates |
| MX2022014103A (en) * | 2020-05-11 | 2022-12-08 | Huntsman Int Llc | A binder composition. |
| KR102515229B1 (en) * | 2023-01-26 | 2023-03-30 | 더본드 주식회사 | Urethane modified epoxy resin composition with improved adhesion and flexibility and construction method of thin polmer surface treatment pavement using the same |
| KR102755619B1 (en) * | 2024-07-29 | 2025-01-22 | 시원글로벌 주식회사 | Epoxy Paving Composition for Road Paving and Low-noise Drainage Paving Method using Thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257995A (en) * | 1979-05-03 | 1981-03-24 | The Upjohn Company | Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor |
| DE2921689A1 (en) * | 1979-05-29 | 1980-12-11 | Bayer Ag | SELF-SEPARATING ISOCYANATE-BASED BINDERS AND THE USE THEREOF IN A METHOD FOR THE PRODUCTION OF MOLDED BODIES |
| US4376088A (en) * | 1981-03-18 | 1983-03-08 | The Upjohn Company | Process for preparing a particle board using a self-releasing binder comprising a polyisocyanate and a sulfur-containing release agent |
| US4382108A (en) * | 1981-12-21 | 1983-05-03 | The Upjohn Company | Novel compositions and process |
| US4772442A (en) * | 1986-11-28 | 1988-09-20 | Jim Walter Research Corp. | Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites |
| US4933232A (en) * | 1986-11-28 | 1990-06-12 | Jim Walter Research Corp. | Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites |
-
1995
- 1995-06-30 KR KR1019960701106A patent/KR960704979A/en not_active Application Discontinuation
- 1995-06-30 CN CN95190739A patent/CN1131958A/en active Pending
- 1995-06-30 AU AU29155/95A patent/AU679645B2/en not_active Expired - Fee Related
- 1995-06-30 EP EP95924769A patent/EP0719303A1/en not_active Withdrawn
- 1995-06-30 JP JP8503952A patent/JPH09502763A/en active Pending
- 1995-06-30 BR BR9506013A patent/BR9506013A/en not_active Application Discontinuation
- 1995-06-30 WO PCT/US1995/008333 patent/WO1996001293A1/en not_active Application Discontinuation
- 1995-06-30 CA CA002170397A patent/CA2170397A1/en not_active Abandoned
- 1995-07-05 MY MYPI95001874A patent/MY130593A/en unknown
-
1996
- 1996-03-04 NO NO960868A patent/NO960868L/en unknown
- 1996-03-04 FI FI960997A patent/FI960997A0/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113103396A (en) * | 2020-01-13 | 2021-07-13 | 万华化学集团股份有限公司 | Artificial board without aldehyde addition and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| MY130593A (en) | 2007-07-31 |
| NO960868L (en) | 1996-05-03 |
| WO1996001293A1 (en) | 1996-01-18 |
| NO960868D0 (en) | 1996-03-04 |
| BR9506013A (en) | 1997-08-19 |
| JPH09502763A (en) | 1997-03-18 |
| FI960997A (en) | 1996-03-04 |
| KR960704979A (en) | 1996-10-09 |
| AU679645B2 (en) | 1997-07-03 |
| CA2170397A1 (en) | 1996-01-18 |
| AU2915595A (en) | 1996-01-25 |
| EP0719303A1 (en) | 1996-07-03 |
| FI960997A0 (en) | 1996-03-04 |
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