DK148359B - PROCEDURE FOR MANUFACTURING Aqueous POLYISOCYANATE EMULSIONS FOR LIMITING CHIPBOARDS - Google Patents
PROCEDURE FOR MANUFACTURING Aqueous POLYISOCYANATE EMULSIONS FOR LIMITING CHIPBOARDS Download PDFInfo
- Publication number
- DK148359B DK148359B DK038278AA DK38278A DK148359B DK 148359 B DK148359 B DK 148359B DK 038278A A DK038278A A DK 038278AA DK 38278 A DK38278 A DK 38278A DK 148359 B DK148359 B DK 148359B
- Authority
- DK
- Denmark
- Prior art keywords
- isocyanate
- emulsion
- diisocyanate
- emulsions
- parts
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6446—Proteins and derivatives thereof
-
- 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
-
- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
140359 i140359 i
Opfindelsen angår en fremgangsmåde til fremstilling af vandige polyisocyanat-emulsioner til limning af spånplader, af den i kravet angivne art.The invention relates to a process for preparing aqueous polyisocyanate emulsions for bonding particleboard, of the kind specified in the claim.
Anvendelsen af isocyanater som spånpladebindemiddel er 5 kendt (se f.eks. H.-J. Deppe og K. Ernst, Holz als Roh und Werkstoff, årg. 2£, side 45, 1971). Særligt kendt er bindemidler på grundlag af diphenylmethan-4,4'-diisocyanat.The use of isocyanates as particle board binder is known (see, e.g., H.-J. Deppe and K. Ernst, Holz als Roh und Werkstoff, year 2 £, page 45, 1971). Particularly known are binders based on diphenylmethane-4,4'-diisocyanate.
Som opløsningsmiddel frie, flydende produkter kan man anvende sådanne, der kan anvendes i de forarbejdningsanlæg, 10 der er sædvanlige i træindustrien.Solvent free liquid products may be used which can be used in the processing plants customary in the wood industry.
Det er dog en ulempe, især ved lave doseringer, at binde-midler på grundlag af isocyanater kun vanskeligt lader sig fordele regelmæssigt på spånmaterialet. Derved kan de teknologiske egenskaber af den færdige spånplade hvad angår 15 styrken forringes. Det er også en ulempe, at apparater eller maskindele, der er forurenet med isocyanat, ikke uden videre lader sig rense med vand. Det er ganske vist kendt, at man til fortynding af isocyanater kan anvende organiske opløsningsmidler. Velegnede opløsningsmidler, såsom dichlor-20 methan og andre, er imidlertid praktisk talt uanvendelige af toxicologiske grunde, og andre opløsningsmidler, såsom acetaler, er praktisk talt uanvendelige på grund af brandfaren.However, it is a disadvantage, especially at low doses, that binder based on isocyanates is difficult to dispense regularly on the chip material. Thereby, the technological properties of the finished chipboard in terms of strength can be impaired. It is also a disadvantage that appliances or machine parts contaminated with isocyanate are not easily cleansed with water. It is well known that organic solvents can be used to dilute isocyanates. However, suitable solvents such as dichloromethane and others are practically unusable for toxicological reasons and other solvents such as acetals are practically unusable due to the fire hazard.
Man har derfor i DE-offentliggørelsesskrift nr. 2 610 552, 25 jfr. DK-ans. nr. 1073/76, foreslået at anvende de isocya nater, der kommer i betragtning som bindemidler for ligno-celluloseholdige partikler, i form af en vandig emulsion.Accordingly, in DE Publication 2,610,552, 25, cf. DK-ans. No. 1073/76, proposed to use the isocyanates considered as binders for lignocellulosic particles in the form of an aqueous emulsion.
Man må dog i den forbindelse - hvilket også ses af resultaterne af de i offentliggørelsesskriftet angivne forsøg -30 stille særlige krav både til selve isocyanaterne og til de anvendte emulgatorer. Som (poly)isocyanater anvendes fortrinsvis præpolymere, dvs. omsætningsprodukter af egentlige polyisocyanater med polyester- eller polyetherpoly- 2 148359 oler, hvilke præpolymere endnu udviser isocyanat-endegrup-per. Som emulgatorer eller overfladeaktive midler anvendes nonioniske produkter, som desuden skal være fri for hydroxyl-, amino- eller carboxylsyregrupper.However, in this connection - as can also be seen from the results of the experiments mentioned in the publication specification - 30 have to make special requirements both for the isocyanates themselves and for the emulsifiers used. Preferably, as (poly) isocyanates, prepolymers are used, i.e. reaction products of actual polyisocyanates with polyester or polyether polymers, which prepolymers still exhibit isocyanate end groups. As emulsifiers or surfactants, nonionic products are used which must also be free of hydroxyl, amino or carboxylic acid groups.
5 Som det fremgår af offentliggørelsesskriftet er det imid lertid på trods af anvendelsen af betydelige mængder af specielle hydrofobe polyoler, ved fremstillingen af de nævnte præpolymere, heller ikke muligt at fremstille emulsioner, der udviser en tilstrækkelig holdbarhed; af eksem- 10 pel 2 i offentliggørelsesskriftet fremgår det desuden, at tabet af isocyanat-grupper i emulsionen i løbet af i hvert tilfælde to timer ved stuetemperatur i gunstigste fald andrager 14 til 17?0, og i ugunstigere tilfælde over 50¾.5 However, as is apparent from the disclosure, despite the use of significant amounts of special hydrophobic polyols, in the preparation of said prepolymers, it is also not possible to prepare emulsions which exhibit a sufficient durability; In addition, from Example 2 of the disclosure, it appears that the loss of isocyanate groups in the emulsion during the two cases at least two hours at room temperature is most advantageously 14 to 17 0, and in the less favorable case above 50 °.
For den sagkyndige på det område, der omfatter fremstil-15 ling af træmaterialer, er det således klart, at et sådant bindemiddel er af mindre praktisk værdi, fordi de i teknisk henseende nødvendige henstandstider mellem tilberedningen af en emulsion og sammenpresningen, givet ved kapaciteten af forrådsbeholderen for lim og limet spånmateri-20 ale, ikke opnås.It will thus be apparent to those skilled in the art which comprise the manufacture of wood materials, that such a binder is of less practical value, because of the technically necessary lag times between the preparation of an emulsion and the compression, given the capacity of the storage container for glue and glued particle material are not obtained.
Det er derfor opfindelsens formål at angive en fremgangsmåde til fremstilling af isocyanatemulsioner, der ikke udviser de angivne ulemper eller kun udviser disse i ringe omfang, dvs. at angive en fremgangsmåde til fremstilling 25 af mere lagerstabile, vandige emulsioner af polyisocya- nater.It is therefore the object of the invention to provide a process for the preparation of isocyanate emulsions which do not exhibit the disadvantages stated or exhibit only a slight extent, i.e. to disclose a process for preparing 25 more stock-stable, aqueous emulsions of polyisocyanates.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i den kendetegnende del af kravet angivne. Det har overraskende vist sig, at de i henhold til fremgangsmåden i-30 følge opfindelsen fremstillede vandige polyisocyanatemul- suiner udviser større lagerstabilitet end de kendte poly-isocyanatemulsioner.The process according to the invention is characterized by the characterizing part of the claim. Surprisingly, it has been found that the aqueous polyisocyanate emulsions prepared according to the invention exhibit greater storage stability than the known polyisocyanate emulsions.
148359 3148359 3
Fortrinsvis anvender man som emulgator en polyglycol, hvortil der yderligere er tilsat 1-30 vægt-Si af et polypeptid, beregnet på polyglycolen.Preferably, as an emulsifier, a polyglycol is used, to which is added 1 to 30 wt Si of a polypeptide, calculated on the polyglycol.
Resultatet af opfindelsen er overraskende, fordi det -5 ikke mindst fra det angivne DE-offentliggørelsesskrift - er kendt, at netop aromatiske isocyanater reagerer hurtigt med vand; lagerstabile isocyanatemulsioner er hidtil ikke beskrevet.The result of the invention is surprising because, not least from the disclosed DE publication specification, it is known that precisely aromatic isocyanates react rapidly with water; storage stable isocyanate emulsions have not been described so far.
Man kender ganske vist fra USA patentskrift nr. 3 428 592 10 vandige polyisocyanatemulsioner, der som dispers fase indeholder en opløsning af et aromatisk polyisocyanat i et organisk opløsningsmiddel. Udover, at de vandige polyisocyanatemulsioner, der fremstilles ved fremgangsmåden ifølge opfindelsen, ikke indeholder nogen organiske opløsnings-15 midler, anvendes de kendte polyisocyanatemulsioner til et helt andet formål, nemlig til imprægnering af papir.It is admittedly known from US Patent No. 3,428,592 to 10 aqueous polyisocyanate emulsions which contain as a dispersion phase a solution of an aromatic polyisocyanate in an organic solvent. In addition to the fact that the aqueous polyisocyanate emulsions produced by the process of the invention contain no organic solvents, the known polyisocyanate emulsions are used for a completely different purpose, namely, for impregnating paper.
Eksempler på organiske polyisocyanater, som kan anvendes ved fremgangsmåden ifølge opfindelsen, er aromatiske isocyanater, især diisocyanater som m- og p-phenylendiiso-20 cyanat, tolylen-2,4- og 2,6-diisocyanater, diphenylmethan-4,4'-diisocyanat, chlorphenylen-2,4-diisocyanat, napht-hylen-1,5-diisocyanat, diphenylen-4,4'-diisocyanat, 3,3'— dimethyldiphenyl-4,4'-diisocyanat-, 3-methyldiphenylme-than-4,4'-diisocyanat og diphenyletherdiisocyanat, og tri-25 isocyanater, som 2,4,6-triisocyanattotoluen og 2,4,4'-tri-isocyanatodiphenylether. De fremstilles blandt andet ved phosgenering af tilsvarende aminer på kendt måde. Blandinger af isocyanater kan f.eks. fås i handelen i form af blandinger af 2,4- og 2,6-isomere af tolylendiisocyanatet 30 samt blandingerne af di- og højere polyisocyanater, som fremstilles ved phosgenering af anilin-formaldehyd-konden-sater. Sådanne blandinger er i praksis alment kendt, og de omfatter de rå phosgeneringsprodukter, som indeholder 4 148359 blandinger af methylenbroholdige polyphenylpolyisocyanater, herunder diisocyanat, triisocyanat og højere polyisocyana-ter.sammen med phosgeneringsbiprodukterne.Examples of organic polyisocyanates which can be used in the process of the invention are aromatic isocyanates, especially diisocyanates such as m- and p-phenylene diisocyanate, tolylene-2,4- and 2,6-diisocyanates, diphenylmethane-4,4'- diisocyanate, chlorophenylene-2,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3-methyldiphenylmethane 4,4'-diisocyanate and diphenyl ether diisocyanate, and tri-isocyanates, such as 2,4,6-triisocyanatotoluene and 2,4,4'-tri-isocyanatodiphenyl ether. They are prepared, inter alia, by phosgenation of corresponding amines in a known manner. Mixtures of isocyanates may e.g. are commercially available in the form of mixtures of 2,4- and 2,6-isomers of the tolylene diisocyanate 30 as well as the mixtures of di- and higher polyisocyanates prepared by the phosgenation of aniline-formaldehyde condensates. Such mixtures are generally known in practice, and they comprise the crude phosgenation products which contain 4 148359 mixtures of methylene bridge-containing polyphenyl polyisocyanates including diisocyanate, triisocyanate and higher polyisocyanates together with the phosgenation by-products.
Foretrukne polyisocyanater, som kan anvendes ifølge opfin-5 delsen, er sådanne, hvori isocyanatet er et aromatisk di isocyanat eller polyisocyanat med højere funktionalitet, især rå blandinger af methylenbroholdige polyphenylpolyiso-. cyanater, som indeholder diisocyanater, triisocyanater eller polyisocyanater med højere funktionalitet. Methylen-10 broholdige polyphenylpolyisocyanater er alment kendt, og de udviser den almene formel O'®2—O^-(Jp) -Preferred polyisocyanates which can be used according to the invention are those in which the isocyanate is an aromatic di isocyanate or higher functionality polyisocyanate, especially crude mixtures of methylene bridged polyphenyl polyiso. cyanates containing diisocyanates, triisocyanates or polyisocyanates with higher functionality. Methylene-bridged polyphenyl polyisocyanates are well known in the art and exhibit the general formula O 2 - O - (Jp) -
NCO NCO NCONCO NCO NCO
J n-1 hvor n er over 1, og som i tilfælde af rå blandinger repræsenterer en middelværdi på over 1. Disse forbindelser fremstilles ved phosgenering af tilsvarende blandinger af po-15 lyaminer, som fremstilles ved kondensation af anilin og formaldehyd. Det er sædvanligt at betegne rå blandinger af methylenbroholdige polyphenylpolyisocyanater, som indeholder diisocyanat, triisocyanat og polyisocyanater med højere funktionalitet, som MDI.J n-1 where n is greater than 1 and, in the case of crude mixtures, represents an average value greater than 1. These compounds are prepared by phosgenation of similar mixtures of polyamines produced by condensation of aniline and formaldehyde. It is customary to designate crude mixtures of methylene bridge-containing polyphenyl polyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates, such as MDI.
20 Mindre velegnede isocyanater, som kan anvendes ifølge op findelsen, er isocyanatgruppeholdige præpolymere, der er fremstillet ved omsætning af et overskud af diisocyanat eller af et polyisocyanat med højere funktionalitet med en 148359 5 polyester eller polyether med endestillede hydroxylgrupper samt produkter, der er fremkommet ved omsætning af et overskud af diisocyanat eller polyisocyanat med højere funktio-nalitet med monomer polyol eller en blanding af monomere 5 polyoler, såsom ethylenglycol, trimethylolpropan og butan-diol.Less suitable isocyanates which can be used according to the invention are isocyanate group-containing prepolymers prepared by reaction of an excess of diisocyanate or of a higher functionality polyisocyanate with a polyester or polyether having terminated hydroxyl groups and products obtained by reaction of an excess of diisocyanate or higher functionality polyisocyanate with monomeric polyol or a mixture of monomeric polyols such as ethylene glycol, trimethylolpropane and butanediol.
Det er ganske vist muligt, at der under fremstillingen i-følge opfindelsen i ringe mængder dannes sådanne præpolymere.Admittedly, it is possible that during the preparation according to the invention, such prepolymers are formed in small amounts.
10 Højmolekylære, kommercielle polyglycoler, især polyethylen-glycoler, polypropylenglycoler samt blandede glycoler med molekylvægte fra 4000 til 20 000, fortrinsvis fra 6000 til 12 000, er velegnede emulgatorer til fremstilling af emulsioner af polyisocyanater. De fremstillede emulsioner an- 15 ses for at være stabile over et oplagringstidsrum på f.eks.High molecular weight commercial polyglycols, especially polyethylene glycols, polypropylene glycols, and mixed glycols of molecular weights of 4000 to 20,000, preferably from 6000 to 12,000, are suitable emulsifiers for preparing emulsions of polyisocyanates. The emulsions produced are considered to be stable over a storage period of e.g.
1 til 10 timer. Emulsionerne indeholder f.eks. 5 til 70¾ polyisocyanat, 2 til 20¾ polyglycol og iøvrigt vand. De fremstilles på den for emulsioner sædvanlige måde ved omrøring af bestanddelene med velegnede apparater.1 to 10 hours. The emulsions contain e.g. 5 to 70¾ polyisocyanate, 2 to 20¾ polyglycol and other water. They are prepared in the usual way for emulsions by stirring the ingredients with suitable apparatus.
20 Polyvinylalkoholer med det angivne molekylvægtsinterval kan fås på markedet og kræver ingen nærmere forklaring.20 Polyvinyl alcohols with the specified molecular weight range are available on the market and require no further explanation.
De tilsættes fortrinsvis til emulgeringsvandet i tilsvarende koncentration og tillader en høj emulgeringshastighed .They are preferably added to the emulsifying water at a corresponding concentration and allow a high emulsification rate.
25 Han opnår særligt velegnede emulsioner, når man som emulgator anvender polyglycol og yderligere 1 til 30 vægt-* af et polypeptid, beregnet i forhold til polyglycolen.He obtains particularly suitable emulsions when using as an emulsifier polyglycol and an additional 1 to 30 weight percent of a polypeptide calculated relative to the polyglycol.
Der opstår vandige emulsioner af isocyanater, der i sammenligning med dem, der kan opnås i henhold til kravet, 30 udviser en forøget brugsvarighed og desuden er billigere, fordi der til deres fremstilling kun behøves en mindre 6 148359 mængde emulgator. I almindelighed er en mængde på ca. 0,5-5% emulgator, beregnet i forhold til den totale emulsionsvægt, tilstrækkelig til at fremstille en emulsion, hvis titrerbare indhold af isocyanatgrupper i løbet af 10 ti-5 mer ikke reduceres med mere end ca. 5%.Aqueous emulsions of isocyanates occur which, in comparison with those obtainable according to the claim, exhibit an increased useful life and are also cheaper because only a small amount of emulsifier is required for their preparation. In general, an amount of approx. 0.5-5% emulsifier, calculated in relation to the total emulsion weight, sufficient to produce an emulsion whose titratable content of isocyanate groups over 10 hours is not reduced by more than approx. 5%.
Polypeptider i henhold til opfindelsen er f.eks. gelatine, knoglelim og lignende af proteinstoffer udvindelige produkter. Disse kan fås på markedet og behøver ingen nærmere·forklaring. De tilsættes fortrinsvis til emul-10 geringsvandet i tilsvarende koncentration og tillader en høj emulgeringshastighed. I almindelighed andrager indholdet af polyglycol i emulsionen 1-10%, mens der anvendes 0,1-1% polypeptid.Polypeptides of the invention are e.g. gelatin, bone glue and the like of protein extractable products. These are available on the market and need no further explanation. They are preferably added to the emulsifying water at similar concentration and allow a high emulsification rate. In general, the content of polyglycol in the emulsion is 1-10%, while 0.1-1% polypeptide is used.
I almindelighed er en mængde på ca. 0,5-5% polyvinylalko-15 hol, beregnet på den totale emulsionsvægt, tilstrækkelig til fremstilling af en emulsion, hvis titrerbare indhold af isocyanatgrupper i løbet af 10 timer ikke reduceres med mere end ca. 2%. Den tabel, der blev anført i eksempel 2 nedenfor, viser dette.In general, an amount of approx. 0.5-5% polyvinyl alcohol, calculated on the total weight of the emulsion, sufficient to prepare an emulsion whose titratable content of isocyanate groups is not reduced by more than about 10 hours. 2%. The table set forth in Example 2 below shows this.
20 For at adskille opfindelsen fra den kendte teknik må man i sammenhæng med fremstillingen af emulsionerne kort henvise til følgende:In order to separate the invention from the prior art, in the context of the preparation of the emulsions, one must briefly refer to the following:
Da det er kendt, at hydroxylgruppeholdige forbindelser reagerer med isocyanater, skal mængderne af glycol eller 25 PVA under hensyn til de pågældende molvægte og indhold af reaktionsdygtige grupper vælges således, at de i emulgatoren tilstedeværende hydroxylgrupper kun udgør en brøkdel, f.eks. ikke over 10 til højst 40% af de til rådighed stående isocyanatgrupper, jævnfør kravet. Den minimale 30 mængde kan udledes af blandingernes tekniske emulgerbar-hed.Since it is known that hydroxyl group-containing compounds react with isocyanates, the amounts of glycol or PVA must be selected, taking into account the respective molecular weights and content of reactive groups, that the hydroxyl groups present in the emulsifier constitute only a fraction, e.g. not more than 10 to a maximum of 40% of the available isocyanate groups, as required. The minimum amount of 30 can be deduced from the technical emulsification of the mixtures.
148359 7148359 7
Man må herefter antage, at de færdige emulsioner indeholder emulgatoren, i det mindste delvist som reaktionsprodukt med dele af isocyanatet, men at de emulgerede partikler alligevel også indeholder relativt uændrede bestand-5 dele af polyisocyanatet, der er beskyttet mod påvirknin gen f.eks. fra hydrolyse med vand.It must then be assumed that the finished emulsions contain the emulsifier, at least partly as a reaction product with parts of the isocyanate, but that the emulsified particles nevertheless also contain relatively unchanged components of the polyisocyanate which are protected against the effect e.g. from hydrolysis with water.
EKSEMPEL 1EXAMPLE 1
En typisk emulsion fremstilles af 30 dele diphenylmethan-4,4'-diisocyanat, 10 dele polyethylenglycol og 60 dele 10 vand på følgende måde:A typical emulsion is prepared from 30 parts of diphenylmethane-4,4'-diisocyanate, 10 parts of polyethylene glycol and 60 parts of 10 water as follows:
Polyethylenglycolen (gennemsnitlig molekylvægt 9 000, f.eks. det under handelsnavnet "Pluriol E 9000" rekvirer-bare produkt fra BASF AG) opløses i 60 dele vand, og i den under omrøring stående opløsning indrøres diphenyl-15 methan-4,4'-diisocyanat (f.eks. "Kauranat CE 5043" fra BASF AG). Emulgeringen ved hjælp af et hurtigtgående røre-værk (f.eks. fabrikatet Tornado eller Turrax) kræver ca.The polyethylene glycol (average molecular weight 9,000, for example, under the trade name "Pluriol E 9000" obtainable product from BASF AG) is dissolved in 60 parts of water, and in the stirring solution, diphenyl-methane-4.4 is stirred. diisocyanate (eg "Kauranate CE 5043" from BASF AG). Emulsification using a fast-moving agitator (for example, the Tornado or Turrax brand) requires approx.
10-30 sekunder.10-30 seconds.
Stabiliteten af isocyanat-emulsionen kan måles ved'hjælp 20 af kendte metoder, f.eks. ved titrering mod bromphenol- blåt. Til dette formål udtager man med bestemte tidsintervaller prøver af emulsionen, og disse blandes med overskud af dibutylamin-opløsning, og ikke forbrugt amin til-bagetitreres med methanolisk saltsyre. Som kendetal "R" 25 vælges forholdet mval dibutylamin/g diisocyanat.The stability of the isocyanate emulsion can be measured using 20 known methods, e.g. by titration against bromophenol blue. For this purpose, samples of the emulsion are taken at specified time intervals and these are mixed with excess dibutylamine solution and unused amine is titrated back with methanolic hydrochloric acid. As the characteristic "R" 25, the ratio mval dibutylamine / g diisocyanate is selected.
Kendetal R = mv/al dibutylamin g diisocyanatNumber R = mv / all dibutylamine and diisocyanate
Til bedømmelse af stabiliteten bestemmes R-værdien af rent isocyanat, den vandige isocyanat-emulsion måles lø-30 bende, og reduktionen af i hvert tilfælde bestemte R- værdier (i % af begyndelsesværdien; optegnes som ordinater mod tiden som abscisse, jfr. figuren.To assess the stability, the R value of pure isocyanate is determined, the aqueous isocyanate emulsion is continuously measured and the reduction of determined R values in each case (in% of the initial value; plotted as ordinates against time as abscissa), cf. .
8 148359 TABEL 1 R. . R- R Tid Isocyanat imer værdier (timer) (¾) R 7,162 7,160 0 100 5 U 7,190 7,1298 148359 TABLE 1 R.. R- R Time Isocyanate in values (hours) (¾) R 7,162 7,160 0 100 5 U 7,190 7,129
Rn 9C. 7,249 7,159 0,25 99,99 U’- 7,072 7,155 10 R, 7,194 7,220 1,25 100,84 7,196 7,269 R„ 6,997 7,038 2,00 98,30 Z 7,048 15 7,070 R, 6,959 6,969 3,00 97,33 · J 6,971 6,976 R^ 6,959 6,997 4,00 97,72 20 7,033 6,999 R- 6,930 6,897 5,00 96,33 6,871 6,889 25 Figuren og tabel 1 visér reduktionen af isocyanat-indhol-det ved en temperatjur på 23 °C i afhængighed af tiden (0-5 timer). Mellem isocyanatindholdet og lagringstiden foreligger der følgende empiriske sammenhæng: Y = 100 - 0,793 · tid (i timer) % 30 , Isocyanat-indholdet aftager altså kun gennemsnitligt 0,793?ό pr. time. Det skraverede område omkring regressionsgraden angiver konfidensintervallet for en signifikans. på 95¾. De to udenfor liggende kurver indeslutter 95¾ af enkeltmålingernes spredningsområde.Rn 9C. 7,249 7,159 0.25 99.99 U'- 7,072 7,155 10 R, 7,194 7,220 1.25 100.84 7,196 7,269 R 6,997 7,038 2.00 98.30 Z 7,048 15 7,070 R, 6,959 6,969 3.00 97.33 J 6,971 6,976 R ^ 6,959 6,997 4,00 97,72 20 7,033 6,999 R- 6,930 6,897 5,00 96,33 6,871 6,889 The figure and Table 1 show the reduction of the isocyanate content at a temperature of 23 ° C. time dependence (0-5 hours). Between the isocyanate content and the storage time, there is the following empirical correlation: Y = 100 - 0.793 · time (in hours)% 30, so the isocyanate content decreases only on average 0.793? hour. The shaded area around the regression degree indicates the confidence interval for a significance. at 95¾. The two outside curves enclose 95¾ of the scattering range of the individual measurements.
148359 9148359 9
Denne undersøgelse dokumenterer en indenfor de i praksis anvendte forarbejdningstider tilstrækkelig lagerstabilitet af emulsionen.This study documents a sufficient storage stability of the emulsion within the processing times used in practice.
Med polyisocyanat-emulsionen fremstillede man spånplader, 5 og deres teknologiske anvendelse blev undersøgt i eksempel 4.The polyisocyanate emulsion produced particleboard, 5 and their technological use was investigated in Example 4.
EKSEMPEL 2EXAMPLE 2
En typisk emulsion fremstilledes af 30 dele teknisk di-phenylmethan-4,4'-diisocyanat (MDI) og 70 dele 5¾ vandig 10 emulgatoropløsning på følgende måde:A typical emulsion was prepared from 30 parts of technical diphenylmethane-4,4'-diisocyanate (MDI) and 70 parts of 5¾ aqueous 10 emulsifier solution as follows:
Der fremstilles en 5% vandig opløsning af polyvinylalkoholen, idet f.eks. en polyvinylalkohol med handelsnavnet "Denka Poval B 17" opløses varmt i vand. Emulgeringen ved hjælp af et hurtigtgående røreværk kræver ca. 10-30 se-15 kunder.A 5% aqueous solution of the polyvinyl alcohol is prepared, e.g. a polyvinyl alcohol of the trade name "Denka Poval B 17" dissolves hot in water. The emulsification using a fast-moving agitator requires approx. 10-30 se-15 customers.
Til bestemmelse af stabiliteten af emulsionen sætter man isocyanatindholdet på tidspunktet for fremstillingen lig 100?□, og reduktionen måles løbende. Således fremkommer der ved den beskrevne 5% emulsion indenfor 7 timer kun 20 en reduktion på 1,5¾ klæbestofindhold.To determine the stability of the emulsion, the isocyanate content at the time of preparation is set to 100? □ and the reduction is continuously measured. Thus, at the described 5% emulsion within 7 hours, only a reduction of 1.5¾ adhesive content occurs.
De følgende tabeller viser en oversigt over de bestemte isocyanatindhold for en emulsion af 30 dele diphenylme-than-4,4'-diisocyanat med 70 dele 5¾ vandig emulgator-opløsning eller med 70 dele 4¾ vandig emulgatoropløsning.The following tables show an overview of the determined isocyanate content for an emulsion of 30 parts of diphenyl methane-4,4'-diisocyanate with 70 parts of 5¾ aqueous emulsifier solution or with 70 parts of 4¾ aqueous emulsifier solution.
10 14835910 148359
TABELTABLE
30 dele MDI 30 dele MDI30 parts MDI 30 parts MDI
70 dele 535 emulg.-opl. 70 dele 4¾ emulg.-opl.70 parts 535 emulsif. 70 parts 4¾ emulsion solution
Timer Isocyanat (35) Isocyanat (35) 5 0 100 100 0,5 99,9 99,4 1 99,5 98,5 2 99,7 99,8 3 99,0 98,3 10 4 99,4 98,7 5 98,3 95,0 6 97,6 97,4 7 98,5 95,7 EKSEMPEL 3 15 En typisk emulsion fremstilles af 38 dele teknisk diphe-nylmethan-4,4'-diisocyanat (MDI) og 62 dele 3,535 vandig emulgator-opløsning på følgende måde:Hours Isocyanate (35) Isocyanate (35) 5 100 100 0.5 99.9 99.4 1 99.5 98.5 2 99.7 99.8 3 99.0 98.3 10 4 99.4 98, EXAMPLE 3 A typical emulsion is prepared from 38 parts of technical diphenylmethane-4,4'-diisocyanate (MDI) and 62 parts of 3,535. aqueous emulsifier solution as follows:
Man fremstiller en 3,535 opløsning af 0,5 dele gelatine og 3 dele af en polyglycol (f.eks. med handelsnavnet "Pluri-20 ol") i varmt vand. I 62 dele af den afkølede opløsning indrøres 38 dele diphenylmethan-4,4'-diisocyanat. Emulgeringen ved hjælp af et hurtigtgående røreværk kræver ca.A 3,535 solution of 0.5 parts of gelatin and 3 parts of a polyglycol (for example, with the trade name "Pluri-20ol") is prepared in hot water. In 62 parts of the cooled solution, 38 parts of diphenylmethane-4,4'-diisocyanate are stirred. The emulsification using a fast-moving agitator requires approx.
10-15 sekunder.10-15 seconds.
Til bestemmelse af stabiliteten af emulsionen sætter man 25 isocyanatindholdet på tidspunktet for fremstillingen til 10035, og reduktionen måles løbende. Således fremkommer der ved den beskrevne 3835 emulsion indenfor 7 timer kun en reduktion på 2,635 klæbestofindhold.To determine the stability of the emulsion, the isocyanate content at the time of preparation is set to 10035 and the reduction is continuously measured. Thus, within the described 3835 emulsion within 7 hours, only a reduction of 2,635 adhesive content is obtained.
148359 11148359 11
Den følgende tabel wiser en oversigt over de bestemte iso-cyanatindhold for en emulsion af 38 dele diphenylmethan-4,4'-diisocyanat med 62 dele 3,5¾ vandig emulgatoropløsning.The following table gives an overview of the determined isocyanate content for an emulsion of 38 parts of diphenylmethane-4,4'-diisocyanate with 62 parts of 3.5¾ aqueous emulsifier solution.
5 TABEL5 TABLE
Timer Isocyanat (¾) 0 100,0 0,5 99,8 1 99,5 10 2 99,0 3 98,6 4 98,4 5 97,8 6 97,6 15 7 97,4 EKSEMPEL 4 - (Anvendelseseksempel til eksempel 1)Hours of Isocyanate (¾) 0 100.0 0.5 99.8 1 99.5 10 2 99.0 3 98.6 4 98.4 5 97.8 6 97.6 15 7 97.4 EXAMPLE 4 - (Application Example for example 1)
Granspåner, der var fremstillet under tekniske betingelser, og som har et fugtighedsindhold på ca. 4%, behandles i et sædvanligt limeapparat (Drais-blander) med de i de 20 følgende eksempler angivne klæbestofblandinger. Som hydro fober ingsmiddel tjener en 50K paraffinemulsion, mængden andrager i alle tilfælde IS fast voks i forhold til absolut tørre (atro) spåner. Til indstilling af et fugtig-hedsindhold af de harpiksbehandlede spåner på ca. 12S 25 sprøjtes den nødvendige mængde vand før harpiksbehandlin gen på spånerne.Spruce shavings made under technical conditions and having a moisture content of approx. 4%, is treated in a conventional adhesive (Drais mixer) with the adhesive mixtures indicated in the following 20 examples. As a hydrophobic agent, a 50K paraffin emulsion is used, the amount being in all cases IS solid wax relative to absolutely dry (atro) chips. For setting a moisture content of the resin treated chips of approx. 12S 25 the required amount of water is sprayed before the resin treatment on the chips.
Fremstillingen af klæbestofemulsionen foregår i henhold til den i eksempel 1 beskrevne metode. Klæbestofemulsio-nen fordeles ved hjælp af en blander sådan på spånerne, 30 at der foreligger 2-4S isocyanat på tørt træ. Som sammen ligning gennemføres forsøget med ikke emulgeret isocyanat.The preparation of the adhesive emulsion is carried out according to the method described in Example 1. The adhesive emulsion is distributed by means of a mixer such on the chips that there is 2-4S isocyanate on dry wood. By comparison, the test is performed with non-emulsified isocyanate.
12 14835912 148359
De således forbehandlede spåner tildannes i et forsøgs- drysseanlæg til en spånkage. Pressetemperaturen andrager 165 °C ved en pressetid på 4 minutter og et specifikt o tryk på 2,5 N/mm . På grund af klæbetendensen af isocya-5 naterne arbejdes der med separatorpapir. Tykkelsen af de . fremstillede spånplader andrager 18,5 mm, tætheden ca.The thus-prepared chips are formed in an experimental sprinkler system for a chip cake. The pressing temperature is 165 ° C at a pressing time of 4 minutes and a specific o pressure of 2.5 N / mm. Due to the adhesive tendency of the isocyanates, separator paper is used. The thickness of the. manufactured chipboard is 18.5 mm, the density approx.
610 kg/rn^.610 kg / rn ^.
Undersøgelsen af pladerne foretages i henhold til DIN 52 360-65.Examination of the plates is carried out in accordance with DIN 52 360-65.
10 Isocyanat ber. 100¾ Rent isocyanat Isocyanat på tørre spåner sammenligning emulgeretIsocyanate ber. 100¾ Pure isocyanate Isocyanate on dry shavings comparison emulsified
Plade undersøgelse 2¾ 3¾ 4¾ 2¾ 3¾ 4¾ Bøjebrudstyrke (N/mm^) 19,80 22,40 26,70 20,50 22,60 24,70Plate examination 2¾ 3¾ 4¾ 2¾ 3¾ 4¾ Bending breaking strength (N / mm ^) 19.80 22.40 26.70 20.50 22.60 24.70
Tværtrækstyrke V 20 (kp/cm^) 2,50 4,50 5,00 3,80 6,20 7,50 15 Tværtrækstyrke V 100 0,47 1,50 2,20 1,00 2,50 3,00Tensile strength V 20 (kp / cm 2) 2.50 4.50 5.00 3.80 6.20 7.50 15 Tensile strength V 100 0.47 1.50 2.20 1.00 2.50 3.00
Kvældning efter 2 h (¾) 2,20 1,70 1,10 1,70 1,50 1,20Swelling after 2 hours (¾) 2.20 1.70 1.10 1.70 1.50 1.20
Kvældning efter 24 h (¾) 13,00 10,00 8,50 11,30 9,10 7,80Swelling after 24 hours (¾) 13.00 10.00 8.50 11.30 9.10 7.80
Resultaterne viser, at der ved den samme klæbestofmængde under anvendelse af forholdsreglerne ifølge opfindelsen 20 opnås en bedre mekanisk styrke, og at følsomheden overfor vand tydeligt aftager.The results show that at the same amount of adhesive, using the precautions of the invention 20, a better mechanical strength is obtained and that the sensitivity to water clearly decreases.
EKSEMPEL 5 - (Anvendelseseksempel til eksempel 2)EXAMPLE 5 - (Application Example for Example 2)
Med den beskrevne emulsion, der er fremstillet på basis af 5¾ emulgatoropløsning, fremstillede man på sædvanlig 25 måde spånplader, og deres teknologiske anvendelighed blev undersøgt.With the described emulsion prepared on the basis of 5¾ emulsifier solution, chipboards were usually prepared in the usual way and their technological applicability was investigated.
148359 13148359 13
Isocyanat ber. 100?ό på absolut tørre (atro) spåner 2% 3?ί 4%Isocyanate ber. 100? Ό on absolutely dry (atro) chips 2% 3? 4%
Pladeundersøgelse i hen-5 hold til DIN 32 360-65 Bøjebrudstyrke (N/mm^) 20,2 23,2 24,2Plate examination according to DIN 32 360-65 Bending breaking strength (N / mm ^) 20.2 23.2 24.2
Tværtrækstyrke V 20 (kp/cm^) .3,5 5,6 7,6Transverse tensile strength V 20 (kp / cm 2) .3.5 5.6 7.6
Tværtrækstyrke \l 100 (kp/cnr) 0,1 0,9 2,3Transverse tensile strength \ l 100 (kp / cm) 0.1 0.9 2.3
Kvældning efter 2 h (%) 2,5 2,3 1,8 10 Kvældning efter 24 h (¾) 11,9 10,7 9,4 EKSEMPEL 6 - (Anvendelseseksempel til eksempel 3)Swelling after 2 hours (%) 2.5 2.3 1.8 10 Swelling after 24 hours (¾) 11.9 10.7 9.4 EXAMPLE 6 - (Application Example for Example 3)
Med den i eksempel 3 beskrevne emulsion, der blev fremstillet ved hjælp af 5% emulgatoropløsning, fremstillede man på sædvanlig måde spånplader, og deres teknologiske 15 anvendelighed blev undersøgt.With the emulsion described in Example 3, which was prepared by means of 5% emulsifier solution, chipboard was prepared in the usual way and their technological applicability was investigated.
Isocyanat ber. 100?ό på absolut tørre (atro) spåner 2% 3?ό 4?όIsocyanate ber. 100? Ό on absolutely dry (atro) chips 2% 3? Ό 4? Ό
Pladeundersøgelsfe i hen-20 hold til DIN 52 360-65 Bøjebrudstyrke (N/mm^) 21,2 23,4 26,2Plate study fair according to DIN 52 360-65 Bending breaking strength (N / mm ^) 21.2 23.4 26.2
Tværtrækstyrke V· 20 (kg/cm^) 3,1 5,9 7,9 ·Transverse tensile strength V · 20 (kg / cm 2) 3.1 5.9 7.9 ·
Tværtrækstyrke V 100 (kp/cm^) 0,2 1,4 2,4Transverse tensile strength V 100 (kp / cm 2) 0.2 1.4 2.4
Kvældning efter 2 h (¾) 2,4 2,4 2,2Swelling after 2 hours (¾) 2.4 2.4 2.2
Kvældning efter 24 h {%) 12,0 9,0 8,4Swelling after 24 hours (%) 12.0 9.0 8.4
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2703271 | 1977-01-27 | ||
DE2703271A DE2703271C3 (en) | 1977-01-27 | 1977-01-27 | Preparation of aqueous isocyanate emulsions |
DE2724363A DE2724363C3 (en) | 1977-05-28 | 1977-05-28 | Aqueous isocyanate emulsions for gluing chipboard |
DE2724364 | 1977-05-28 | ||
DE2724363 | 1977-05-28 | ||
DE2724364A DE2724364C2 (en) | 1977-05-28 | 1977-05-28 | Process for the preparation of aqueous polyisocyanate emulsions |
Publications (3)
Publication Number | Publication Date |
---|---|
DK38278A DK38278A (en) | 1978-07-28 |
DK148359B true DK148359B (en) | 1985-06-17 |
DK148359C DK148359C (en) | 1986-04-01 |
Family
ID=27187103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK38278A DK148359C (en) | 1977-01-27 | 1978-01-26 | PROCEDURE FOR MANUFACTURING Aqueous POLYISOCYANATE EMULSIONS FOR LIMITING CHIPBOARDS |
Country Status (7)
Country | Link |
---|---|
AT (1) | AT370749B (en) |
CH (1) | CH633303A5 (en) |
DK (1) | DK148359C (en) |
FR (1) | FR2378810A1 (en) |
IT (1) | IT1090372B (en) |
NL (1) | NL186170C (en) |
SE (1) | SE440363B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK152584B (en) * | 1980-04-18 | 1988-03-21 | Boise Cascade Corp | HANDY POLYISOCYANATE-LIGNIN ADHESIVE FOR ADJUSTABLE WOOD TABLES |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4670068A (en) * | 1981-02-19 | 1987-06-02 | Hercules Incorporated | Polyfunctional isocyanate crosslinking agents for propellant binders |
IT1174111B (en) * | 1984-05-30 | 1987-07-01 | Resem Spa | PROCEDURE FOR PREPARING AQUEOUS POLYISOCYANATE EMULSIONS |
US5106290A (en) * | 1987-04-14 | 1992-04-21 | Northrop Corporation | Assembly data model tool system |
GB8722973D0 (en) * | 1987-09-30 | 1987-11-04 | Ici America Inc | Aqueous polymer compositions |
EP1201695A1 (en) * | 2000-10-23 | 2002-05-02 | Huntsman International Llc | The use of polyisocyanate compositions as a binder for composite lignocellulosic materials |
EP1201696A1 (en) * | 2000-10-23 | 2002-05-02 | Huntsman International Llc | The use of polyisocyanate compositions as a binder for composite lignocellulosic materials |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5645955B2 (en) * | 1973-10-08 | 1981-10-29 | ||
GB1523601A (en) * | 1975-03-12 | 1978-09-06 | Ici Ltd | Sheets or moulded bodies |
-
1977
- 1977-12-28 IT IT31357/77A patent/IT1090372B/en active
-
1978
- 1978-01-02 NL NLAANVRAGE7800040,A patent/NL186170C/en not_active IP Right Cessation
- 1978-01-23 SE SE7800804A patent/SE440363B/en not_active IP Right Cessation
- 1978-01-24 CH CH73978A patent/CH633303A5/en not_active IP Right Cessation
- 1978-01-26 DK DK38278A patent/DK148359C/en not_active IP Right Cessation
- 1978-01-26 AT AT0058278A patent/AT370749B/en not_active IP Right Cessation
- 1978-01-27 FR FR7802356A patent/FR2378810A1/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK152584B (en) * | 1980-04-18 | 1988-03-21 | Boise Cascade Corp | HANDY POLYISOCYANATE-LIGNIN ADHESIVE FOR ADJUSTABLE WOOD TABLES |
Also Published As
Publication number | Publication date |
---|---|
DK148359C (en) | 1986-04-01 |
DK38278A (en) | 1978-07-28 |
CH633303A5 (en) | 1982-11-30 |
FR2378810A1 (en) | 1978-08-25 |
NL186170C (en) | 1990-10-01 |
SE440363B (en) | 1985-07-29 |
AT370749B (en) | 1983-04-25 |
NL186170B (en) | 1990-05-01 |
FR2378810B1 (en) | 1984-06-22 |
IT1090372B (en) | 1985-06-26 |
ATA58278A (en) | 1982-09-15 |
NL7800040A (en) | 1978-07-31 |
SE7800804L (en) | 1978-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4546039A (en) | Process for bonding lignocellulose-containing raw materials with a prepolymer based on a urethane-modified diphenylmethane diisocyanate mixture | |
US5128407A (en) | Urea extended polyisocyanates | |
FI64621B (en) | PROCEDURE FOR THE FRAMSTATION OF A CLEANER WITH A CROSS PARAGRAPH OF ANALYZING THE ENVIRONMENT OF AN ORGANIC P OLISOCYANAT | |
CA2244190C (en) | Method of producing press-moulding materials with polyisocyanate binders and using latent, heat-activable catalysts | |
US3870665A (en) | Process for making pressure molded lignocellulose articles comprising isocyanurate group forming mold release agent | |
EP0346059A2 (en) | Composite materials | |
RU2275390C2 (en) | Employment of polyisocyanate compositions as binding agent for composite lignocellulose materials | |
SE447391B (en) | BINDING COMPOSITION FOR THE PREPARATION OF FORMPRESSABLE LIGNOCELLULOSART ICLAR, FORMPRESSABLE AND FORMPRESSED LIGNOCELLULOSA COMPOSITION AND PROCEDURE FOR THE PREPARATION OF FORMPRESSED LINGOCELLULOSA COMPOSITION ARTICLES | |
JPS5950510B2 (en) | Manufacturing method of particle board | |
DK148359B (en) | PROCEDURE FOR MANUFACTURING Aqueous POLYISOCYANATE EMULSIONS FOR LIMITING CHIPBOARDS | |
US4260532A (en) | Aqueous isocyanate emulsions prepared with polyglycol and polymerized unsaturated acid amide | |
EP0013112A1 (en) | Emulsifiable compositions and aqueous emulsions of organic isocyanates, and process using them as binders for manufacturing lignocellulose sheets | |
DE2703271C3 (en) | Preparation of aqueous isocyanate emulsions | |
RU2608028C2 (en) | Adhesive composition and use thereof | |
US20030109604A1 (en) | Storage-stable isocyanate binders containing latent catalysts | |
US5130419A (en) | Process for preparing lignocellulosic bodies | |
JPS6340832B2 (en) | ||
US10414853B2 (en) | Method of manufacturing of press materials | |
NO844136L (en) | PROCEDURE FOR MANUFACTURING COMPOSITE, CASTED LIGNOCELLULOSIDE | |
EP0464781B1 (en) | Process for the preparation of aqueous polyisocyanate emulsions and emulsions obtained thereby | |
EP0335342B1 (en) | Aqueous emulsions of polyisocyanates and process for preparing them | |
JP4596352B2 (en) | Adhesive composition for lignocellulosic material, hot-press molded body using the same, and method for producing hot-press molded body | |
JP2001271051A (en) | Adhesive composition for lignocellulose-based material, and hot-press formed body and method for manufacturing the same using the adhesive composition | |
US20050020799A1 (en) | Alternative moisture cure catalysts and cold curing polyisocyanate adhesives prepared therefrom | |
CA2530700A1 (en) | Alternative moisture cure catalysts and cold curing polyisocyanate adhesives preparted therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PBP | Patent lapsed |