DK155189B - PROCEDURE FOR THE PREPARATION OF A WATER-URINE FORMAL HYDRAULIC ADHESIVE AND APPLICATION OF THIS LIMED - Google Patents
PROCEDURE FOR THE PREPARATION OF A WATER-URINE FORMAL HYDRAULIC ADHESIVE AND APPLICATION OF THIS LIMED Download PDFInfo
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- DK155189B DK155189B DK537581A DK537581A DK155189B DK 155189 B DK155189 B DK 155189B DK 537581 A DK537581 A DK 537581A DK 537581 A DK537581 A DK 537581A DK 155189 B DK155189 B DK 155189B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
- C08G12/422—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds based on urea or thiourea
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Glass Compositions (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
iin
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Opfindelsen angår en fremgangsmåde til fremstilling af ' en vandig urinstofformaldehyd-trælim af den i indledningen til krav 1 angivne art samt anvendelse af denne lim.The invention relates to a process for the preparation of an aqueous urea formaldehyde glue of the kind specified in the preamble of claim 1 and to the use of this glue.
Det er kendt, at formaldehydkondensater af urinstof fra-5 spalter formaldehyd, især ved påvirkning af fugtighed.It is known that formaldehyde condensates of urea decompose formaldehyde, especially when affected by humidity.
Når man anvender dem som lim til fremstilling af træmaterialer (limharpikser), får man materialer, der under og efter fremstilling kan afgive formaldehyd til omgivelserne.When they are used as glue for the production of wood materials (glue resins), you get materials that can, during and after manufacture, release formaldehyde to the surroundings.
10 Som middel til påvirkning af denne ubehagelige egenskab tilsætter man til limen før forarbejdningen f.eks. fast eller frit urinstof. Man antager, at der, især i nærværelse af den naturlige træ- eller luftfugtighed, fremkommer en reaktion mellem urinstoffet og det frigjorte form-15 aldehyd, dvs. at urinstoffet fungerer som opfangnings-middel for formaldehydet.As a means of affecting this unpleasant property, one is added to the adhesive before processing, e.g. solid or free urea. It is believed that, especially in the presence of natural wood or humidity, a reaction occurs between the urea and the released formaldehyde, ie. that the urea acts as a scavenger for the formaldehyde.
Man kan også nedsætte forholdet mellem formaldehyd og bundet urinstof, hvilket forhold oprindeligt blev valgt til 1,6 til 1,8 (mol/mol), især på grund af den opnåeli-20 ge styrke af limningerne, hvorved tendensen hos konden saterne til igen at spaltes til de tilsvarende udgangsprodukter reduceres.It is also possible to reduce the ratio of formaldehyde to bound urea, which ratio was initially chosen to be 1.6 to 1.8 (mol / mol), especially because of the attainable strength of the adhesives, thereby reducing the tendency of the condensate being cleaved to the corresponding starting products is reduced.
Der er dog sat grænser for reduktionen af formaldehydandelen i limen, idet bindingsstyrken og også lagerstabili-25 teten aftager, således at "formaldehyd-fattige" urinstof-harpikslim i dag i almindelighed udviser et molforhold på mindst 1,4. Åbenbart har lagerstabiliteten intet at gøre med den kemiske stabilitet mod formaldehyd-tab.However, limits have been set for the reduction of the formaldehyde content in the adhesive, with the bond strength and also the storage stability decreasing, so that "formaldehyde-poor" urea resin adhesives generally exhibit at least a molar ratio of at least 1.4. Obviously, the storage stability has nothing to do with the chemical stability against formaldehyde loss.
Nu er det allerede fra DE-OS 22 62 197 kendt kontinuer-30 ligt og ved en flertrinsproces at fremstille urinstofharpikser med et slutteligt molforhold på 1,4 til 1,65, hvor-It is already known continuously from DE-OS 22 62 197 to produce uranium resins having a final molar ratio of 1.4 to 1.65, in a multi-step process, whereby
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2 ved man med henblik på forbedring af lagerstabiliteten i et af kondensationstrinene tilsætter en ringe mængde methanol og overholder en bestemt rækkefølge af forholdsregler. Alle de harpikser, der er fremstillet i henhold 5 til kendte flertrinsprocesser, har dog den ulempe, at lagerholdbarheden aftager med aftagende molforhold, hvilket der også er henvist til i det før angivne DE-OS. Resultatet af det i det angivne DE-OS forslag er ligeledes harpiksopløsninger, der mindst må udvise et molforhold 10 på 1,4.2, in order to improve the storage stability of one of the condensation steps, a small amount of methanol is added and a certain order of precautions is observed. However, all the resins produced in accordance with 5 known multistage processes have the disadvantage that the storage life decreases with decreasing molar ratio, which is also referred to in the previously mentioned DE-OS. The result of the proposed DE-OS proposal is also resin solutions which must exhibit at least a molar ratio 10 of 1.4.
Det er derfor opfindelsens formål at angive en fremgangsmåde til fremstilling af særligt formaldehydfattige urinstofharpiks lime, af den i indledningen til krav 1 angivne art, hvilke er lagerstabile og som desuden frembringer 15 en god bindingsstyrke.It is therefore the object of the invention to provide a process for the production of particularly formaldehyde-poor urea resin glue, of the kind specified in the preamble of claim 1, which is stable in storage and which further produces a good bonding strength.
Det har ifølge opfindelsen vist sig, at man ved en speciel et- eller totrinsproces og under samtidig anvendelse af en ringe mængde af en lavmolekylær mono- eller polyvalent alkohol (f.eks. methanol, ethanol eller iso-20 propanol samt f.eks. ethylenglycol), kan fremstille en lim med et molforhold på under 1,4, sådan som dette nærmere er angivet i' den kendetegnende del af krav 1, og at man kan anvende denne lim til fremstilling af spånplader.It has been found, according to the invention, that in a particular one or two step process and with the simultaneous use of a small amount of a low molecular weight mono- or polyhydric alcohol (eg methanol, ethanol or iso-propanol and e.g. ethylene glycol), can produce a glue having a molar ratio of less than 1.4, as further specified in the characterizing part of claim 1, and that this glue can be used for the manufacture of particle board.
Ifølge opfindelsen udviser urinstoflimene i den brugsfær-25 dige tilstand et molforhold mellem formaldehyd og urinstof på mindre end 1,4, fortrinsvis mindre end 1,35, indtil 1,05.According to the invention, in the ready-to-use condition the urea adhesives exhibit a molar ratio of formaldehyde to urea of less than 1.4, preferably less than 1.35, up to 1.05.
Derved foreligger slutteligt en del af urinstoffet i fri form, dvs. urinstofformaldehyd-trælimen fremstillet ved 30 fremgangsmåden ifølge opfindelsen er en vandig blanding af kondensater af urinstof og formaldehyd, frit urinstof og eventuelt en ringe residualmængde af frit formaldehyd.Finally, part of the urea is in free form, ie. The urea formaldehyde glue made by the process of the invention is an aqueous mixture of condensates of urea and formaldehyde, free urea and optionally a small residual amount of free formaldehyde.
I harpiksopløsninger, der udviser et tørstofindhold påIn resin solutions exhibiting a dry matter content of
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3 66,5%/ kan man nemlig, f.eks. ved nedbrydning med urease, måle et indhold på ca. 10 til 15% frit urinstof (vægt-%, beregnet i forhold til opløsningen), undertiden også mere. Dette svarer til en andel af f.eks. 0,25 til 0,40 mol, 5 beregnet på den totalt anvendte mængde urinstof.3 66.5% / can be namely, e.g. when decomposing with urease, measure a content of approx. 10 to 15% free urea (weight%, calculated in relation to the solution), sometimes even more. This corresponds to a proportion of e.g. 0.25 to 0.40 moles, 5 based on the total amount of urea used.
Med henblik på sondring mellem opfindelsen og kendt teknik må det iøvrigt anføres, at man til sædvanlige urinstofharpiks lime ikke kan tilsætte noget frit urinstof uden at lagerstabiliteten skades. Den allerede angivne 10 tilsætning foretages derfor i reglen først umiddelbart før forarbejdningen.For the purpose of distinguishing between the invention and the prior art, it should be further stated that, for ordinary urea resin glue, no free urea can be added without damaging the storage stability. As a rule, the 10 additions already mentioned are usually made immediately prior to processing.
Den væsentlige forskel mellem opfindelsen og den kendte teknik, der er beskrevet i DE-OS 22 62 197, beror på den overraskende erkendelse, at lagerstabiliteten af harpiks-15 opløsninger med særligt lav formaldehydandel og disses øvrige egenskaber påvirkes på fordelagtig måde, når kondensationen i det "formaldehyd-rige" første trin sker i et særligt stort omfang. Kondensationsgraden kan udtrykkes ved viskositeten af opløsningen og skal - ved 20 °C og i for-20 hold til 66,5% opløsning - andrage mindst 600, fortrinsvis mindst 700 mPas.The substantial difference between the invention and the prior art described in DE-OS 22 62 197 is due to the surprising recognition that the storage stability of resin solutions with particularly low formaldehyde content and their other properties are advantageously affected when the condensation in the "formaldehyde-rich" first step occurs to a particularly large extent. The degree of condensation can be expressed by the viscosity of the solution and must - at 20 ° C and relative to 66.5% solution - be at least 600, preferably at least 700 mPas.
Til udøvelse af fremgangsmåden går man sædvanligvis ud fra vandigt formaldehyd og urinstof eller fra - sædvanligvis urinstofholdige - formaldehyddonorer og urinstof.The practice is usually based on aqueous formaldehyde and urea or - usually urea - formaldehyde donors and urea.
25 Eventuelt kan man også anvende paraformaldehyd og lignende stoffer. Man lader sædvanligvis under svagt alkaliske betingelser en forreaktion (methylolering) forløbe, hvis formaldehyddonoren ikke allerede medfører en tilsvarende struktur. Velegnede koncentrerede formaldehyddonorer, der 30 også er kommercielle, er f.eks. dem, der er beskrevet i DE-OS 24 51 990 eller DE-OS 22 24 258. Også det i DE-OS 22 62 197 angivne såkaldte Formurea er velegnet.Optionally, paraformaldehyde and similar substances may also be used. A pre-reaction (methylation) is usually allowed under mildly alkaline conditions if the formaldehyde donor does not already have a similar structure. Suitable concentrated formaldehyde donors, which are also commercial, are e.g. those described in DE-OS 24 51 990 or DE-OS 22 24 258. The so-called Formurea also specified in DE-OS 22 62 197 is also suitable.
Ved forreaktionen falder pH-værdien sædvanligvis af sig selv og bringes nu ind i et pH-område mellem 4 og 6, for-In the pre-reaction, the pH usually decreases by itself and is now brought into a pH range between 4 and 6, preferably
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4 trinsvis mellem 4 og 5, hvorpå kondensationen sættes ind.4 incrementally between 4 and 5, and the condensation is inserted.
En tilstrækkelig høj temperatur, nemlig mellem 90 og 100 °C, må overholdes for at opnå tilstrækkeligt korte reaktionstider. Også en lavere pH-værdi forkorter reaktions-5 varigheden.A sufficiently high temperature, namely between 90 and 100 ° C, must be observed to achieve sufficiently short reaction times. A lower pH also shortens the reaction duration.
De sure betingelser under kondensationen muliggør en for-etheringsreaktion, således at den alkohol, der foreligger ifølge opfindelsen, formodentligt bliver indbygget i harpiksen.The acidic conditions during the condensation enable an etherification reaction so that the alcohol present in the invention is presumably incorporated into the resin.
10 Kondensationen fortsættes ifølge opfindelsen til en be grænset vandfortyndelighed, og tillige må man indstille på en kondensationsgrad, der svarer til et uklarhedspunkt på 50 &C eller derunder (en opløsning, der er fortyndet i forholdet 1:5 med varmt vand) eller en viskositet i den 15 færdige limopløsning på 600 mPas, fortrinsvis 700 eller derover (ved 20 °C, limopløsning med 66,5 vægt-% tørstofindhold). På grund af den kendsgerning, at harpikserne overhovedet kan kondenseres til en begrænset vandfortyn-delighed, foreligger der iøvrigt en væsentlig forskel i 20 forhold til fuldstændigt eller approximativt fuldstændigt foretherede harpikser, der som bekendt er vilkårligt vandfortyndelige ved praktisk talt enhver kondensationsgrad.The condensation is continued according to the invention to a limited water dilution, and also must be set to a degree of condensation corresponding to a cloud point of 50 & C or less (a solution diluted in a 1: 5 ratio with hot water) or a viscosity in water. the final glue solution of 600 mPas, preferably 700 or more (at 20 ° C, glue solution with 66.5 wt% solids content). Moreover, because of the fact that the resins can be condensed at all to a limited water dilution, there is a substantial difference in relation to completely or approximately completely etherified resins which, as is well known, are arbitrarily water-dilutable at virtually any degree of condensation.
Afhængigheden af viskositeten og koncentrationen af en 25 harpiksopløsning er et kendt fænomen; opfindelsen er der for ikke begrænset til sådanne harpikser, der foreligger i 66,5% opløsning. En stærkere fortyndet opløsning har som følge deraf en ringere mindsteviskositet end 600 mPas, og en koncentreret opløsning har en højere mindstevisko-30 sitet.The dependence on the viscosity and concentration of a resin solution is a known phenomenon; the invention is not limited to such resins present in 66.5% solution. As a result, a stronger diluted solution has a lower minimum viscosity than 600 mPas, and a concentrated solution has a higher minimum viscosity.
Den målte afhængighed repræsenteres ved en kurve, der er gengivet på figuren.The measured dependence is represented by a curve depicted in the figure.
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55
Kondensationsreaktionen afbrydes som sædvanligt ved indstilling af en pH-værdi på 7 til 8. Herefter foretager man i de fleste tilfælde et fremgangsmådetrin, ved hvilket overskydende vand ved moderat forhøjet temperatur 5 (40 til 70 °C) fjernes i et sådant omfang (såkaldt kon centrering), at kondensaterne netop lige kan håndteres.The condensation reaction is interrupted as usual by setting a pH of 7 to 8. Thereafter, in most cases, a process step is carried out at which excess water at moderately elevated temperature 5 (40 to 70 ° C) is removed to such an extent (so-called con centering) that the condensates can just be handled.
De efter det følgende trin fremkomne harpikser skal udvise mellem 60 og 70% harpiksmateriale. Hvad angår begrebet harpiksmateriale (tørstofindhold) skal der henvises 10 til følgende afsnit.The resins obtained after the next step must exhibit between 60 and 70% resin material. As regards the concept of resin material (dry matter content), reference should be made to 10 to the following sections.
Ifølge opfindelsen tilsætter man til kondensatet - eventuelt efter koncentrering - urinstof indtil et molforhold på under 1,4. Det er nødvendigt, at i det mindste en del deraf tilsættes ved afslutningen, dvs. efter koncentre- 15 ringen. Deh tekniske handling, der omfatter koncentrering, er ikke afgørende; hvis man gør brug heraf, foretrækkes det, at man tilsætter den totale urinstofmængde efter koncentreringen, og at man umiddelbart derpå afkøler til stuetemperatur.According to the invention, urea is added to the condensate - possibly after concentration - up to a molar ratio of less than 1.4. It is necessary that at least part of it be added at the end, ie. after concentration. This technical action involving concentration is not essential; if used, it is preferable to add the total amount of urea after the concentration and immediately cool to room temperature.
20 De limharpiksopløsninger, der fremkommer ifølge opfindelsen, kan forarbejdes på sædvanlig måde, dvs. under tilsætning af sædvanlige hærdemidler, på sædvanlige anlæg (f.eks. til spånpladefremstilling) og med sædvanlige forarbejdningstider .The adhesive resin solutions obtained according to the invention can be processed in the usual manner, i.e. with the addition of conventional curing agents, at conventional plants (eg for chipboard manufacturing) and with usual processing times.
25 Tørstofindholdet af limharpikser er vægten af en under definerede betingelser (temperatur, tid) tørret prøve-mængåe, beregnet i forhold til den oprindelige prøvevægt.The solids content of glue resins is the weight of a sample amount of dried under defined conditions (temperature, time), calculated in relation to the original sample weight.
Da der ved tørstofindholdsbestemmelsen ikke tørres til konstant vægt, drejer det sig om en konventionel metode.As the dry matter content determination is not dried to constant weight, this is a conventional method.
30 Man indvejer en prøvemængde på f.eks. ca. 1 g i en lille vejeskål (man bør derved drage omsorg for, at prøvemængden er repræsentativ; eventuelt bør man først homogenise-30 Weigh a sample amount of e.g. ca. 1 g in a small weighing bowl (care should be taken to ensure that the sample quantity is representative;
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6 re prøven ved omrystning eller omrøring). Bunden af den lille vejeskål skal være dækket med et nogenlunde regelmæssigt tykt lag af det produkt, der skal tørres.6 re the sample by shaking or stirring). The bottom of the small weighing bowl should be covered with a fairly regular layer of the product to be dried.
Prøven tørres enten i tørreskab ved 120 °C i 2 timer el-5 ler ved 103 °C i 15 timer. Den angivne tid og temperatur må nøje overholdes.The sample is either dried in a drying cabinet at 120 ° C for 2 hours or at 103 ° C for 15 hours. The specified time and temperature must be strictly observed.
Tørreskabet muliggør naturlig gennemluftiiing af udtagelige indsætningsbunde med en åben sigteflade på 70%. Med henblik på løbende kontrol af skabstemperaturen skal man 10 stikke et termometer gennem indføringsåbningen, hvorved skaladelen af termometeret ligger udenfor skabet, og hvorved temperaturføleren deraf befinder sig i det nyttige rum på den position, hvor de små afvejningsglas, der anbringes regelmæssigt fordelt, er stillet ind. Prø-15 verne må ikke berøre de opvarmede skabsvægge. Da temperaturforholdene i skabet forstyrres på grund af den stærke belægning med prøver, må man i afhængighed af skabets størrelse ikke tørre mere end f.eks. 10 prøver på en gang. Efter den foreskrevne tørretid afkøler og udvejer man 20 prøverne i en med partikelformet calciumchlorid forsynet ekssikkator.The drying cabinet allows natural ventilation of removable insert bottom with an open screen surface of 70%. For continuous control of the cabinet temperature, a thermometer must be inserted through the introductory opening, leaving the shell portion of the thermometer outside the cabinet, whereby the temperature sensor thereof is in the useful space at the position where the small balancing glasses, which are regularly distributed, are positioned. in. The samples must not touch the heated cupboard walls. As the temperature conditions in the cabinet are disturbed due to the strong coating of samples, depending on the size of the cabinet, do not dry more than e.g. 10 samples at a time. After the prescribed drying time, the 20 samples are cooled and weighed in a particulate calcium chloride desiccator.
Man gennemfører hver gang 3 bestemmelser og udregner den aritmetiske middelværdi.Three determinations are performed each time and the arithmetic mean is calculated.
EKSEMPEL 1 25 1 kg af-et vandigt forkondensationsprodukt, der i til urinstof bundet form indeholder 485 g formaldehyd i molforholdet 4:1, blandes med 323 g urinstof-opløsning (68%, 70 °C varm) og 131 g methanol, indstilles med 25% natronlud på en pH-værdi af 7,3 og opvarmes under omrøring til 30 90 °C. Man lader reaktionsblandingen henstå i 10 minut ter ved denne temperatur, hvorved pH-værdien synker. Der-EXAMPLE 1 25 kg of an aqueous precondensation product containing in urea-bound form 485 g of formaldehyde in a 4: 1 molar ratio are mixed with 323 g of urea solution (68%, 70 ° C warm) and 131 g of methanol are adjusted with 25% baking soda at a pH of 7.3 and heated with stirring to 90 ° C. The reaction mixture is allowed to stand for 10 minutes at this temperature, thereby lowering the pH. DER-
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7 på indstiller man med 20% myresyre til en pH-værdi på 4,5, og ved 90 til 98 °C kondenserer man til et uklarhedspunkt på 25 °C (1 del reaktionsblanding fortyndet med 5 dele varmt vand). Kondensationen forløber i ca. 50 mi-5 nutter. Viskositeten af en prøve andrager 620 mPas (målt ved 20 °C).At 7, set with 20% formic acid to a pH of 4.5, and at 90 to 98 ° C condense to a cloud point of 25 ° C (1 part reaction mixture diluted with 5 parts hot water). The condensation runs for approx. 50 mi-5 nuts. The viscosity of a sample is 620 mPas (measured at 20 ° C).
Efter at uklarhedspunktet er nået, afbrydes reaktionen ved tilsætning af 25% natronlud indtil en pH-værdi på 7,5, og der tilsættes 312 g varm urinstofopløsning. Efter 10 afkøling til 50 °C afdestillerer man under reduceret tryk 370 g vand, og derpå tilsætter man endnu en gang 312 g urinstofopløsning. Den således fremkomne harpiksopløsning afkøles hurtigt til under 20 °C. Den har følgende egenskaber: 15 Molforhold 1,1:1After the cloud point is reached, the reaction is quenched by the addition of 25% sodium hydroxide solution to a pH of 7.5 and 312 g of hot urea solution are added. After 10 cooling to 50 ° C, 370 g of water is distilled off under reduced pressure and then 312 g of urea solution is added again. The resin solution thus obtained is rapidly cooled to below 20 ° C. It has the following properties: 15 Mole ratio 1.1: 1
Vandforligelighed (20 °C) 1 : 3,5Water compatibility (20 ° C) 1: 3.5
Viskositet (20 °C) 708 mPas (20 °C) pH-værdi 8,6Viscosity (20 ° C) 708 mPas (20 ° C) pH 8.6
Lagerstabilitet ved 20 °C mindst 3 månederStorage stability at 20 ° C for at least 3 months
20 Geleringstid ved 50 °CGelling time at 50 ° C
(efter tilsætning af 10% 113 min.(after adding 10% 113 min.
af en 15% NH.Cl-opløsning) * *3of a 15% NH.Cl solution) * * 3
Massefylde ved 20 °C 1,2775 g/cinDensity at 20 ° C 1.2775 g / cin
Sammenligningsforsøgcomparison Tests
Hvis man går frem som beskrevet under eksempel 1, idet man dog ikke tilsætter methanol, adskiller den i så fald 25 fremkomne harpiks sig fra den i eksempel 1 fremkomne ved første øjekast ved en ringere vandfortyndelighed (1:1,1). Lagerstabiliteten andrager kun 1 måned under sammenlig-nélige betingelser.If you proceed as described in Example 1, except that methanol is not added, then the resin obtained in Example 1 differs from the one obtained at Example 1 at a lower water dilution (1: 1.1). Storage stability is only 1 month under comparable conditions.
Hvis man af begge harpikser i hvert tilfælde fremstiller 30 forsøgs-spånplader, ligger klippestyrken, målt ved den 2If each of the resins in each case produces 30 test particle boards, the cutting strength measured by the 2
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8 samme metode, ved 3,0 N/mm , når man som lim anvendte den i henhold til eksempel 1 fremstillede, mens man kun opnår 2 en værdi af 2,6 N/mm uden methanoltilsætning.8 the same method, at 3.0 N / mm, when used as the adhesive prepared according to Example 1, while only 2 obtains a value of 2.6 N / mm without methanol addition.
EKSEMPEL 2 5 Man går først frem som beskrevet i eksempel 1. Efter at have opnået uklarhedspunktet neutraliserer man og afkøler til 50 °C, man afdestillerer 180 g vand, og man tilsætter 425 kg fast urinstof til reaktionsblandingen. Efter at der er indstillet en pH-værdi på 8,9, afkøler man hurtigt 10 til under 20 °C. Den fremkomne harpiksopløsning har følgende egenskaber:EXAMPLE 2 First, proceed as described in Example 1. After reaching the cloud point, neutralize and cool to 50 ° C, distill 180 g of water and add 425 kg of solid urea to the reaction mixture. After a pH value of 8.9 is set, 10 is quickly cooled to below 20 ° C. The resulting resin solution has the following properties:
Viskositet: 719 mPas (20 °C) pH-værdi: 8,9Viscosity: 719 mPas (20 ° C) pH: 8.9
Lagerstabilitet ved 20 °C: mindst 4 måneder 15 Geleringstid ved 50 °C: 95 min.Storage stability at 20 ° C: at least 4 months 15 Gelation time at 50 ° C: 95 min.
(efter tilsætning af 10% af en 15% NH^Cl-opløsning)(after adding 10% of a 15% NH 2 Cl solution)
Massefylde ved 20 °C: 1,271 g/cm^ EKSEMPEL 3Density at 20 ° C: 1.271 g / cm 2 Example 3
Man går først frem som beskrevet i det foregående, hvorved man dog i stedet for 131 g methanol kun tilsætter 73 20 g. Kondensationen fortsættes i ca. 30 minutter.It is first proceeded as described above, whereby instead of 131 g of methanol only 73 20 g are added. The condensation is continued for approx. 30 minutes.
Efter indstilling af en pH-værdi på 6,6 afdestillerer man 275 g vand under reduceret tryk ved 50 °C. Efter at der (ligesom ovenfor) er tilsat 637 g urinstofopløsning, afkøler man hurtigt opløsningen, og den til oplagringen 25 tilsigtede pH-værdi indstilles.After setting a pH of 6.6, 275 g of water is distilled off under reduced pressure at 50 ° C. After adding (as above) 637 g of urea solution, the solution is rapidly cooled and the pH value intended for storage 25 is adjusted.
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Egenskaber af harpiksopløsningen:Properties of the resin solution:
Viskositet: 717 mPas (20 °C) pH-værdi: 8,95Viscosity: 717 mPas (20 ° C) pH: 8.95
Lagerstabilitet: mindst 3 måneder 5 Geleringstid ved 50 °C: (efter tilsætning af 10% 73 min.Storage stability: at least 3 months 5 Gelling time at 50 ° C: (after addition of 10% 73 min.
af en 15% NH^Cl-opløsning):of a 15% NH 3 Cl solution):
Massefylde ved 20 °C: 1,280 g/cm^ EKSEMPEL 3Density at 20 ° C: 1,280 g / cm 2 Example 3
Man går frem som beskrevet i oksempel 3, men i stedet for 10 methanol anvender man en lige så stor mængde ethanol.Proceed as described in Example 3, but instead of methanol, an equal amount of ethanol is used.
Man opnår en opløsning med følgende egenskaber:A solution with the following properties is obtained:
Viskositet: 735 mPas (20 °C) pH-værdi: 8,65Viscosity: 735 mPas (20 ° C) pH: 8.65
Lagerstabilitet: mindst 3 måneder 15 EKSEMPEL 5 3744 kg af en opløsning, der på udregningsbasis indeholder et forkondensationsprodukt af 1872 kg formaldehyd og 936 kg urinstof, indføres sammen med 824 kg af en 68%, 70 °C varm urinstofopløsning, 358 kg methanol og 130 kg 20 af en 25% ammoniak-opløsning i en opvarmelig og afkølelig rørebeholder med et indhold på 6 nf*; derved indstiller der sig en pH-værdi på 8,3, som ved opvarmning til ca. 90 °C synker til 7,2 .Temperaturen holdes i 10 minutter ved denne pH-værdi. Derpå tilsættes 600 kg 68% urin-25 stofopløsning, og pH-værdien indstilles med 10% myresyre på en værdi af 4,5-4,6. Opløsningen omsættes under omrøring ved 98 °C i så lang tid, at der opnås et uklarhedspunkt (1:5 med vand) på 30 til 32 °C. Derpå indstillestil en pH-værdi på 6,6 med 25% natronlud.Storage stability: at least 3 months EXAMPLE 5 3744 kg of a solution containing, on a calculation basis, a pre-condensation product of 1872 kg of formaldehyde and 936 kg of urea are introduced together with 824 kg of a 68%, 70 ° C urea solution, 358 kg of methanol and 130 20 kg of a 25% ammonia solution in a heatable and coolable stirrer having a content of 6 nf *; thereby a pH value of 8.3 is adjusted, which when heated to approx. 90 ° C drops to 7.2. The temperature is kept for 10 minutes at this pH. Then 600 kg of 68% urine solution is added and the pH is adjusted with 10% formic acid to a value of 4.5-4.6. The solution is reacted with stirring at 98 ° C for so long that a cloud point (1: 5 with water) of 30 to 32 ° C is obtained. Then set a pH of 6.6 with 25% baking soda.
DK 155189 BDK 155189 B
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Umiddelbart derpå tilsættes yderligere 772 kg 68% varm urinstofopløsning. Ved hjælp af en cirkulationspumpe overføres opløsningen til et inddampningsanlæg. Efter tilsætning af yderligere 598 kg 68% urinstofopløsning 5 bliver tyndlimen ved 100 mbar og 48 °C indirekte koncentreret ved hjælp af 11 bar damp til en massefylde på 1,23 g/cm3 ved 48 °C.Immediately thereafter, an additional 772 kg of 68% hot urea solution is added. By means of a circulation pump, the solution is transferred to an evaporation plant. After adding an additional 598 kg of 68% urea 5, the thin adhesive at 100 mbar and 48 ° C is indirectly concentrated using 11 bar of steam to a density of 1.23 g / cm 3 at 48 ° C.
Den således fremkomne reaktionscharge afkøles ved hjælp af pladekølere eller afspændingsafkøling meget hurtigt 10 til en temperatur af 20 °C. Derpå indstiller man meget hurtigt på den ønskede pH-værdi ved hjælp af 25% natronlud.The reaction charge thus obtained is cooled by plate coolers or relaxation cooling very quickly to a temperature of 20 ° C. Then the desired pH value is adjusted very quickly with 25% baking soda.
Kendingsdata:Distinguishing features:
Viskositet: 1 147 mPas 15 pH-værdi: 8,8Viscosity: 1,147 mPas pH: 8.8
Lagerstabilitet ved 20 °C: mindst 3 månederStorage stability at 20 ° C: at least 3 months
Geleringstid ved 20 °C 80 min.Gelling time at 20 ° C 80 min.
(efter tilsætning af 10% af en 15% NH^Cl-opløsning):(after adding 10% of a 15% NH 2 Cl solution):
Massefylde ved 20 °C: 1,27 g/cm3Density at 20 ° C: 1.27 g / cm 3
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803046033 DE3046033A1 (en) | 1980-12-06 | 1980-12-06 | METHOD FOR THE PRODUCTION OF GLUE RESIN |
DE3046033 | 1980-12-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
DK537581A DK537581A (en) | 1982-06-07 |
DK155189B true DK155189B (en) | 1989-02-27 |
DK155189C DK155189C (en) | 1989-07-10 |
Family
ID=6118481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK537581A DK155189C (en) | 1980-12-06 | 1981-12-04 | PROCEDURE FOR THE PREPARATION OF A WATER-URINE FORMAL HYDRAULIC ADHESIVE AND APPLICATION OF THIS LIMED |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0053762B1 (en) |
AT (1) | ATE20593T1 (en) |
DE (2) | DE3046033A1 (en) |
DK (1) | DK155189C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0103131A3 (en) * | 1982-09-10 | 1985-11-06 | Borden, Inc. | Amino-formaldehyde resins and use thereof in lignocellulosic composites |
GB8404758D0 (en) * | 1984-02-23 | 1984-03-28 | Bip Chemicals Ltd | Resin manufacture |
US6356656B1 (en) | 1994-06-17 | 2002-03-12 | Canon Kabushiki Kaisha | Contour-information extraction apparatus and method |
BRPI0513971A (en) | 2004-07-30 | 2008-05-20 | Hexion Specialty Chemicals Inc | aqueous reaction product of a composition, curable urea / formaldehyde resin composition, methods for the manufacture thereof, and for the manufacture of a reconstituted wood product, reconstituted wood panel, and concentrate for forming an intensifying composition of the polymerization |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB546410A (en) * | 1939-12-08 | 1942-07-13 | Du Pont | Improvements in or relating to the manufacture of urea-formaldehyde resinous composit |
US2881153A (en) * | 1955-03-18 | 1959-04-07 | American Cyanamid Co | Stable thiourea and urea mixed resins and their preparation |
IT951964B (en) * | 1971-12-27 | 1973-07-10 | Sir Soc Italiana Resine Spa | PERFECTED PROCESS FOR THE PREPARATION OF RESINS FROM UREA AND FORMALDEHYDE |
FR2199543A1 (en) * | 1972-09-21 | 1974-04-12 | Nobel Hoechst Chimie | U-F resin prodn using two-stage process, - esp for wood chip boards mfr |
DE2334380B1 (en) * | 1973-07-06 | 1974-09-05 | Basf Ag | Process for making a wood glue |
GB1480787A (en) * | 1975-09-11 | 1977-07-27 | Ciba Geigy Ag | Ureaformaldehyde resins |
DE2745809A1 (en) * | 1977-10-12 | 1979-04-26 | Basf Ag | Urea!-formaldehyde! resin soln. contg. sulphite waste liquor - as wood glue with better pre-bonding strength |
DE2825590C2 (en) * | 1978-06-10 | 1983-05-05 | Th. Goldschmidt Ag, 4300 Essen | Process for the production of thermosetting urea-formaldehyde resins and their use |
-
1980
- 1980-12-06 DE DE19803046033 patent/DE3046033A1/en not_active Withdrawn
-
1981
- 1981-11-26 EP EP81109921A patent/EP0053762B1/en not_active Expired
- 1981-11-26 DE DE8181109921T patent/DE3174904D1/en not_active Expired
- 1981-11-26 AT AT81109921T patent/ATE20593T1/en active
- 1981-12-04 DK DK537581A patent/DK155189C/en active
Also Published As
Publication number | Publication date |
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ATE20593T1 (en) | 1986-07-15 |
DE3174904D1 (en) | 1986-08-07 |
EP0053762A1 (en) | 1982-06-16 |
DK155189C (en) | 1989-07-10 |
EP0053762B1 (en) | 1986-07-02 |
DE3046033A1 (en) | 1982-07-15 |
DK537581A (en) | 1982-06-07 |
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