DE1225630B - Process for the preparation of stable concentrated aqueous solutions of methylolurea compounds - Google Patents
Process for the preparation of stable concentrated aqueous solutions of methylolurea compoundsInfo
- Publication number
- DE1225630B DE1225630B DEC22861A DEC0022861A DE1225630B DE 1225630 B DE1225630 B DE 1225630B DE C22861 A DEC22861 A DE C22861A DE C0022861 A DEC0022861 A DE C0022861A DE 1225630 B DE1225630 B DE 1225630B
- Authority
- DE
- Germany
- Prior art keywords
- moles
- methylolurea
- formaldehyde
- compounds
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical class NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 title claims description 20
- 239000007864 aqueous solution Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- -1 methylol groups Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 claims description 4
- 229950005308 oxymethurea Drugs 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 3
- 239000000243 solution Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
- C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL:Int. CL:
C07cC07c
Deutsche KL: 12 ο-17/03 German KL: 12 ο -17/03
Nummer: 1225 630Number: 1225 630
Aktenzeichen: C22861IVb/12oFile number: C22861IVb / 12o
Anmeldetag: 30. November 1960 Filing date: November 30, 1960
Auslegetag: 29. September 1966Opening day: September 29, 1966
Um Textilien knitter-, krumpf- und quellfest zu machen, werden sie mit Lösungen von Methylolverbindungen des Harnstoffs und mit säurespendenden Härtungsmitteln behandelt. Die Methylolverbindungen des Harnstoffs besitzen gegenüber den Methylolverbindungen anderer gebräuchlicher Stickstoffverbindungen die Vorteile des niedrigen Preises und der unnötigen Nachkondensation bei Verwendung von Ammoniumsalzen als Härtungsmittel. Vornehmlich werden solche Methylolverbindungen angewandt, in denen das Molverhältnis zwischen Harnstoff und Formaldehyd 1:1,6 bis 1: 2 beträgt. Diese Methylolharnstoffe haben jedoch den Nachteil, pastenförmige Produkte zu bilden, welche sich nur unter Erwärmen zur Behandlungsflotte verdünnen lassen und eine begrenzte Lagerfähigkeit besitzen. Eine konzentrierte wäßrige, leicht verdünnbare Lösung von Methylolverbindungen des Harnstoffs ist daher von größtem technischen Interesse.To make textiles crease, shrink and swell resistant, they are made with solutions of methylol compounds of urea and treated with acidic hardeners. The methylol compounds of urea have other common nitrogen compounds compared to the methylol compounds the advantages of the low price and the unnecessary post-condensation when using Ammonium salts as hardeners. Such methylol compounds are mainly used in where the molar ratio between urea and formaldehyde is 1: 1.6 to 1: 2. These methylolureas however, have the disadvantage of forming paste-like products which only dissolve when heated can be diluted to the treatment liquor and have a limited shelf life. A concentrated one aqueous, easily dilutable solution of methylol compounds of urea is therefore of greatest importance technical interest.
In der französischen Patentschrift 1 238 651 ist die Umsetzung von 3 Mol Methylolharnstoff mit 1 Mol Ammoniak beschrieben. Die erhaltenen Produkte sind starke Basen und bilden mit starken Säuren Salze. Die Produkte gemäß vorliegender Erfindung werden durch starke Säuren unlöslich und gehärtet. Sie enthalten im Gegensatz zu den Produkten der Vorveröffentlichung keine am Stickstoff gebundenen Wasserstoffatome, die zu einer Methylolbildung befähigt wären.In the French patent 1 238 651, the reaction of 3 moles of methylolurea with 1 mole Ammonia described. The products obtained are strong bases and form salts with strong acids. the Products according to the present invention become insoluble and hardened by strong acids. They contain in the In contrast to the products of the prior publication, no hydrogen atoms bonded to nitrogen, the would be capable of methylol formation.
Aus der USA.-Patentschrift 2 340 045 ist die Herstellung von Bis-ureidomethyl-alkylaminen aus Ammoniak oder primären Aminen und Monomethylolharnstoff sowie die eventuelle weitere Umsetzung mit Formaldehyd bekannt. Diese Bis-ureidomethyl-alkylamine werden bei Temperaturen von höchstens O0C gewonnen und lassen sich in kristalliner Form isolieren. Sie sind Basen und bilden auch mit starken Säuren Salze. Im Gegensatz dazu erfolgt die erfindungsgemäße Umsetzung der Amine mit Monomethylolharnstoff unter Erhitzen, und es entstehen keine in kristalliner Form gewinnbaren Verbindungen von basischem, salzbildendem Charakter. Soweit eine Umsetzung dieser basischen Verbindungen nach der USA.-Patentschrift mit Formaldehyd vorgesehen ist, entstehen naturgemäß auch andere Verbindungen. Außerdem ist bei dem Verfahren der USA.-Patentschrift nicht vorgesehen, daß alle Aminowasserstoffe in Methylolgruppen verwandelt werden müssen.US Pat. No. 2,340,045 discloses the preparation of bis-ureidomethyl-alkylamines from ammonia or primary amines and monomethylolurea and the possible further reaction with formaldehyde. These bis-ureidomethyl-alkylamines are obtained at temperatures of at most 0 ° C. and can be isolated in crystalline form. They are bases and also form salts with strong acids. In contrast, the inventive reaction of the amines with monomethylolurea takes place with heating, and no compounds of a basic, salt-forming character which can be obtained in crystalline form are formed. If these basic compounds are to be reacted with formaldehyde according to the USA patent, other compounds are naturally also formed. In addition, the US patent process does not provide that all amino hydrogens must be converted to methylol groups.
Das erfindungsgemäße Verfahren zur Herstellung stabiler konzentrierterwäßrigerLösungenvonMethylolharnstoffverbindungen
durch Umsetzung von Methylolharnstoff mit primären Aminen ist dadurch gekennzeichnet,
daß man ein primäres Amin mit 1 bis Verfahren zur Herstellung von stabilen
konzentrierten wäßrigen Lösungen von
MethylolharnstoffverbindungenThe process according to the invention for the preparation of stable, concentrated aqueous solutions of methylolurea compounds by reacting methylolurea with primary amines is characterized in that a primary amine is obtained with 1 to Process for the preparation of stable
concentrated aqueous solutions of
Methylolurea compounds
Anmelder:Applicant:
Chemische Fabrik Pfersee G. m. b. H.,
Augsburg, Färberstr. 4Chemical factory Pfersee G. mb H.,
Augsburg, Färberstr. 4th
Als Erfinder benannt:
Heinz Enders, Stadtbergen bei Augsburg;
Dipl.-Ing. Rolf Zörkendörfer, Augsburg;
Günter Pusch, Stadtbergen bei AugsburgNamed as inventor:
Heinz Enders, Stadtbergen near Augsburg;
Dipl.-Ing. Rolf Zörkendörfer, Augsburg;
Günter Pusch, Stadtbergen near Augsburg
4 Kohlenstoffatomen, wobei 1 Wasserstoffatom am endständigen Kohlenstoffatom durch eine weitere Aminogruppe oder durch eine Hydroxylgruppe ersetzt sein kann, mit 2 Mol Monomethylolharnstoff je Aminogruppe in konzentrierter wäßriger Lösung erhitzt und dann in üblicher Weise die restlichen Wasserstoffatome der Amidogruppen durch Behandlung mit Formaldehyd in Methylolgruppen überführt.4 carbon atoms, with 1 hydrogen atom on the terminal carbon atom through another Amino group or can be replaced by a hydroxyl group, with 2 moles of monomethylolurea each Amino group heated in concentrated aqueous solution and then the remaining ones in the usual way Hydrogen atoms of the amido groups converted into methylol groups by treatment with formaldehyde.
Als primäre Amine sind vorzugsweise solche mitThe primary amines are preferably those with
2 Kohlenstoffatomen und insbesondere Monoäthanolamin geeignet. Verwendbar ist aber auch Äthyl- oder2 carbon atoms and especially monoethanolamine suitable. But ethyl or ethyl can also be used
Propylamin oder Äthylendiamin. Es ist anzunehmen, daß die zwei Wasserstoffe der Aminogruppe mit den Hydroxylgruppen des Monomethylolharnstoffs unter Wasseraustritt reagieren.Propylamine or ethylenediamine. It can be assumed that the two hydrogens of the amino group with the Hydroxyl groups of the monomethylolurea react with the escape of water.
Die gebildeten Methylolverbindungen sind in konzentrierter Lösung beständig und vermögen noch die 3fache Molmenge Dimethylolharnstoff zu lösen und beim Lagern am Auskristallisieren zu verhindern.The methylol compounds formed are stable in concentrated solution and are still capable of the Dissolve 3 times the molar amount of dimethylolurea and prevent it from crystallizing during storage.
Ein besonders vorteilhaftes Herstellungsverfahren besteht darin, daß man eine Aminogruppe des Amins mit 2 Mol Monomethylolharnstoff in Gegenwart von etwa 2 bis 3 Mol Harnstoff und 6 bis 10 Mol Wasser umsetzt und anschließend durch Zusatz von Formaldehyd die restlichen Wasserstoffatome der Amidogruppen in Methylolgruppen überführt. Auf diese Weise sind Produkte mit besonders hohem Gehalt an Dimethylolharnstoff (3 Mol je Mol des Umsetzungsproduktes aus Methylolharnstoff und primärem Amin) erhältlich, während bei nachträglichem Zusatz nur etwa 2 Mol Dimethylolharnstoff zu haltbaren Lösungen eingearbeitet werden können.A particularly advantageous production process consists in that one amino group of the amine with 2 moles of monomethylolurea in the presence of about 2 to 3 moles of urea and 6 to 10 moles of water converts and then the remaining hydrogen atoms of the amido groups by adding formaldehyde converted into methylol groups. In this way, products are particularly high in content Dimethylolurea (3 mol per mol of the reaction product of methylolurea and primary amine) available, while with subsequent addition only about 2 moles of dimethylolurea to durable solutions can be incorporated.
Die Anwendung der erfindungsgemäß herstellbaren Lösungen erfolgt unter Zugabe säurespendender Mittel in üblicher Weise zur Behandlung von TextilienThe solutions that can be prepared according to the invention are used with the addition of acid-donating agents in the usual way for treating textiles
609 668/456609 668/456
aus natürlicher oder Regeneratcellulose. Eine Nachkondensation ist bei Verwendung von Ammoniumsalzen als Härtungskatalysator nicht erforderlich.made from natural or regenerated cellulose. Post-condensation occurs when using ammonium salts not required as a curing catalyst.
Die Lösung eines Vorkondensats, welches 2 Mol Monomethylolharnstoff und 3 Mol freien Harnstoff enthält und die durch Lösen von 5 Mol Harnstoff in 200 g 30°/0iger Formalinlösung (2MoI), Einstellen mit Triäthanolamin auf pH 7,4 und Erwärmen auf 400C während 2 Stunden erhalten worden ist, wird mit 1 Mol Monoäthanolamin während 60 Minuten unter Rückfluß gekocht. Es reagieren dabei die 2 Mol -Monomethylolharnstoff mitMonoäthanolamin.Schließlich werden 1100 g einer neutralisierten 30°/oigen Formalinlösung (11 Mol) zugesetzt und durch kurzes (15 Minuten).Erwärmen auf 90°C die Amidgruppen des freien Harnstoffs und des gebildeten Kondensationsproduktes methyloliert. Sofern dabei der pH- -Wert unter 7,0 sinkt, wird mit Triäthanolamin neutralisiert. The solution of a precondensate which contains 2 moles monomethylolurea and 3 moles of free urea and the strength by dissolving 5 mole of urea in 200 g of 30 ° / 0 formalin (2MoI), adjusting with triethanolamine to pH 7.4 and heating to 40 0 C has been obtained for 2 hours is refluxed with 1 mol of monoethanolamine for 60 minutes. It thereby react the 2 moles -Monomethylolharnstoff mitMonoäthanolamin.Schließlich 1100 g of a neutralized 30 ° / o by weight formalin (11 moles) was added and briefly (15 minutes) .Erwärmen to 90 ° C methylolated amide groups of free urea and condensation product formed . If the pH value sinks below 7.0, it is neutralized with triethanolamine.
Die erhaltene klare Lösung, die auch nach monatelangem Lagern unverändert bleibt, besitzt gegenüber anderen konzentrierten Harzvorkondensatlösungen, •wie denen des cyclischen Dimethyloläthylenharnstoffs sowie des verätherten Methylolharnstoffs, den Vorteil der wesentlich.besseren Reaktionsfreudigkeit, d. h., es ist z. B. bei Verwendung von Ammoniumsalzen als Härtungskatalysatoren eine besondere Nacherhitzung -der behandelten und getrockneten Textilien überflüssig.The clear solution obtained, even after months Storage remains unchanged, has, compared to other concentrated resin precondensate solutions, • like those of the cyclic dimethylolethylene urea as well as the etherified methylolurea, the advantage of the much better responsiveness, d. h., it is z. B. when using ammonium salts as curing catalysts, a special post-heating -of the treated and dried textiles superfluous.
Eine Lösung, die 2 Mol Monomethylolharnstoff und j 2 Mol freien Harnstoff enthält und die durch Lösen --■von · 4 Mol Harnstoff in 200 g 30°/0iger Formalinilösung (2 Mol), welche mit Triäthanolamin auf pH 7,4 - gestellt ist, durch l^stündiges Erwärmen auf 450C .erhalten worden ist, wird mit 1 Mol Äthylamin während 60 Minuten unter Rückfluß gekocht. Hierauf ^werden 800 g einer neutralisierten 30°/0igen Formalin-4ösung (8 Mol) zugesetzt und bei 90° C während ;" 15 Minuten die Methylolierung der noch vorhandenen -Amidgruppen vorgenommen. Sofern der pH-Wert "dabei unter 7,0 sinkt, wird mit Triäthanolamin neutralisiert. - 'A solution containing 2 mol monomethylolurea and j 2 moles of free urea and obtained by dissolving - ■ of x 4 M urea in 200 g of 30 ° / 0 hydrochloric Formalinilösung (2 moles) provided with triethanolamine to pH 7.4 - provided is, hour by heating l ^ has been .erhalten at 45 0 C, is cooked with 1 mol of ethylamine for 60 minutes under reflux. Then ^, 800 g of a neutralized 30 ° / 0 aqueous formalin 4ösung (8 moles) was added and at 90 ° C while. "; 15 minutes, the methylolation of the remaining -Amidgruppen carried If the pH" here below 7.0 decreases, is neutralized with triethanolamine. - '
; - B ei spiel 3; - Example 3
Eine Lösung von Monomethylolharnstoff, die in bekannter Weise aus 2 Mol Harnstoff und 2 Mol Formaldehyd (in Form neutralisierter 30°/0iger Lösung), erhalten worden ist, wird durch Kochen unter Rückfluß während 40 Minuten mit 1 Mol Propylamin umgesetzt. Das gebildete Kondensationsprodukt wird zusammen mit 2 Mol Harnstoff und 8 Mol Formaldehyd (mit Triäthanolamin neutralisierte Lösung) bei etwa 85° C vorkondensiert und dabei durch eventuelle Zugabe geringer Mengen Triäthanolamin für einen konstanten pH-Wert von etwa 7,3 bis 7,4 gesorgt.A solution of monomethylolurea, which in a known manner from 2 moles of urea and 2 moles of formaldehyde (neutralized in the form of 30 ° / 0 by weight solution), is obtained, is reacted by refluxing for 40 minutes with 1 mole of propylamine. The condensation product formed is precondensed together with 2 moles of urea and 8 moles of formaldehyde (solution neutralized with triethanolamine) at about 85 ° C. and a constant pH of about 7.3 to 7.4 is ensured by adding small amounts of triethanolamine.
Die wäßrige Lösung von 3 Mol Monomethylolharnstoff, die durch 5stündiges Erwärmen auf 3O0CThe aqueous solution of 3 mol monomethylolurea represented by 5stündiges heating at 3O 0 C
ίο einer Lösung von 180 g (3 Mol) Harnstoff in 300 g 30°/oiger, mit Triäthanolamin neutralisierter Formaldehydlösung gebildet ist, wird nach Zugabe von g (1,5 Mol) l-Hydroxy-3-aminopropan 50 Minuten am Rückfluß gekocht. Hierauf werden 600 g (6 Mol) neutralisierter 3O°/oiger Formalinlösung zugegeben und bei 85° C während 20 Minuten die Methylolierung der restlichen Amidogruppen vorgenommen. Dieses Produkt vermag 1,5 Mol Dimethylölharnstoff in Form einer 47%igen wäßrigen Paste beim Erhitzen auf 90° C zu lösen, und nach dem Abkühlen resultiert eine konzentrierte wäßrige, beständige Lösung.ίο a solution of 180 g (3 moles) of urea in 300 g of 30 ° / o sodium, triethanolamine neutralized with formaldehyde solution is formed is, after addition of g (1.5 mol) of l-hydroxy-3-aminopropane 50 minutes refluxed . 600 g (6 mol) of neutralized 30% formalin solution are then added and the remaining amido groups are methylolated at 85 ° C. for 20 minutes. This product is able to dissolve 1.5 mol of dimethyl oil urea in the form of a 47% strength aqueous paste when heated to 90 ° C., and after cooling a concentrated aqueous, stable solution results.
Claims (3)
Französische Patentschrift Nr. 1 238 651;
USA.-Patentschrift Nr. 2 340 045.Considered publications:
French Patent No. 1,238,651;
U.S. Patent No. 2,340,045.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC22861A DE1225630B (en) | 1960-11-30 | 1960-11-30 | Process for the preparation of stable concentrated aqueous solutions of methylolurea compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC22861A DE1225630B (en) | 1960-11-30 | 1960-11-30 | Process for the preparation of stable concentrated aqueous solutions of methylolurea compounds |
| FR880448A FR1312644A (en) | 1961-11-30 | 1961-11-30 | Process for the preparation of methylol compounds and products obtained |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1225630B true DE1225630B (en) | 1966-09-29 |
Family
ID=25969360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC22861A Pending DE1225630B (en) | 1960-11-30 | 1960-11-30 | Process for the preparation of stable concentrated aqueous solutions of methylolurea compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1225630B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2340045A (en) * | 1941-08-30 | 1944-01-25 | Gen Electric | Condensation product and process of making the same |
| FR1238651A (en) * | 1958-10-13 | 1960-08-12 | Marblette Corp | Process for preparing stable plastic combinations from methylol urea and products conforming to those obtained |
-
1960
- 1960-11-30 DE DEC22861A patent/DE1225630B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2340045A (en) * | 1941-08-30 | 1944-01-25 | Gen Electric | Condensation product and process of making the same |
| FR1238651A (en) * | 1958-10-13 | 1960-08-12 | Marblette Corp | Process for preparing stable plastic combinations from methylol urea and products conforming to those obtained |
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