NO126953B - - Google Patents
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- NO126953B NO126953B NO02600/69A NO260069A NO126953B NO 126953 B NO126953 B NO 126953B NO 02600/69 A NO02600/69 A NO 02600/69A NO 260069 A NO260069 A NO 260069A NO 126953 B NO126953 B NO 126953B
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- Prior art keywords
- condensation
- formaldehyde
- mol
- products
- ammonium
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 71
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 38
- 235000013877 carbamide Nutrition 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 23
- 230000005494 condensation Effects 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 19
- 239000007859 condensation product Substances 0.000 claims description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- -1 amine salt Chemical class 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 150000003672 ureas Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 235000020354 squash Nutrition 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- AKTDWFLTNDPLCH-UHFFFAOYSA-N 1,1,3,3-tetrakis(hydroxymethyl)urea Chemical compound OCN(CO)C(=O)N(CO)CO AKTDWFLTNDPLCH-UHFFFAOYSA-N 0.000 description 1
- XJBNELXWSXDUFP-UHFFFAOYSA-N 1,1,3-tris(hydroxymethyl)urea Chemical compound OCNC(=O)N(CO)CO XJBNELXWSXDUFP-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
- C07D241/52—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
Fremgangsmåte for fremstilling av kationiske kondenseringsprodukter. Process for the production of cationic condensation products.
Det er kjent, at man ved kondensering It is known that one by condensation
av dicyandiamid, formaldehyd og ammoniumsalter får produkter, som kan anvendes til å forhøye våtektheten av substan-tive farvninger på cellulosefibere. Kondenseringen av dicyandiamid, urinstoff, ammoniumsalter og formaldehyd samt av cy-anamid, aldehyder og ammonium- eller of dicyandiamide, formaldehyde and ammonium salts give products which can be used to increase the wet fastness of substantive dyeings on cellulose fibres. The condensation of dicyandiamide, urea, ammonium salts and formaldehyde as well as of cyanamide, aldehydes and ammonium or
aminsalter er likeledes kjent. Til teknik-kens nivå hører også at ved kondensering amine salts are likewise known. The technique's level also includes that in the case of condensation
av kullstofforbindelser, som inneholder of carbon compounds, which contain
amino- eller iminogrupper, med formaldehyd og bestemte mengder ammoniumsalter dannes der produkter som er oppløse-lige i litt syre. amino or imino groups, with formaldehyde and certain amounts of ammonium salts are formed where products are soluble in a little acid.
De etter kjente fremgangsmåter erholdte kationiske kondenseringsprodukter The cationic condensation products obtained according to known methods
har en meget uensartet molekylstørrelse. have a very heterogeneous molecular size.
Produktenes egenskaper er dessuten van-skelig reproduserbare. For fikseringen av The product's properties are also difficult to reproduce. For the fixation of
garvestoffer eller utfelning av harpikssyre tanning substances or precipitation of resin acid
på cellulosefibrene kreves det imidlertid however, on the cellulose fibers it is required
produkter, hvis molekylstørrelse er mest products, whose molecular size is the most
mulig ensartet og som kan reproduseres as uniform and reproducible as possible
med sikkerhet, da der bare med slike produkter fåes jevne fikseringseffekter og utfellinger. Disse forutsetninger er særlig with certainty, as only with such products can even fixation effects and deposits be obtained. These assumptions are particular
viktige når det ønskes meget tungtopp-løselige utfellinger eller utfellinger av stoffer med liten anion. important when very poorly soluble precipitations or precipitations of substances with a small anion are desired.
Det er videre kjent ved kondensering It is further known by condensation
av karbamider med formaldehyd å tilsette of carbamides with formaldehyde to add
dicyandiamid og dessuten salter av ammoniakk eler aminer med anorganiske eller dicyandiamide and also salts of ammonia or amines with inorganic or
organiske syrer. Herunder tilsettes de syre-avspaltende forbindelser bare i katalytiske organic acids. Here, the acid-releasing compounds are added only in catalytic ones
mengder for at det skal fåes herdbare lim-harpikser. Ikke herdbare kationiske kon- quantities in order to obtain curable adhesive resins. Non-curable cationic con-
denseringsprodukter kan imidlertid ikke fåes på denne måte. however, densification products cannot be obtained in this way.
Ved foreliggende fremgangsmåte frem-stilles ikke herdbare kationiske kondenseringsprodukter ved den fremgangsmåte at på kjent måte erholdte kondenseringsprodukter av ensartet kondenseringsgrad av karbamider, f. eks. urinstoff, alkylurin-stoffer, acetylendiurinstoff eller diuretaner, og formaldehyd, eller formaldehyd avspaltende forbindelser, kondenseres i et annet trinn med dicyandiamid og salter av ammoniakk eller alifatiske aminer med anorganiske eller sterke organiske syrer og eventuelt ytterligere formaldehyd, eller en formaldehyd avspaltende forbindelse og det karakteristiske for fremgangsmåten er at det anvendes 1 til 3 mol ammonium- eller aminsalt, beregnet på 1 mol karbamid. Herved oppnås de kationiske, ikke herdbare kondenseringsprodukter av ønsket og ensartet molekylstørrelse. En formaldehyd avspaltende forbindelse i overensstemmelse med oppfinnelsen er f. eks. paraformaldehyd. In the present method, curable cationic condensation products are not produced by the method that, in a known manner, condensation products of a uniform degree of condensation of carbamides, e.g. urea, alkylureas, acetylene diurea or diurethanes, and formaldehyde, or formaldehyde-releasing compounds, are condensed in another step with dicyandiamide and salts of ammonia or aliphatic amines with inorganic or strong organic acids and possibly further formaldehyde, or a formaldehyde-releasing compound and the characteristic of the method is that 1 to 3 mol of ammonium or amine salt is used, calculated for 1 mol of carbamide. Hereby, the cationic, non-curable condensation products of the desired and uniform molecular size are obtained. A formaldehyde-releasing compound in accordance with the invention is e.g. paraformaldehyde.
Fordelaktig kan man i det annet trinn også innkondensere heksametylentetramin. Advantageously, hexamethylenetetramine can also be condensed in the second step.
Kondenseringsproduktene fra det før-ste, i og for seg kjente fremgangsmåtetrinn av karbamidene, f. eks. urinstoff, urinstoffderivater som glykolmonourin, eller diuretaner og formaldehyd kan frem-stilles ved kondensering i alkalisk eller surt medium. Molforholdet mellom karbamid og formaldehyd kan være forskjellig, i alminnelighet kommer i betraktning 2 til 4 mol på et mol karbamid. The condensation products from the first, per se known process step of the carbamides, e.g. urea, urea derivatives such as glycol monourine, or diurethanes and formaldehyde can be produced by condensation in an alkaline or acidic medium. The molar ratio between carbamide and formaldehyde can be different, in general 2 to 4 moles are taken into account on one mole of carbamide.
Som utgangsmateriale for det annet fremgangsmåtetrinn kan man anvende lav-molekylære forbindelser. Disse er f. eks. når urinstoff er kondensert med formaldehyd, forbindelser som dimetylolurinstoff, trimetylolurinstoff og tetrametylolurin-stoff. Imidlertid kan også anvendes de ved viderekondensering erholdte høyeremole-kylære, fremdeles vannoppløselige produkter. Man kan også anvende de ved kondensering ved pH-verdier under 7,0 erholdte allerede hydrofobe kondenseringsprodukter. Kondenseringsgraden av d^se produkter kan f. eks. kjennetegnes ved deres viskositet eller ved deres evne til å tåle vann. Man bestemmer f. eks. det tem-peraturpunkt ved hvilket 1 volumdel av kondenseringsoppløsningen fortynnet med 1 volumdel hett vann ved avkjøling nett-opp viser harpiksutskillelse og får således et mål for oppløseligheten og hermed for produktets kondenseringsgrad. Low-molecular compounds can be used as starting material for the second method step. These are e.g. when urea is condensed with formaldehyde, compounds such as dimethylolurea, trimethylolurea and tetramethylolurea. However, the higher molecular, still water-soluble products obtained by further condensation can also be used. You can also use the already hydrophobic condensation products obtained by condensation at pH values below 7.0. The degree of condensation of these products can e.g. characterized by their viscosity or by their ability to withstand water. One decides, e.g. the temperature point at which 1 part by volume of the condensation solution diluted with 1 part by volume of hot water on cooling shows resin separation and thus obtains a measure of the solubility and thus of the degree of condensation of the product.
Urinstoffderivater som kan kondenseres med formaldehyd, er f. eks. N-alkyl-eller N,N'-dialkylurinstoffer, hvis alkylres-ter er grupper som inneholder metyl-, etyl-, propyl- eller flere kullstoffatomer. Diuretaner får man f. eks. ved omsetning av 1,3-propandiol eller 1,4-butandiol med urinstoff. Urea derivatives that can be condensed with formaldehyde are e.g. N-alkyl or N,N'-dialkyl ureas, whose alkyl residues are groups containing methyl, ethyl, propyl or more carbon atoms. Diuretans can be obtained e.g. by reacting 1,3-propanediol or 1,4-butanediol with urea.
Overføringen av de nøytrale kondenseringsprodukter fra det første trinn til kationiske produkter med dicyandiamid, ammonium- eller aminsalter og eventuelt ytterligere formaldehyd er mulig etter flere fremgangsmåter. Man kan f. eks. tilsette komponentene fra det annet trinn uten videre til reaksjonssatsen i det første trinn. Man kan også konsentrere reaksjonssatsen fra det første trinn før videreforarbeidel-sen, f. eks. ved vakuuminndampning. Kondenseringen av det annet trinn utføres i surt miljø. Kondenseringstemperaturen kan ligge mellom 50 og 100°, og reaksjons-tiden kan andra til 15 til 120 minutter eller mere. Ved valg av passende reaksjonsbe-tingelser kan man på en lett reproduser-bar måte få kationiske kondenseringsprodukter av definert kondenseringsgrad. Kondenseringsgraden kan også her innstilles ved kontroll av viskositeten eller av det punkt, hvor der inntrer uklarhet (se Eksempel 2) eller av pH-verdien. The transfer of the neutral condensation products from the first step to cationic products with dicyandiamide, ammonium or amine salts and possibly additional formaldehyde is possible by several methods. One can e.g. add the components from the second step without further ado to the reaction batch in the first step. You can also concentrate the reaction rate from the first step before further processing, e.g. by vacuum evaporation. The condensation of the second step is carried out in an acidic environment. The condensation temperature can be between 50 and 100°, and the reaction time can vary from 15 to 120 minutes or more. By choosing suitable reaction conditions, cationic condensation products of a defined degree of condensation can be obtained in an easily reproducible manner. The degree of condensation can also be set here by checking the viscosity or the point where cloudiness occurs (see Example 2) or the pH value.
Ammoniumsalter av anorganiske og sterke organiske syrer kommer i betraktning. Nevnes skal f. eks. ammoniumklorid, Ammonium salts of inorganic and strong organic acids come into consideration. Mention should be made, e.g. ammonium chloride,
-bromid, -jodid, -sulfat, -nitrat, -fosfat, ammoniumformiat-, kloracetat. Som al'fa-tiske aminer for saltdannelsen skal f. eks. nevnes alkyl- eller <d>ialkylamin, likeledes alkylol- og alkylalkylolaminer, f. eks. me- -bromide, -iodide, -sulfate, -nitrate, -phosphate, ammonium formate, chloroacetate. As alpha amines for salt formation, e.g. mention is made of alkyl or <di>ialkylamine, likewise alkylol and alkylalkylolamines, e.g. me-
tylamin, dimetylamin, etyl- eller etanol-amin, trietanolamin. tylamine, dimethylamine, ethyl or ethanolamine, triethanolamine.
Aminene kan også tilsettes reaksjonssatsen som sådanne, såfremt der er tilstede et tilstrekkelig overskudd av syre. The amines can also be added to the reaction mixture as such, provided there is a sufficient excess of acid.
For mengden av reaksjonskomponen-tene kan gis følgende holdepunkter: beregnet på kondenseringsproduktet fra det første trinn, erholdt av 1 mol urinstoff, kan der anvendes omtrent 0,5 til 2 mol dicyandiamid, 1 til 3 mol ammonium- eller aminsalt eller blandinger av sådanne salter og i begge trinn tilsammen 3 til 6 mol formaldehyd. Formaldehydet kan anvendes i form av den handelsvanlige 30 pst.'s (vekt) eller 40 pst.'s (volum) vandige opp-løsning, men man kan imidlertid også tilsette det som paraformaldehyd til den vandige oppløsning av karbamidet. The following guidelines can be given for the quantity of the reaction components: calculated on the condensation product from the first step, obtained from 1 mol of urea, approximately 0.5 to 2 mol of dicyandiamide, 1 to 3 mol of ammonium or amine salt or mixtures of such salts can be used and in both steps a total of 3 to 6 moles of formaldehyde. The formaldehyde can be used in the form of the commercially available 30% (weight) or 40% (volume) aqueous solution, but it can also be added as paraformaldehyde to the aqueous solution of the carbamide.
Ved anvendelse av ammonium- respektive aminsalter av saltsyren får man produkter, som er oppløselige i vann i ethvert forhold, forutsatt at der i det minste ble innkondensert så mange mol formaldehyd som der er tilstede mol karbamid, dicyandiamid og ammonium respektive aminsalt. Derimot gir sulfater eller, rent generelt, anioner med stor ionradius be-grenset vannoppløselige kondenseringsprodukter. When using ammonium or amine salts of the hydrochloric acid, products are obtained which are soluble in water in any ratio, provided that at least as many moles of formaldehyde were condensed as there are moles of carbamide, dicyandiamide and ammonium or respective amine salt present. In contrast, sulfates or, quite generally, anions with a large ionic radius give limited water-soluble condensation products.
Vannoppløseligheten av de ikke i ethvert forhold med vann fortynnbare produkter eller bestandigheten av i og for seg fullstendig vannoppløselige kondenseringsprodukter like overfor fellende reagenser, f. eks. nitrat- eller sulfationer, kan for-høyes når man i det annet fremgangsmåtetrinn innkondenserer omtrent 1/6 til 1/3 mol heksametylentetramin. Denne ekstra forholdsregel er av særlig fordel, når der ved kondenseringen er blitt anvendt ammoniumsalter med anioner av stor radius, som NO—3, S04= og J—. Vannoppløselighe-ten av slike kondenseringsprodukter er nemlig i alminnelighet mindre enn vann-oppløseligheten av under forøvrig samme betingelser med f. eks. ammoniumklorid og ammoniumbromid erholdte produkter. Anvender man ved det første trinn for kon - denseringen mer enn 1 mol formaldehyd per mol karbamid og per de i det annet trinn tilsatte mol dicyandiamid og ammonium- eller aminsalter, så kan man omsette det overskytende mol formaldehyd ved tilsetning av den tilsvarende mengde ammoniakk til heksametylentetramin og gi avkall på tilsetningen av heksametylentetramin. The water solubility of the products that are not dilutable in any ratio with water or the stability of in and of themselves completely water-soluble condensation products equally towards precipitating reagents, e.g. nitrate or sulfate ions, can be increased when approximately 1/6 to 1/3 mol of hexamethylenetetramine is condensed in the second process step. This extra precaution is of particular advantage when ammonium salts with anions of large radius, such as NO—3, SO4= and J—, have been used during the condensation. Namely, the water solubility of such condensation products is generally less than the water solubility of under otherwise the same conditions with e.g. ammonium chloride and ammonium bromide obtained products. If more than 1 mol of formaldehyde per mol of carbamide and per mol of dicyandiamide and ammonium or amine salts added in the second step is used in the first step for the condensation, then the excess mol of formaldehyde can be converted by adding the corresponding amount of ammonia to hexamethylenetetramine and forego the addition of hexamethylenetetramine.
De i henhold til oppfinnelsen erholdte produkter kan på kjent måte, f. eks. ved forstøvningstørkning eller på valsetørkere, overføres til ikke-hygroskopiske pulvere. The products obtained according to the invention can be used in a known manner, e.g. by spray drying or on roller dryers, are transferred to non-hygroscopic powders.
Fremgangsmåteproduktene er fortrin-lige felnings- og fikseringsmidler for garvestoffer, harpikssyrer og farvestoffer. The process products are excellent folding and fixing agents for tanning substances, resin acids and dyes.
Eksempel 1: Example 1:
Den 30 pst.'s vandige oppløsning av 3 mol formaldehyd lar man koke under til-bakeløpskjøling med 1 mol urinstoff i en time ved en pH 7,0. Man tilsetter derpå 1 mol dicyandiamid og avkjøler til 40°. Etter tilsetning av 1 mol ammoniumklorid opphetes til 100° og der holdes i to timer ved denne temperatur. pH-verdien andrar til å begynne med til 3,8 og stiger med fremadstigende kondensering til 5,6 til 5,8. Man nøytraliserer nu med 20 pst.'s soda-oppløsning og får en klar oppløsning med 50 pst. innhold av faste stoffer av meget utpreget kationisk karakter. Forstøvnings-tørkningen gir et farveløst, ikke-hygro-skopisk pulver, som lett oppløser seg i vann og i ethvert forhold. The 30% aqueous solution of 3 moles of formaldehyde is allowed to boil under reflux with 1 mole of urea for one hour at a pH of 7.0. 1 mol of dicyandiamide is then added and cooled to 40°. After adding 1 mol of ammonium chloride, heat to 100° and hold for two hours at this temperature. The pH initially changes to 3.8 and rises with advancing condensation to 5.6 to 5.8. You now neutralize with a 20% soda solution and get a clear solution with a 50% solids content of a very pronounced cationic character. The spray-drying produces a colourless, non-hygroscopic powder, which dissolves easily in water and in any condition.
Eksempel 2: Example 2:
Den 30 pst.'s vandige oppløsning av 2 mol formaldehyd lar man koke under til-bakeløpskjøling med 1 mol urinstoff først ved pH 7,5, derpå ved 4,5 inntil en volumdel av en til 20° avkjølt prøve gir harpiksutskillelse med 1 volumdel vann. Viskositeten av satsen som ved begyn-nelsen av den sure kondensering, målt i Fordberger 3 mm, androg til 26 sekunder, er steget til 32 sekunder. Man tilsetter nu ytterligere 1 mol formaldehyd og dessuten 1 mol dicyandiamid, innfører etter avkjøling til 40 til 50° 1 mol ammoniumklorid og fortsetter kondenseringen ved 80 til 82°. Forløpet av kendenseringen gir føl-gende bilde: The 30% aqueous solution of 2 moles of formaldehyde is allowed to boil under reflux with 1 mole of urea first at pH 7.5, then at 4.5 until one part by volume of a sample cooled to 20° gives resin separation with 1 part by volume water. The viscosity of the batch, which at the beginning of the acidic condensation, measured in Fordberger 3 mm, was 26 seconds, has risen to 32 seconds. A further 1 mol of formaldehyde and also 1 mol of dicyandiamide are now added, after cooling to 40 to 50°, 1 mol of ammonium chloride is introduced and the condensation is continued at 80 to 82°. The course of the condensation gives the following picture:
Etter nøytralisering med soda får man en klar 50 pst.'s vandig oppløsning. Pro- After neutralization with soda, a clear 50% aqueous solution is obtained. Pro-
duktet har samme egenskaper som det produkt som ble erholdt etter Eksempel 1. the duct has the same properties as the product obtained according to Example 1.
Eksempel 3: Example 3:
600 vektsdeler urinstoff og 4000 vektsdeler 30 pst.'s vandig formaldehyd-oppløs-ning kondenseres ved 90° først i 20 minutter ved pH 7.6 og derpå i 30 minutter ved pH 4.0. Etter nøytralisering befries for vann i vakuum inntil en spesifik vekt 1.32/ 20°. Kondenseringsproduktet er en viskos 85 pst.'s oppløsning, i hvilken urinstoff og 600 parts by weight of urea and 4000 parts by weight of a 30% aqueous formaldehyde solution are condensed at 90° first for 20 minutes at pH 7.6 and then for 30 minutes at pH 4.0. After neutralization, water is freed in a vacuum up to a specific weight of 1.32/ 20°. The condensation product is a viscous 85% solution, in which urea and
formaldehyd foreligger i et molforhold formaldehyde is present in a molar ratio
1 : 3,7. 200 vektsdeler av den inndampede 1 : 3.7. 200 parts by weight of the evaporated
oppløsning blandes nu med 150 vektsdeler vann, 84 vektsdeler dicyandiamid, 30 vektsdeler av en 25 pst.'s vandig ammoniakkopp-løsning og 54 vektsdeler ammoniumklorid og oppvarmes til 100°. I løpet av 90 minutter stiger pH-verdien fra 3.9 til 5.8, uklarhetspunktet faller fra 20° til under null. Også dette produkt har tilsvarende egenskaper som det produkt som erholdes i henhold til Eksempel 1. solution is now mixed with 150 parts by weight of water, 84 parts by weight of dicyandiamide, 30 parts by weight of a 25% aqueous ammonia solution and 54 parts by weight of ammonium chloride and heated to 100°. Within 90 minutes the pH value rises from 3.9 to 5.8, the cloud point falls from 20° to below zero. This product also has similar properties to the product obtained according to Example 1.
Eksempel 4: Example 4:
Den 30 pst.'s vandige oppløsning av 4 mol formaldehyd lar man koke under til-bakeløpskjøling med 1 mol urinstoff i 30 minutter ved pH 7. I reaksjonssatsen opp-løser man derpå 1 mol dicyandiamid. Til den til 40° avkjølte oppløsning tilsetter man 0.66 mol ammoniakk (svarende til 1/6 mol heksametylentetramin) og 1 mol ammoniumklorid og kondenserer i 90 minutter ved 100°. Etter nøytralisering med soda får man et produkt hvis oppløsning er særlig uømfintlig like overfor fellende reagenser, f. eks. sulfationer. The 30% aqueous solution of 4 mol formaldehyde is boiled under reflux with 1 mol urea for 30 minutes at pH 7. 1 mol dicyandiamide is then dissolved in the reaction mixture. To the solution cooled to 40°, 0.66 mol of ammonia (corresponding to 1/6 mol of hexamethylenetetramine) and 1 mol of ammonium chloride are added and condensed for 90 minutes at 100°. After neutralization with soda, a product is obtained whose solution is particularly insensitive to precipitating reagents, e.g. sulfate ions.
Eksempel 5: Example 5:
Den 30 pst.'s vandige oppløsning av 3 mol formaldehyd lar man koke under til-bakeløpskjøling i 20 minutter med 1 mol urinstoff ved pH 7.5. Derpå tilsettes 1 mol dicyandiamid og etter avkjøling til 40° 1 mol ammoniumnitrat. Etter to timers kon-denseringstid ved 100° er visstnok pH-verdien steget til 5.6, men uklarhetspunktet ligger ved 30°, og produktet er ikke bland-bart med vann. Tilsetter man derimot før tilsetningen av ammoniumnitrater 1/6 mol heksametylentetramin så faller under de samme kondenseringsbetingelser uklarhetspunktet til 10° og produktet er for-tynnbart i vann i ethvert forhold. The 30% aqueous solution of 3 moles of formaldehyde is allowed to boil under reflux for 20 minutes with 1 mole of urea at pH 7.5. 1 mol of dicyandiamide is then added and, after cooling to 40°, 1 mol of ammonium nitrate. After two hours of condensing at 100°, the pH value has apparently risen to 5.6, but the cloud point is at 30°, and the product is not miscible with water. If, on the other hand, 1/6 mol of hexamethylenetetramine is added before the addition of ammonium nitrate, under the same condensation conditions the cloud point drops to 10° and the product is dilutable in water in any ratio.
Eksempel 6: Example 6:
1 mol acetylendiurinstoff opphetes ved 90° og pH 7,2 inntil oppløsning med 4 mol 30 pst.'s vandig formaldehydoppløsning. 1 mol of acetylenediurea is heated at 90° and pH 7.2 until dissolved with 4 mol of 30% aqueous formaldehyde solution.
Deretter tilsettes 1 mol dicyandiamid og 1 Then 1 mol of dicyandiamide and 1
mol ammoniumklorid. Man kondenserer moles of ammonium chloride. One condenses
videre ved 85 til 90°. pH-verdien av be-gynnelsesverdien 3.0 stiger i løpet av 80 further at 85 to 90°. The pH value of the initial value 3.0 rises during 80
minutter til 4.5, hvorpå der ved tilsetning minutes to 4.5, after which by addition
av sodaoppløsning innstilles en pH av 6.6. of soda solution, a pH of 6.6 is set.
Man får en vannklar, i et hvilket som helst You get a water clear, in any
forhold fortynnbar oppløsning av produktet med utpreget kationisk karakter. relatively dilute solution of the product with a pronounced cationic character.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO346571A NO128404B (en) | 1968-06-24 | 1971-09-17 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73919168A | 1968-06-24 | 1968-06-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO126953B true NO126953B (en) | 1973-04-16 |
Family
ID=24971204
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO02600/69A NO126953B (en) | 1968-06-24 | 1969-06-23 |
Country Status (13)
Country | Link |
---|---|
AT (1) | AT286306B (en) |
BE (1) | BE734969A (en) |
CH (1) | CH518312A (en) |
DE (1) | DE1931466C3 (en) |
DK (1) | DK128680B (en) |
FI (1) | FI52577C (en) |
FR (1) | FR2011565A1 (en) |
GB (1) | GB1218519A (en) |
IE (1) | IE33377B1 (en) |
IL (1) | IL32324A (en) |
NL (1) | NL159096B (en) |
NO (1) | NO126953B (en) |
SE (2) | SE350510B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE756621A (en) * | 1969-09-26 | 1971-03-25 | Hoffmann La Roche | PHENAZINE DERIVATIVES |
US3760075A (en) * | 1971-04-23 | 1973-09-18 | Hoffmann La Roche | Ultrasonic deaggregation of the copper complex of -methoxy-1-phenazinol 5,10-dioxide |
DE2216892C2 (en) * | 1971-04-23 | 1983-01-05 | F. Hoffmann-La Roche & Co AG, 4002 Basel | Aqueous suspension for the treatment of otological and ophthalmic infections |
CH574741A5 (en) * | 1971-05-07 | 1976-04-30 | Hoffmann La Roche |
-
1969
- 1969-06-02 IL IL32324A patent/IL32324A/en unknown
- 1969-06-06 CH CH872269A patent/CH518312A/en not_active IP Right Cessation
- 1969-06-19 FI FI691826A patent/FI52577C/en active
- 1969-06-20 DE DE1931466A patent/DE1931466C3/en not_active Expired
- 1969-06-20 GB GB31201/69A patent/GB1218519A/en not_active Expired
- 1969-06-20 IE IE853/69A patent/IE33377B1/en unknown
- 1969-06-23 BE BE734969D patent/BE734969A/xx not_active IP Right Cessation
- 1969-06-23 FR FR6920922A patent/FR2011565A1/fr not_active Withdrawn
- 1969-06-23 NL NL6909566.A patent/NL159096B/en not_active IP Right Cessation
- 1969-06-23 AT AT592769A patent/AT286306B/en not_active IP Right Cessation
- 1969-06-23 SE SE08901/69A patent/SE350510B/xx unknown
- 1969-06-23 NO NO02600/69A patent/NO126953B/no unknown
- 1969-06-23 SE SE00701/72A patent/SE361886B/xx unknown
- 1969-06-24 DK DK338469AA patent/DK128680B/en unknown
Also Published As
Publication number | Publication date |
---|---|
GB1218519A (en) | 1971-01-06 |
NL159096B (en) | 1979-01-15 |
DK128680B (en) | 1974-06-17 |
SE350510B (en) | 1972-10-30 |
FR2011565A1 (en) | 1970-03-06 |
DE1931466C3 (en) | 1979-06-13 |
IE33377L (en) | 1969-12-24 |
BE734969A (en) | 1969-12-23 |
NL6909566A (en) | 1969-12-30 |
AT286306B (en) | 1970-12-10 |
DE1931466B2 (en) | 1978-10-19 |
IL32324A0 (en) | 1969-08-27 |
IL32324A (en) | 1972-01-27 |
IE33377B1 (en) | 1974-06-12 |
FI52577C (en) | 1977-10-10 |
FI52577B (en) | 1977-06-30 |
CH518312A (en) | 1972-01-31 |
DE1931466A1 (en) | 1970-01-02 |
SE361886B (en) | 1973-11-19 |
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