DE867857C - Process for the preparation of the ammonium compounds sulfomethylated phenolic condensation products - Google Patents
Process for the preparation of the ammonium compounds sulfomethylated phenolic condensation productsInfo
- Publication number
- DE867857C DE867857C DEF2823D DEF0002823D DE867857C DE 867857 C DE867857 C DE 867857C DE F2823 D DEF2823 D DE F2823D DE F0002823 D DEF0002823 D DE F0002823D DE 867857 C DE867857 C DE 867857C
- Authority
- DE
- Germany
- Prior art keywords
- weight
- preparation
- parts
- condensation products
- ammonium compounds
- 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.)
- Expired
Links
- 239000007859 condensation product Substances 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 150000002989 phenols Chemical class 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 claims description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000010985 leather Substances 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 sulfomethyl groups Chemical group 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- MBSMABGDHZLUNL-UHFFFAOYSA-N benzo[c][1,2,5]benzodioxathiepine 11,11-dioxide Chemical compound O1OC2=CC=CC=C2S(=O)(=O)C2=CC=CC=C21 MBSMABGDHZLUNL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
- C07G99/002—Compounds of unknown constitution containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
Verfahren zur Herstellung der Ammoniumverbindungen sulfomethylierter phenolischer Kondensationsprodukte Es ist bekannt, Phenole oder phenolische Harze zur Überführung in wasserlösliche Form mit Formaldehyd und den Salzen der schwefligen Säure zu behandeln, wobei Sulfomethylgruppen die Löslichkeit bewirken. Diese Reaktion geht im verhältnismäßig stark alkalischen Gebiet vor sich unter Bildung der Salze der fixen Alkalien, je nachdem die Natrium-oder Kaliumverbindungen der schwefligen Säure bei der Umsetzung angewandt wurden. Die gewonnenen wasserlöslichen phenolischen Verbindungen enthalten gemäß ihrer Herstellung Aschebestandteile, deren Anwesenheit z. B. im Hinblick auf die Verwendung in der Gerberei unerwünscht ist, da bei der üblichen fortlaufenden Verwendung eine störende Anreicherung an Salzen fixer Alkalien in den Gerbbrühen entsteht.Process for the preparation of the sulfomethylated ammonium compounds Phenolic Condensation Products It is known phenols or phenolic resins for conversion into water-soluble form with formaldehyde and the salts of the sulphurous To treat acid, with sulfomethyl groups causing the solubility. This reaction takes place in the relatively strongly alkaline area with the formation of salts of the fixed alkalis, depending on the sodium or potassium compounds of the sulphurous Acid were used in the implementation. The obtained water-soluble phenolic According to their production, compounds contain ash constituents, their presence z. B. with regard to use in the tannery is undesirable because in the usual continuous use a disruptive accumulation of salts of fixed alkalis arises in the tanning liquor.
Es wurde nun gefunden, daß bei der Einwirkung von Formaldehyd und Ammoniumsalzen der schwefligen Säure, insbesondere Ammoniumbisulfit, auf Phenole bei Temperaturen über ioo°, zweckmäßig bei 13o bis 15o°, ebenfalls wasserlösliche Produkte erhalten werden. Die Umsetzung findet unter Druck und je nach der phenolischen Komponente im schwach sauren bis sehr schwach alkalischen, dem Neutralpunkt naheliegenden Gebiet, d. h. bei pI-I-Werten von etwa 4 bis 8, statt. Es entstehen dabei die Ammoniumverbindungen sulfomethylierter Phenole. Sie zeichnen sich vor den bekannten Umsetzungsprodukten durch das Fehlen von Aschebestandteilen aus. Die Möglichkeit, die Umsetzung erfindungsgemäß in diesem pH-Gebiet vorzunehmen, ist überraschend, da eine entsprechende Reaktion mit den Alkalisalzen der schwefligen Säure unter den gleichen Bedingungen nicht gelingt.It has now been found that when exposed to formaldehyde and Ammonium salts of sulphurous acid, especially ammonium bisulphite, on phenols at temperatures above 100 °, expediently at 13o to 15o °, likewise water-soluble Products are obtained. The implementation takes place under pressure and depending on the phenolic Component in weakly acidic to very weakly alkaline, close to the neutral point Area, d. H. at pI-I values of about 4 to 8, instead. It arise the ammonium compounds of sulfomethylated phenols. You stand out the known reaction products due to the lack of ash components. the Possibility of carrying out the implementation according to the invention in this pH range is Surprising, since a corresponding reaction with the alkali salts of the sulphurous Acid fails under the same conditions.
Als Ausgangsmaterial für die Durchführung der vorliegenden Erfindung seien folgende phenolischen Verbindungen genannt: Phenol, seine Homologen und die Halogensubstitutionsprodukte desselben, ferner mehrwertige - Phenole und höhenmolekulare Verbindungen, wie sie durch Umsetzung von Phenolen mit Formaldehyd oder anderen kernverbindend wirkenden Mitteln erhalten werden können. Auch kommen solche, phenolische Hydroxylgruppen enthaltende Verbindungen in Betracht, die durch Verkettung mit anderen als Kohlenstoff enthaltenden Brücken entstanden sind, so z. B. Dioxydiphenylsulfid oder -disulfid, ferner Dioxydiphenylsulfon, das als Zwischenprodukt für synthetische Gerbstoffe einen hervorragenden Platz einnimmt. Weiter kommen auch höhenmolekulare phenolische Verbindungen in Frage, wie sie z. B. aus den Ligninen oder den Ligninsulfon-'säuren erhältlich sind. Beispiel x In einem innen verbleiten Rührautoklav werden 94o Gewichtsteile Phenol mit 225o Gewichtsteilen einer 5ogewichtsprozentigen Lösung von Ammoniumbisulfit und 134o Gewichtsteilen Formaldehyd technisch 3o°/oig unter beständigem Rühren während i2 Stunden auf 15o° erhitzt. Das erhaltene wasserlösliche Kondensationsprodukt hat, mit einer organischen Säure auf einen End-pH-Wert der Gerblösung von ungefähr 4,4 gestellt, gut gerbende Eigenschaften und ergibt ein helles, volles Leder. Beispiel 2 165o Gewichtsteile eines technischen Gemisches zweiwertiger Phenole, bestehend aus etwa 43 bis 47 °/o Homo- bzw. Isohomobrenzcatechin, 38 bis 4o0/, Brenzcatechin, 7 bis 911/, Resorcin und 7 bis 90/, einwertigen Phenolhomologen, wie es bei der Extraktion von Braunkohlen-Schwelwässern anfällt, werden mit einer Mischung aus ii2o Gewichtsteilen Ammoniumbisulfitlösung 3o0 Be (= 50 % N H4 H S 03 Gehalt) und 15oo Gewichtsteilen Formaldehyd technisch 3o°/oig in einem Silberautoklav unter Rühren 3 Stunden bei 15o° kondensiert. Man erhält ein wasserlösliches Reaktionsprodukt, das bei einem pH-Wert von 4,3 bis 4,6 ein volles Leder mit bräunlicher Eigenfarbe ergibt.The following phenolic compounds may be mentioned as starting materials for carrying out the present invention: phenol, its homologues and its halogen substitution products, and also polyhydric phenols and high molecular weight compounds, as can be obtained by reacting phenols with formaldehyde or other agents that bind the nucleus. Also those compounds containing phenolic hydroxyl groups come into consideration which have arisen by chaining with bridges other than carbon-containing, so z. B. Dioxydiphenyl sulfide or disulfide, also Dioxydiphenylsulfon, which occupies an excellent place as an intermediate for synthetic tanning agents. Next, higher molecular weight phenolic compounds come into question, as z. B. from the lignins or the ligninsulphonic 'acids are available. EXAMPLE x In an internally leaded stirred autoclave, 940 parts by weight of phenol with 225o parts by weight of a 5% by weight solution of ammonium bisulfite and 1340 parts by weight of formaldehyde are heated to 150 ° for 12 hours with constant stirring. The water-soluble condensation product obtained has good tanning properties when adjusted with an organic acid to a final pH of the tanning solution of approximately 4.4 and results in a light, full leather. Example 2 165o parts by weight of a technical mixture of dihydric phenols, consisting of about 43 to 47% homo- or isohomobrenzcatechol, 38 to 400 /, pyrocatechol, 7 to 911 /, resorcinol and 7 to 90 /, monohydric phenol homologues, as in the extraction of lignite smoldering water is obtained with a mixture of 100 parts by weight of ammonium bisulfite solution 3o0 Be (= 50% N H4 HS 03 content) and 1500 parts by weight of formaldehyde technically 30% in a silver autoclave with stirring for 3 hours at 15o °. A water-soluble reaction product is obtained which, at a pH of 4.3 to 4.6, gives a full leather with a brownish inherent color.
Beispiel 3 33o Gewichtsteile Resorcin werden mit 45o Gewichtsteilen Ammoniumbisulfitlösung 5o"/oig und 225 Gewichtsteilen Formaldehyd technisch 3o°/oig in einem verbleiten Autoklav 3 Stunden bei i4o bis Z45° unter Rühren erhitzt. Das wasserlösliche, tief rotbraune Kondensationsprodukt liefert, mit einer organischen Säure gestellt, bei einem Gerb-pH-Wert von 3,8 bis 4,0 ein festes Leder von rotbrauner Eigenfarbe. Beispiel 4 5oo Gewichtsteile mit Ammoniak neutral gestelltes 4,4@-Dioxydiphenylsulfon vom Schmelzpunkt 247 bis 249° werden mit einer Mischung aus 3oo Gewichtsteilen Wasser, 40o Gewichtsteilen Ammoniumbisulfitlösung 5o°/oig und 35o Gewichtsteilen Formaldehyd technisch 3o°/oig in einem verbleiten Rührautoklav i2 Stunden bei 15o0 kondensiert. Man erhält ein lösliches Produkt, das bei einem Gerb-pH-Wert von 4,o bis 4,5 ein kerniges Leder mit guter Fülle ergibt. Beispiel 5 3oo Gewichtsteile eines in bekannter Weise aus einer kalkfreien Sulfitablauge durch Erhitzen mit Ätznatron auf 18o0 hergestellten, trockenen, entsulfonierten Sulfitablaugederivates werden in neutralem Zustand mit 225 Gewichtsteilen Wasser, 75 Gewichtsteilen Ammoniumbisulfitlösung 5o°/oig und 32,25 Gewichtsteilen Formaldehyd technisch 3o°/oig in einem verbleiten Rührautoklav 3 Stunden auf 14o° erhitzt. Das entstandene Reaktionsprodukt zeigt sich in jedem Verhältnis mit Wasser löslich. Es ergibt bei der quantitativen Bestimmung des Gerbstoffgehaltes nach dem Filterverfahren 42,804 Gerbstoffe und 7,20/0 Nichtgerbstoffe.Example 3 33o parts by weight of resorcinol become 45o parts by weight Ammonium bisulfite solution 50% and 225 parts by weight formaldehyde technically 30% heated in a leaded autoclave for 3 hours at 14 ° to 45 ° with stirring. That provides water-soluble, deep red-brown condensation product, with an organic Provided acid, a firm leather of reddish brown at a tanning pH of 3.8 to 4.0 Own color. Example 4 500 parts by weight of 4,4 @ -Dioxydiphenylsulfon neutralized with ammonia from a melting point of 247 to 249 ° with a mixture of 300 parts by weight of water, 40o parts by weight of ammonium bisulfite solution 50% and 35o parts by weight of formaldehyde technically 30% condensed in a leaded stirred autoclave for 12 hours at 150. A soluble product is obtained which, at a tanning pH of 4.0 to 4.5 grainy leather with good fullness results. Example 5 300 parts by weight of a known Way made from a lime-free sulphite waste liquor by heating with caustic soda to 18o0, dry, desulphonated sulphite waste liquor derivatives are in a neutral state with 225 parts by weight of water, 75 parts by weight of ammonium bisulfite solution 5o% and 32.25 parts by weight of formaldehyde technically 30% in a leaded stirred autoclave Heated to 14o ° for 3 hours. The resulting reaction product shows up in each Ratio soluble in water. It results from the quantitative determination of the tannin content after the filter process 42,804 tannins and 7.20 / 0 non-tanning agents.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2823D DE867857C (en) | 1944-01-18 | 1944-01-18 | Process for the preparation of the ammonium compounds sulfomethylated phenolic condensation products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2823D DE867857C (en) | 1944-01-18 | 1944-01-18 | Process for the preparation of the ammonium compounds sulfomethylated phenolic condensation products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE867857C true DE867857C (en) | 1953-02-19 |
Family
ID=7083499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF2823D Expired DE867857C (en) | 1944-01-18 | 1944-01-18 | Process for the preparation of the ammonium compounds sulfomethylated phenolic condensation products |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE867857C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1040564B (en) * | 1955-08-18 | 1958-10-09 | Bayer Ag | Process for the preparation of water-soluble condensation products containing sulfomethylene groups |
| DE1153857B (en) * | 1956-12-11 | 1963-09-05 | Bayer Ag | Process for tanning bare animals |
-
1944
- 1944-01-18 DE DEF2823D patent/DE867857C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1040564B (en) * | 1955-08-18 | 1958-10-09 | Bayer Ag | Process for the preparation of water-soluble condensation products containing sulfomethylene groups |
| DE1153857B (en) * | 1956-12-11 | 1963-09-05 | Bayer Ag | Process for tanning bare animals |
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