DE1068010B - Process for the production of polyureas - Google Patents
Process for the production of polyureasInfo
- Publication number
- DE1068010B DE1068010B DENDAT1068010D DE1068010DA DE1068010B DE 1068010 B DE1068010 B DE 1068010B DE NDAT1068010 D DENDAT1068010 D DE NDAT1068010D DE 1068010D A DE1068010D A DE 1068010DA DE 1068010 B DE1068010 B DE 1068010B
- Authority
- DE
- Germany
- Prior art keywords
- polyureas
- phosgene
- polyamines
- diamines
- imidazole
- 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
- 229920002396 Polyurea Polymers 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 title description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbamate Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N carbamoyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- -1 hydrochloric acid amine salts Chemical class 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RTZHEHKDVQNGKO-UHFFFAOYSA-N C(=O)(Cl)Cl.[N-]=C=O Chemical compound C(=O)(Cl)Cl.[N-]=C=O RTZHEHKDVQNGKO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000001588 bifunctional Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229960000539 carbamide Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHES /M*m, PATENTAMTGERMAN / M * m, PATENT OFFICE
kl. 39c 6kl. 39c 6
B 43906 IVb/39 c B 43906 IVb / 39 c
ANMELDETAG: 14.MÄRZ1957REGISTRATION DATE: MARCH 14, 1957
BEKANNTMACHUNG
DER ANMELDUNG
UND AUSGABE DER
AUSLEGESCHRIFT: 29. OKTOBER 1959NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: OCTOBER 29, 1959
Die Polykondensation bifunktioneller Verbindungen mit von der Kohlensäure abgeleiteten funktionellen Gruppen ist oft bearbeitet worden, ohne daß technisch verwertbare Verfahren entwickelt werden konnten. Erst in letzter Zeit wurde die Darstellung von Polykohlensäureester!! aus Phosgen und Dioxydiphenylalkanen bei Anwesenheit von säurebindenden Mitteln beschrieben und deren Darstellung bis zur technischen Reife entwickelt (vgl. Angew. Chem., 68 [1956], S. 633). Die Umsetzung von Dioxydiphenylalkanen mit Phosgen in Gegenwart säurebindender Mittel verläuft hierbei nach folgender Gleichung:The polycondensation of bifunctional compounds with functional groups derived from carbonic acid has often been worked on without being technically usable processes could be developed. Only recently has the representation of polycarbonate !! described from phosgene and dioxydiphenylalkanes in the presence of acid-binding agents and their representation up to technical Maturity developed (cf. Angew. Chem., 68 [1956], p. 633). The implementation of dioxydiphenylalkanes with phosgene in the presence of acid-binding agents, this proceeds according to the following equation:
OH+ λ; CO Cl2 OH + λ; CO Cl 2
Verfahren zur Herstellung
von PolyharnstoffenMethod of manufacture
of polyureas
Anmelder:Applicant:
P. Beiersdorf & Co. Aktiengesellschaft,
Hamburg 20, Unnastr. 48P. Beiersdorf & Co. Aktiengesellschaft,
Hamburg 20, Unnastr. 48
Dipl.-Chem. Dr. Reinhold Juhrich,Dipl.-Chem. Dr. Reinhold Juhrich,
Hamburg-Lokstedt,
ist als Erfinder genannt wordenHamburg-Lokstedt,
has been named as the inventor
Harnstoffe, Carbamidsäurechloride oder Isocyanate. Symmetrische Harnstoffe werden immer dann gebildet, wenn Phosgen mit einem Überschuß von umzusetzendem Amin zusammentrifft. Wenn man jedoch 25 freie aliphatische oder aromatische Amine zu einer Lösung von überschüssigem Phosgen in einem iner- ->- +2NaCl ten Lösungsmittel unter Kühlung hinzugibt, so entUreas, carbamic acid chlorides or isocyanates. Symmetrical ureas are always formed when phosgene meets an excess of amine to be converted. However, if you add 25 free aliphatic or aromatic amines to a solution of excess phosgene in an inert -> - + 2NaCl th solvent with cooling, so ent
stehen nicht die entsprechenden Harnstoffe, sondern es wird eine Mischung von CarbamidsäurechloridenThe corresponding ureas are not available, but a mixture of carbamic acid chlorides
Werden an Stelle von Dioxydiphenylalkanen Amine 30 und salzsauren Aminsalzen gebildet, die dann durch mit Phosgen umgesetzt, so entstehen bekanntermaßen Erwärmen in Isocyanate übergeführt werden kann je nach den Reaktionsbedingungen symmetrische nach folgender Gleichung:If amines 30 and hydrochloric acid amine salts are formed instead of dioxydiphenylalkanes, which are then carried out by reacted with phosgene, it is known that heating can be converted into isocyanates symmetrical according to the following equation, depending on the reaction conditions:
H2N-R-NH2 + COCl2
CI-CO-NH-R-NH2-HCl + COCl2 H 2 NR-NH 2 + COCl 2
CI-CO-NH-R-NH 2 -HCl + COCl 2
CI-CO-NH-R-NH2-HCl
OCN- R — NCO + 4HClCI-CO-NH-R-NH 2 -HCl
OCN- R - NCO + 4HCl
Geht man von Aminchlorhydraten aus und leitet 40 säurechlorid, welches dann in der Wärme in Isocyanat
Phosgen in die bis zum Rückfluß erwärmte Suspen- und Chlorwasserstoff zerfällt:
sion der Lösung ein, so bildet sich zunächst Carbamid-Assuming that amine chlorohydrates are used as the starting point, acid chloride, which is then decomposed in the heat in isocyanate phosgene into the suspension and hydrogen chloride, which is heated to reflux:
sion of the solution, carbamide
R-NH2HCl + COCl2 R-NH 2 HCl + COCl 2
-> RNHCOCl + 2HCl -> RNHCOCl + 2HCl
RNCO + HClRNCO + HCl
Demgegenüber gelangt man jedoch zu hochmolekularen Polykondensationsprodukten, insbesondere zu Polyharnstoffen, wenn man Diamine bei Anwesenheit von Alkali mit Phosgen umsetzt. Die Durchführung dieser Reaktion birgt eine ganze Reihe von Nachteilen in sich, wie z. B. die Verwendung des starkOn the other hand, however, high molecular weight polycondensation products are obtained, in particular polyureas, if diamines are reacted with phosgene in the presence of alkali. The implementation of this reaction involves a number of disadvantages to such. B. the use of the stark
giftigen Phosgens und von Alkali zur Bindung der Salzsäure.poisonous phosgene and alkali to bind hydrochloric acid.
Es wurde nun gefunden, daß man unter Vermeidung dieser Nachteile Polyharnstoffe mit bestimmtem Molekulargewicht erhält, wenn man Diamine oder Polyamine mit Kohlensäureamiden von Imidazolen,It has now been found that, while avoiding these disadvantages, polyureas with certain Molecular weight obtained when diamines or polyamines with carbonic acid amides of imidazoles,
,---.■ - 909 640/438, ---. ■ - 909 640/438
Triazolen und Tetrazolen zur Umsetzung bringt. Bei Anwendung von Carbonyl-IS^N'-di-imidazol als Car-Brings triazoles and tetrazoles to the implementation. When using carbonyl-IS ^ N'-di-imidazole as a car-
1H2N-R-NH2 + * Im CO Im ->- .,1H 2 NR-NH 2 + * Im CO Im -> -.,
Die Reaktion erfolgt sowohl mit aliphatischen, aromatischen, aliphatisch-aromatischen oder auch mit gemischten primären und sekundären Diaminen und Polyaminen, so daß die Reaktion einer weiten technischen Anwendung zugänglich ist und sie ganz nach den von den Endprodukten geforderten Eigenschaften ausgerichtet werden kann.The reaction takes place with aliphatic, aromatic, aliphatic-aromatic or with mixed primary and secondary diamines and polyamines, so that the reaction of a wide technical Application is accessible and it is completely based on the properties required by the end products can be aligned.
Das vorstehend beschriebene Verfahren hat gegenüber dem bisher bekannten Verfahren zur Herstellung von Polyharnstoffen aus Polyaminen und Phosgen folgende Vorteile:The method described above has compared to the previously known method of production of polyureas from polyamines and phosgene have the following advantages:
1.) Der Reaktionsablauf und damit die Molekülgröße des Polyharnstoffes kann durch die Reaktionstemperatur und das Molverhältnis der Reaktionspartner bestimmt werden. 1.) The course of the reaction and thus the molecular size of the polyurea can be determined by the reaction temperature and the molar ratio of the reactants are determined.
2.) Säurebindende Mittel werden nicht benötigt, so daß die sonst dadurch auftretenden Nebenreaktionen unterbleiben.2.) Acid-binding agents are not required, so that the side reactions that otherwise occur as a result remain under.
3.) Carbonyl-N.N'-di-imidazol ist als kristallisierte Substanz leichter dosierbar als gasförmiges Phosgen. Da es ungiftig ist, ist seine Verwendung im Gegensatz zu der des stark giftigen Phosgens ungefährlich. 3.) Carbonyl-N.N'-di-imidazole is as crystallized Substance easier to dose than gaseous phosgene. Since it is non-toxic, its use in In contrast to that of the highly toxic phosgene, it is harmless.
4.) Das eingesetzte Imidazol kann bei allen Umsetzungen nahezu vollständig zurückgewonnen
werden.
5.) Es kann in einer Schmelze oder in einem einzigen4.) The imidazole used can be recovered almost completely in all reactions.
5.) It can be in a melt or in a single
Lösungsmittel gearbeitet werden.
Die folgenden Beispiele sollen das vorstehende Verfahren erläutern.Solvent to be worked.
The following examples are intended to illustrate the above process.
22,7 g 4,4'-Diamino-diphenyl-2,2-propan, in wasserfreiem Tetrahydrofuran gelöst, werden unter Rühren langsam zu einer Lösung von 16,2 g Carbonyl-Ν,Ν'-di-imidazol in wasserfreiem Tetrahydrofuran gegeben. Die Lösung erwärmt sich hierbei. Nach halbstündigem Rühren und Sieden am Rückfluß, um die Kondensation zu vervollständigen, wird das Tetrahydrofuran bonylüberträger bilden sich die Kondensationsprodukte dabei nach folgender Gleichung:22.7 g of 4,4'-diamino-diphenyl-2,2-propane, in anhydrous Dissolved tetrahydrofuran are slowly stirred into a solution of 16.2 g of carbonyl-Ν, Ν'-di-imidazole given in anhydrous tetrahydrofuran. The solution heats up during this. After half an hour Stir and reflux to complete the condensation, the tetrahydrofuran becomes The condensation products are formed by the following equation:
,. [NHCONH-R-NHCONH...], + #2ImH,. [NHCONH-R-NHCONH ...], + # 2ImH
im Vakuum abdestilliert. Der erhaltene zähe Teig wird in feinverteilter Form mit heißem Wasser gewaschen, um das Imidazol zu entfernen und zurückzugewinnen. Das so erhaltene Polymere kann dann in ίο bekannter Weise im Schmelzfluß zu Fasern, Folien und Lacküberzügen verarbeitet werden.distilled off in vacuo. The tough dough obtained is washed in finely divided form with hot water, to remove and recover the imidazole. The polymer thus obtained can then be used in ίο are processed in a known way in the melt flow to fibers, foils and lacquer coatings.
22,6 g 4,4'-Diamino-2,2'-dimethyl-diphenyl-methan, in wasserfreiem Tetrahydrofuran gelöst, werden unter Rühren langsam zu einer Lösung von 16,2 g Carbonyl-N,N'-di-imidazol in wasserfreiem Tetrahydrofuran gegeben, das Reaktionsgemisch 48 Stunden bei Zimmertemperatur stehengelassen und alsdann 100 ml Aethanol unter Rühren zugesetzt. Der entstandene Niederschlag wird abgesaugt und mit Aceton gewaschen Das erhaltene Polymere ist in Dimethylformamid löslich und kann in bekannter Weise zu Fasern, Folien und Lacküberzügen verarbeitet werden.22.6 g 4,4'-diamino-2,2'-dimethyl-diphenyl-methane, Dissolved in anhydrous tetrahydrofuran are slowly stirred into a solution of 16.2 g of carbonyl-N, N'-di-imidazole given in anhydrous tetrahydrofuran, the reaction mixture left to stand for 48 hours at room temperature and then 100 ml Ethanol added with stirring. The resulting precipitate is filtered off with suction and washed with acetone The polymer obtained is soluble in dimethylformamide and can be added in a known manner Fibers, foils and lacquer coatings are processed.
Claims (3)
Deutsche Patentschriften Nr. 745 684, 896 412.Considered publications:
German patent specifications No. 745 684, 896 412.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1068010B true DE1068010B (en) | 1959-10-29 |
Family
ID=593414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1068010D Pending DE1068010B (en) | Process for the production of polyureas |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1068010B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE745684C (en) * | 1935-01-02 | 1944-05-15 | Ig Farbenindustrie Ag | Process for the production of highly condensed polyamides from diamines and carbonic acid |
| DE896412C (en) * | 1938-09-21 | 1953-11-12 | Basf Ag | Process for the production of high molecular weight condensation products |
-
0
- DE DENDAT1068010D patent/DE1068010B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE745684C (en) * | 1935-01-02 | 1944-05-15 | Ig Farbenindustrie Ag | Process for the production of highly condensed polyamides from diamines and carbonic acid |
| DE896412C (en) * | 1938-09-21 | 1953-11-12 | Basf Ag | Process for the production of high molecular weight condensation products |
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