DE1468295A1 - Urethanes containing perfluoroalkyl groups and processes for their preparation - Google Patents
Urethanes containing perfluoroalkyl groups and processes for their preparationInfo
- Publication number
- DE1468295A1 DE1468295A1 DE19611468295 DE1468295A DE1468295A1 DE 1468295 A1 DE1468295 A1 DE 1468295A1 DE 19611468295 DE19611468295 DE 19611468295 DE 1468295 A DE1468295 A DE 1468295A DE 1468295 A1 DE1468295 A1 DE 1468295A1
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- carbon atoms
- formula
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- isocyanate
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Classifications
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
- D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/438—Sulfonamides ; Sulfamic acids
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/09—Sulfur-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
Description
Patentanwälte Dr.-I.u-;. ; !ANS RUSCHKE ü;j.~ ■ KF.INZ ACULAR Patent Attorneys Dr.-Iu- ;. ; ! ANS RUSCHKE ü; j. ~ ■ KF.INZ ACULAR
M 1502M 1502
U68295U68295
Minnesota Mining and Manufacturing Company St. Paul, Minnesota, USAMinnesota Mining and Manufacturing Company St. Paul, Minnesota, USA
Perfluoralkylgruppen enthaltende Urethane und VerfahrenPerfluoroalkyl Group-Containing Urethanes and Processes
zu deren Herstellungfor their production
Die Erfindung betrifft neue Perfluoralkylgruppen enthaltende Urethane sowie ein Verfahren zu deren Herstellung. Die erfindungsgemäßen neuen Verbindungen besitzen die Eigenschaft, daß sie neben einer öl- und Schmutzabweisung, an damit behandelte Substrate eine erhebliche Sohleifbeständigkeit erteilen.The invention relates to new urethanes containing perfluoroalkyl groups and a process for their production. The invention New compounds have the property that, in addition to repelling oil and dirt, they are treated with them Grant substrates a considerable resistance to soles.
Es sind bereits Imprägnierungen bekannt, um Stoffe duroh Imprägnierung mechanisch widerstandsfähiger zu machen bzw. vor meohanlsoher Abnutzung zu schützen.. Die hierzu in der deutschen Patentschrift 359 039 beschriebene lösliohe Kieselsäure ist jedoch begrenzt wasserlöslich und insbesondere bereits in schwach alkalischen Reinigungsmitteln gut löslioh. Die in der Auslegeβohrift 1 028 076 zu diesem Zweok mittels eines kationenaktiven Dispergiermittels aufgebrachten Polymerisate sind hingegen in organischen Lösungsmitteln oder auoh Ölen löslich. Die nach der amerikanischen Patentschrift 2 833 637 zur Imprägnierung von Poliersoheiben verwendeten fettsauren Salze sind andererseits wieder in Wasser dispergierbar. Die naohImpregnations are already known to impregnate fabrics To make mechanically more resistant or to protect against wear and tear However, the soluble silica described in patent specification 359 039 has limited water solubility and, in particular, is already in weakly alkaline cleaning agents are easily soluble. The in the Auslegerβohrift 1 028 076 for this purpose by means of a cation-active Polymers applied as a dispersant, on the other hand, are soluble in organic solvents or oils. The fatty acid salts used according to US Pat. No. 2,833,637 for impregnating polishing wheels are on the other hand redispersible in water. The naoh
erungsgee. ¥. 4. 9.1967,erungsgee. ¥. 4. 9.1967,
der deutschen Patentschrift 400 105 zum Imprägnieren von Trägern für Schleif- oder Poliermittel verwendeten Gemische aus Asphalt» Bienenwachs und Harzpech sind wiederum in organischen Lösungsmitteln bzw. Ölen, wie sie in erheblichem Umfang in Poliermitteln eingesetzt werden, bzw. während des Gebrauches in diese hineinkommen können, löslich. Aufgrund des Standes der Technik war es deshalb nicht zu erwarten, daß die erfindungsgemäßen neuen Verbindungen gleichzeitig Wasserbeständigkeit, ölbeständigkeit und Alkalibeständigkeit zeigen und hervorragend zur Verhinderung der Schleifabnützung geeignet sind·of the German patent specification 400 105 for impregnating backings for grinding or polishing agents from mixtures used Asphalt »beeswax and resin pitch are in turn in organic solvents or oils, as they are to a considerable extent in Polishing agents are used or can get into them during use, soluble. Because of the state It was therefore not to be expected from technology that the new compounds according to the invention would at the same time be water resistance, oil resistance and alkali resistance show and excellent are suitable for preventing abrasion of the grinding machine
Die erfindungsgemäßen Perfluoralkylgruppen enthaltende Urethane haben die FormelThe urethanes containing perfluoroalkyl groups according to the invention have the formula
in der R einen Kohlenwasserstoffrest, einen durch Alkoxygruppen, Fluor oder Chlor substituierten Kohlenwasserstoffrest, einen Kohlenwasserstoffätherrest oder einen Rest bedeutet, der aus der Reaktion eines Kohlenwasserstoffisocyanate oder eines durch eine Alkoxygruppe, Fluor oder Chlor substituierten Isocyanate mit einem Alkohol, Meroaptan, Phenol, Thiophenol, einer Carbonsäure oder einem Amin herleitbar ist, Q eine Gruppe -Rf m (NR1O1nSO2R1 R1 ein Phenylen- und/oder Alkylenrest mit 1 bis 12 Kohlenstoffatomen, in which R denotes a hydrocarbon radical, a hydrocarbon radical substituted by alkoxy groups, fluorine or chlorine, a hydrocarbon ether radical or a radical resulting from the reaction of a hydrocarbon isocyanate or an isocyanate substituted by an alkoxy group, fluorine or chlorine with an alcohol, meroaptane, phenol, thiophenol, a carboxylic acid or an amine, Q is a group -R f m (NR 1 O 1n SO 2 R 1 R 1 is a phenylene and / or alkylene radical with 1 to 12 carbon atoms,
Rn ein Wasserstoffatom oder ein Alkylrest mit 1 bis 20 Kohlenstoffatomen, R n is a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms,
Rf ein einwertiger fluorierter aliphatisoher Rest, der 3 bis 20 Kohlenstoffatome mit einer Perfluormethylgruppe enthält undR f is a monovalent fluorinated aliphatic radical containing 3 to 20 carbon atoms with a perfluoromethyl group and
909822/1350909822/1350
außer Fluoratomen höchstens ein Wasserstoff- oder Chloratom für je zwei Kohlenstoffatome und außer Kohlenstoffatomen in der Gerüstkette höchstens Sauerstoffatome oder dreiwertige Stickstoffatome, die nur an ein Kohlenstoffatom gebunden sind, aufweist;apart from fluorine atoms at most one hydrogen or chlorine atom for every two carbon atoms and apart from carbon atoms in the skeleton chain has a maximum of oxygen atoms or trivalent nitrogen atoms that are only bonded to one carbon atom, having;
X ein Schwefel- oder Sauerstoffatom, ein Imino-, Sulfonamido- oder Carbonamidorest;X is a sulfur or oxygen atom, an imino, sulfonamido or carbonamido radical;
W ein Isocyanatrest oder der Rest -NHCOR", wobei R"f einem organischen Rest entspricht, der sich von einem Alkohol, Mercaptan, Phenol, Thiophenol, einer Carbonsäure oder einem Amin ableitet; W is an isocyanate radical or the radical -NHCOR ", where R" f corresponds to an organic radical derived from an alcohol, mercaptan, phenol, thiophenol, a carboxylic acid or an amine;
m gleich 0 und/oder 1, η eine ganze Zahl von 1 bis 3, ρ eine ganze Zahl von 1 bis 6 und die Summe von n+(p-1) = 2 bis 6 ist.m is 0 and / or 1, η is an integer from 1 to 3, ρ is a integer from 1 to 6 and the sum of n + (p-1) = 2 to 6.
Das erfindungsgemäße Verfahren zur Herstellung der vorstehenden Perfluoralkylgruppen enthaltenden Urethane besteht darin, daß man eine ein reaktionsfähiges Wasserstoffatom aufweisende Fluorkohlenstoffverbindung der Formel The inventive method for making the above Urethanes containing perfluoroalkyl groups consist in that a fluorocarbon compound having a reactive hydrogen atom of the formula
RfQY ,R f QY,
in der Rf und Q die vorstehend angegebene Bedeutung haben und Y die das reaktionsfähige Wasserstoffatom enthaltende Endgruppe -OH, -COOH, -SH, -NHR", -CONHR" oder -SO2NHR", wobei R" die vor* stehend angegebene Bedeutung aufweist, darstellt, gegebenenfalls zusammen mit einer nicht-fluorierten ein reaktionsfähiges Wasserstoff a torn aufweisenden Verbindung der Formelin which R f and Q have the meaning given above and Y is the end group -OH, -COOH, -SH, -NHR ", -CONHR" or -SO 2 NHR "containing the reactive hydrogen atom, where R" is the above * Has meaning, represents, optionally together with a non-fluorinated compound of the formula having a reactive hydrogen atom
R111Y ,R 111 Y,
in der Rnl ein organischer Rest ist, der eich von einem Alkohol, Mercaptan, Phenol, Thiophenol, einer Carbonsäure oder einemin which R nl is an organic radical which is derived from an alcohol, mercaptan, phenol, thiophenol, a carboxylic acid or a
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Amin ableitet, mit einem Mono- oder Polyisocyanat der FormelAmine derived with a mono- or polyisocyanate of the formula
in der R, η und ρ die vorstehend angegebene Bedeutung haben, umsetzt.in which R, η and ρ have the meaning given above, implements.
Die Polyisocyanate können auch mit einer Perfluoralkyl enthaltenden Verbindung in Mischung mit einer anderen reaktionsfähigen Wasserstoff enthaltenden Verbindung, die keine Perfluoralkylgruppe besitzt, umgesetzt werden. Bei dieser Art reicht die ölabstoßung, die mit einem einfachen Pluorkohlenstoffrest erreicht werden kann, für viele Zwecke aus, da die Wirksamkeit dieser Verbindungen mehr als die Hälfte der Wirksamkeit der entsprechenden Fluorkohlenstoff-Diaddukte ausmacht.The polyisocyanates can also contain a perfluoroalkyl Compound in admixture with another reactive hydrogen-containing compound that does not have a perfluoroalkyl group owns, to be implemented. In this type, the oil repellency, which is achieved with a simple fluorocarbon residue, is sufficient Can be used for many purposes as the effectiveness of these compounds is more than half the effectiveness of the corresponding fluorocarbon diadducts.
Es ist auch möglich, die Perfluoralkyl enthaltende Verbindung mit nur einer der Isocyanatgruppen zur Reaktion zu bringen. Auf diese Weise enthält die Verbindung eine reaktionsfähige Isocyanatgruppe, die mit anderen Verbindungen reagieren kann oder als Mittel zur Vereinigung der Verbindung mit dem zu behandelnden Substrat verwendet werden kann. Z.B. kann bei der Behandlung von reaktionsfähige Zerewitinoff-Wasserstoffatome enthaltenden Substraten, wie Nylon, Cellulose und andere organisohe Stoffe, die reaktionsfähige Isocyanatgruppe mit dem aktiven Zerewitinoff-Wasserstoff des Substrats zur Reaktion gebracht werden; in diesem Pail wird die Verbindung der Erfindung direkt zugegeben und wird zu einem integralen Bestandteil des behandelten Substrates. In dieser Hinsicht kann es erwünschtIt is also possible to react the perfluoroalkyl-containing compound with only one of the isocyanate groups. In this way the compound contains a reactive isocyanate group that can react with other compounds or as a means of combining the compound with the substrate to be treated. E.g. with the Treatment of reactive Zerewitinoff hydrogen atoms containing substrates, such as nylon, cellulose and other organic substances, the reactive isocyanate group with the active Zerewitinoff hydrogen of the substrate reacted will; in this package the compound of the invention is added directly and becomes an integral part of the treated substrate. In this regard, it may be desirable
909822/13 5 0909822/13 5 0
sein, die Ibocyanatgruppe, beispielsweise durch Umsetzen mit einem Phenol, zu "blookieren". Diese "blockierte" Isocyanatgruppe wird danach durch Erhitzen der Verbindung auf eine erhöhte Temperatur unter Bildung des Phenols und der gewünschten Isocyanatgruppe wieder freigemacht.be the ibocyanate group, for example by reacting with a phenol, to "block". This "blocked" isocyanate group is then increased by heating the compound to a Temperature freed again with formation of the phenol and the desired isocyanate group.
Die Polyaddukte der vorliegenden Erfindung können als Oberflächenbehandlungsmittel nach bekannten Überziehmethoden aufgebracht werden, wie z.B. durch Sprühen, Aufwalzen, Aufstreichen oder Eintauchen in organische flüssige Lösungen oder anionische, kationisohe oder nicht-ionische Emulsionen. Sie können aus leicht verfügbaren organischen Lösungsmitteln, wie Alkoholen, Ketonen, Äthern und chlorierten Lösungsmitteln, angewendet werden. Sie können als alleinige Komponente in der Behandlungsflüssigkeit oder als eine Komponente in einem aus vielen Bestandteilen zusammengesetzten Komplex verwendet werden, wie kosmetische Artikel, Wachse, Polituren, Reinigungemischungen und Pharmazeut i ca.The polyadducts of the present invention can be used as surface treatment agents can be applied by known coating methods, such as spraying, rolling or brushing or immersion in organic liquid solutions or anionic, cationic or non-ionic emulsions. You can from readily available organic solvents such as alcohols, ketones, ethers and chlorinated solvents will. They can be used as a sole component in the treatment liquid or as a component in one of many ingredients compound complex can be used, such as cosmetic articles, waxes, polishes, cleaning mixtures and pharmacists i approx.
Spezifische Verbindungen, die mit den reaktionsfähigen Kohlenwasserstoffen unter Bildung der Polyaddukte der Erfindung zur Reaktion gebracht werden können, sind folgende:Specific compounds associated with the reactive hydrocarbons which can be reacted to form the polyadducts of the invention are as follows:
I. CP5(CP2J7SO2N(GH3)OH2GH2OH
II. CP3(CP2)^SO2N(CH3)GH(CH3)CH2OHI. CP 5 (CP 2 J 7 SO 2 N (GH 3 ) OH 2 GH 2 OH
II. CP 3 (CP 2 ) ^ SO 2 N (CH 3 ) GH (CH 3 ) CH 2 OH
III. CF3(CP2J3SO2N(CH2CH3)CH2CH2OHIII. CF 3 (CP 2 J 3 SO 2 N (CH 2 CH 3 ) CH 2 CH 2 OH
IV. CP3(CPg)3SO2N(CH3)CH2CH(CH3)OHIV. CP 3 (CPg) 3 SO 2 N (CH 3 ) CH 2 CH (CH 3 ) OH
Y. CP3(CPg)7SO2N(CH2CH3)CH2CH2OHY. CP 3 (CPg) 7 SO 2 N (CH 2 CH 3 ) CH 2 CH 2 OH
VI. CP3(CP2)9SO2N(GH2CH2GH3)CH2CH2OH VII.VI. CP 3 (CP 2 ) 9 SO 2 N (GH 2 CH 2 GH 3 ) CH 2 CH 2 OH VII.
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VIII.VIII.
Spezifische Isocyanatverb.tndungen mit einem Kohlenwass era toffkern und funktioneilen Gruppen, die mit geeigneten Pluorkohlenetof Verbindungen zur Reaktion gebrecht werden, sind durch ihre Strukturformeln wie folgt wiedergegeben:Specific isocyanate compounds with a hydrocarbon core and functional groups that are prevented from reacting with suitable fluorocarbon compounds are due to their Structural formulas shown as follows:
OCN-OCN-
-NGO-NGO
H NH N
VcVc
COCO
OuN-OuN-
OCN(CHg)6NCOOCN (CHg) 6 NCO
CH3(CH2)3NC0 NCOCH 3 (CH 2 ) 3 NC0 NCO
NOONOO
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Die erflndung-dgemäßen Addukte aus diesen Verbindungen können fol gendermaßen bezeichnet WerdensThe adducts according to the invention from these compounds can fol genderedly denotes becoming
oH Hoo HH o
F3 ( CP2) 7SO2H(CH2CH5 )CHgCHgOCK-^"^ -EC0CH2CH2N{CH2CH5 )SO2 (CP2 }F 3 (CP 2 ) 7 SO 2 H (CH 2 CH 5 ) CHgCHgOCK - ^ "^ -EC0CH 2 CH 2 N {CH 2 CH 5 ) SO 2 (CP 2 }
Addukt V-A-V (das Maddukt)Adduct V-A-V (the Maddukt)
HCOHCO
3 Q oder3 Q or
A^dukt V-A (das Monoaddukt)A ^ duct V-A (the monoadduct)
'Mt/löslich au den fluorierten Verbindungen und dam Isocyanat kann />;t?.-r;tyhe.?.e;*i&31ß eino dritte, nicht f3.uorierte Realctionskomponente, tii.i1 reikt'!.c»ai;ßhige Wasoerntoffat(o;ra® aafi^eist, sur Herstellung der 0T?i*±rA'mFMr?.fr.ev&.fe;n ?^.vodulrk») aniieviondmt werden. Beispiele solcher niE.'l: 'Mt / soluble au the fluorinated compounds and dam isocyanate can />;t?.- r; tyhe e;.?. * I 31ss eino third non f3.uorierte Realctionskomponente, reikt tii.i 1'! .c »ai; ßhige Wasoerntoffat (o; ra® aafi ^ eist, sur making the 0T? i * ± rA'mF M r? .fr.ev &.fe; n ? ^. v odulrk») aniieviondmt. Examples of such niE.'l:
K CH3(CH2)1fjCG0H.K CH 3 (CH 2 ) 1fj CG0H.
909822/1350 BAD ORIGINAL909822/1350 ORIGINAL BATHROOM
Die folgenden Beispiele veranschaulichen die Herstellung" der Verbindungen der Erfindung, worin alle wBeile" in Gewiohtsteilen und alle "Prozente" .in öewichtaprozenten ausgedrückt sind, sofern nicht andere angegeben.The following examples illustrate the preparation "of the compounds of the invention wherein all w Axes" in Gewiohtsteilen and all the "percents" are expressed .in öewichtaprozenten if not other specified.
117 g (0,2 Mol) der Verbindung VII und 17,4 g (0,1 Mol) der Verbindung Λ wurden in Gegenwart von 2 Tropfen Triäthylamin bei einer Temperatur von etwa 60% zur Reaktion gebracht. Das Reaktionsmiechungsaddukt VII-A-VII (Pp.600G) wurde in Methylethylketon (5 Teile) und Ithylendlchlorid (95 Seile) als 0,5*-tge Lösung gelöst. Biese Lösung wurde mit großem Erfolg bei den verschiedenen Substraten verwendet.117 g (0.2 mol) of compound VII and 17.4 g (0.1 mol) of compound Λ were reacted in the presence of 2 drops of triethylamine at a temperature of about 60%. The reaction odor adduct VII-A-VII (p.p. 60 0 G) was dissolved in methyl ethyl ketone (5 parts) and ethylene chloride (95 ropes) as a 0.5% solution. This solution has been used with great success on the various substrates.
58,5 g (0,1 Mol) der Verbindung VII wurde su 17,4 g (0,1 Mol) der Verbindung A in 76 g wasserfreiem Äthylacetat angegeben. Die Mischung wurde einige Stunden auf 40 bis 50 4C ernltst und dann verdünnt auf 1 f> feste Anteile mit Tetrachlorkohlenstoff. Biese Lösung war eine wirksame Fluorkohlenstofflöeung des Addukte· VII-A.58.5 g (0.1 mol) of compound VII were given as follows: 17.4 g (0.1 mol) of compound A in 76 g of anhydrous ethyl acetate. The mixture was ernltst a few hours to 40 to 50 4 C and then diluted to 1 f> solid fractions with carbon tetrachloride. This solution was an effective fluorocarbon solution of the adduct · VII-A.
In einen mit Rührer und RUokfluflkUhler ausgestatteten Glaskolben wurden 1142 g (2 Mol) der Verbindung V und 1316 g trockenes Toluol gegeben. BIe Mlsohung wurde unter Rühren auf 60 0C1142 g (2 moles) of compound V and 1316 g of dry toluene were placed in a glass flask equipped with a stirrer and cooler. Bie Mlsohung was stirred at 60 0 C
909822/1350909822/1350
erhitzt. 174 g (1 Mol) der Verbindung A wurden zugegeben, anschließend eine katalytisch^ Menge von Triäthylamin, Bs trat exotherme Reaktion ein, und das Erhitzen auf 80 bis 100 0C wurde einige Stunden fortgesetzt. Das erhaltene feste Produkt V-A-V (Fp 110 0C) wurde durch Abziehen des Toluole im Vakuum isoliert.heated. 174 g (1 mol) of compound A were added, then a catalytic amount of triethylamine, Bs, an exothermic reaction occurred, and heating to 80 to 100 ° C. was continued for a few hours. The resulting solid product VAV (m.p. 110 0 C) was isolated by stripping off the toluenes in vacuo.
0,1 Mol der Verbindung VIII, wovon etwas in der Anhydridform der Säure vorlag, wurde mit 0,05 Mol der Verbindung A in trokkenem Toluol vereinigt und 45 Stunden unter Rühren auf 97 0C erhitzt. Während dieser Zeit wurde 1 g Kohlendioxyd in Freiheit gesetzt. Naoh dem Abkühlen wurde die obere Toluolsohicht von der unteren, orangen, festen Schicht abdekantiert. Die Feststoffe wurden mit Toluol gewaschen und filtriert. Noch unreagiertes Anhydrid wurde durch Aufschlämmen der Feststoffe in warmem, inertem perfluoriertem Lösungsmittel entfernt, abfiltriert und getrocknet. Das Überziehen mit einer 1 #-igen Lösung des erhaltenen Adduktes VIII-A-VIII führte zu guter ölabstossung. 0.1 mole of the compound VIII, of which some are in the anhydride of the acid was present, of the compound A was combined in dry toluene and heated for 45 hours under stirring at 97 0 C with 0.05 mol. During this time 1 g of carbon dioxide was released. After cooling, the upper toluene layer was decanted from the lower, orange, solid layer. The solids were washed with toluene and filtered. Unreacted anhydride was removed by slurrying the solids in warm, inert perfluorinated solvent, filtered off and dried. Coating with a 1 # solution of the adduct VIII-A-VIII obtained resulted in good oil repellency.
9 0'.} 8 2 2/13509 0 '.} 8 2 2/1350
Claims (2)
1. Perfluoralkylgruppen enthaltende Urethane der FormelClaims
1. Urethanes containing perfluoroalkyl groups of the formula
-1Ue Unterlagen ,λ,· .; . ., 9 09822/1350
- 1 Ue of documents, λ, ·.;
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5362660A | 1960-09-02 | 1960-09-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1468295A1 true DE1468295A1 (en) | 1969-05-29 |
Family
ID=21985521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19611468295 Pending DE1468295A1 (en) | 1960-09-02 | 1961-07-27 | Urethanes containing perfluoroalkyl groups and processes for their preparation |
Country Status (4)
| Country | Link |
|---|---|
| CH (2) | CH378279A (en) |
| DE (1) | DE1468295A1 (en) |
| GB (1) | GB999795A (en) |
| NL (1) | NL139786B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3607773A1 (en) * | 1986-03-08 | 1987-09-10 | Cassella Ag | Polyurethanes containing fluoroalkyl ligands, process for their preparation, and their formulations and their use |
| EP0605105A1 (en) * | 1992-12-30 | 1994-07-06 | Imperial Chemical Industries Plc | Process for rigid foams |
| WO2008040428A2 (en) | 2006-09-29 | 2008-04-10 | Construction Research & Technology Gmbh | Functionalized polyurethane resin, method for the production thereof, and use thereof |
| EP2308908A1 (en) | 2009-10-10 | 2011-04-13 | Bernhard Jansen | Aqueous dispersion of a heat hardened polyurethane composition |
| US8906425B2 (en) | 2003-06-13 | 2014-12-09 | Basf Beauty Care Solutions France S.A.S. | Stimulation of the synthesis of the activity of an isoform of lysyl oxidase-like LOXL for stimulating the formation of elastic fibers |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5931751A (en) * | 1982-08-17 | 1984-02-20 | Daikin Ind Ltd | Urethane compound containing fluorine and use thereof |
| US4525305A (en) * | 1982-10-25 | 1985-06-25 | Minnesota Mining And Manufacturing Company | Leather with fluorochemical finish |
| DE3435618A1 (en) * | 1984-09-28 | 1986-04-10 | Chemische Fabrik Pfersee Gmbh, 8900 Augsburg | METHOD FOR OBTAINING WASHING AND CLEANING-RESISTANT TEXTILE EQUIPMENT WITH REACTIVE (CO) POLYMERS OR PRE-CONDENSATE |
| DE3881560T2 (en) * | 1987-03-20 | 1994-02-03 | Asahi Glass Co Ltd | Fluorine-containing polyurethanes and polyisocyanate compound compositions for their manufacture. |
| US5508370A (en) * | 1991-10-17 | 1996-04-16 | Bayer Aktiengesellschaft | Water-dispersible blocked isocyanates, method of manufacture, and use thereof |
| DE4136768A1 (en) * | 1991-11-08 | 1993-05-13 | Bayer Ag | THE USE OF POLYISOCYANATE SOLUTIONS FOR IMPREGNATING MINERAL SUBSTANCES |
| AU659229B2 (en) | 1991-11-12 | 1995-05-11 | Minnesota Mining And Manufacturing Company | Fluoroaliphatic dimer acid derivatives and use thereof |
| US6803109B2 (en) * | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
| ES2377692B1 (en) * | 2010-01-25 | 2013-02-12 | Main Style Sl | PROCEDURE FOR OBTAINING A JUTE FLOOR FOR FOOTWEAR. |
-
1961
- 1961-07-27 DE DE19611468295 patent/DE1468295A1/en active Pending
- 1961-08-21 CH CH974061A patent/CH378279A/en unknown
- 1961-08-21 CH CH817062A patent/CH410616A/en unknown
- 1961-08-23 NL NL268543A patent/NL139786B/en not_active IP Right Cessation
- 1961-09-04 GB GB3173461A patent/GB999795A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3607773A1 (en) * | 1986-03-08 | 1987-09-10 | Cassella Ag | Polyurethanes containing fluoroalkyl ligands, process for their preparation, and their formulations and their use |
| EP0605105A1 (en) * | 1992-12-30 | 1994-07-06 | Imperial Chemical Industries Plc | Process for rigid foams |
| US8906425B2 (en) | 2003-06-13 | 2014-12-09 | Basf Beauty Care Solutions France S.A.S. | Stimulation of the synthesis of the activity of an isoform of lysyl oxidase-like LOXL for stimulating the formation of elastic fibers |
| WO2008040428A2 (en) | 2006-09-29 | 2008-04-10 | Construction Research & Technology Gmbh | Functionalized polyurethane resin, method for the production thereof, and use thereof |
| EP2308908A1 (en) | 2009-10-10 | 2011-04-13 | Bernhard Jansen | Aqueous dispersion of a heat hardened polyurethane composition |
| DE102009048945A1 (en) | 2009-10-10 | 2011-04-14 | Jansen, Bernhard, Dr. | Aqueous dispersion of a thermosetting polyurethane composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB999795A (en) | 1965-07-28 |
| CH378279A (en) | 1964-07-31 |
| NL139786B (en) | 1973-09-17 |
| DE1418985A1 (en) | 1969-10-02 |
| CH410616A (en) | 1966-03-31 |
| CH974061A4 (en) | 1964-02-28 |
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