DE1645571A1 - Process for the production of a water-dilutable, drying oil with improved film properties - Google Patents
Process for the production of a water-dilutable, drying oil with improved film propertiesInfo
- Publication number
- DE1645571A1 DE1645571A1 DE19661645571 DE1645571A DE1645571A1 DE 1645571 A1 DE1645571 A1 DE 1645571A1 DE 19661645571 DE19661645571 DE 19661645571 DE 1645571 A DE1645571 A DE 1645571A DE 1645571 A1 DE1645571 A1 DE 1645571A1
- Authority
- DE
- Germany
- Prior art keywords
- oil
- polyoxyalkylenes
- oils
- polyisocyanates
- groups
- 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
- 238000000034 method Methods 0.000 title claims description 14
- 238000001035 drying Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003921 oil Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- -1 Polyoxyethylenes Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F7/00—Chemical modification of drying oils
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Polyethers (AREA)
- Paints Or Removers (AREA)
- Lubricants (AREA)
Description
Verfahren zur Herstellung eines mit Wasser verdünnbaren, trocknenden dles mit verbesserten Bilmeigenschaften Es ist bekannt, hydrophobe Stoffe weniger hydrophob bis hydrophil zu machen durch Einfuhrung von Polyoxyalkylenen, meist Palyäthylenoxyd, in das Molekül. Diese Einführung der Polyoxyalkylene kann z.B. durch Veresterung freier Carboxylgruppen oder durch Verätherung freier Hydroxylgruppen erfolgen. Eine Abwandlung letztgenannter Methode ist die direkte Verätherung von Epoxygruppen durch die Polyoxyalkylene. Weiter ist bekannt, daß den zu modifizierenden Stoffen um so mehr hydrophile Eigenschaften verliehen werden, je mehr Polyoxyalkylengruppen eingeführt werden. Process for the production of a water-dilutable, drying dles with improved bilge properties It is known to have less hydrophobic substances to make hydrophobic to hydrophilic by introducing polyoxyalkylenes, mostly polyethylene oxide, into the molecule. This introduction of the polyoxyalkylenes can be carried out, for example, by esterification free carboxyl groups or by etherification of free hydroxyl groups. One A modification of the last-mentioned method is the direct etherification of epoxy groups the polyoxyalkylenes. It is also known that the substances to be modified so more hydrophilic properties are imparted, the more polyoxyalkylene groups introduced will.
Gemäß einem nicht zum bekannten Stand der Technik gehörenden, älteren Vorschlag werden mit Wasser verdunnbare, d. h. in Wasser lösliche oder in Wasser emulgierbare Anstrichmittel aus trocknenden oder haibtrocknenden Ölen dadurch erzeugt, daß ein Teil der Doppelbindungen epoxydiert, und die entstandenen Epoxygruppen mit Polyoxyalkylenen veräthert werden.According to an older one not belonging to the known state of the art Proposal be dilutable with water, d. H. soluble in water or in water emulsifiable paints from drying or semi-drying oils produced by that some of the double bonds epoxidize, and the resulting epoxy groups with Polyoxyalkylenes are etherified.
Gemäß einem anderen, ebenfalls nicht zum bekannten Stand der Technik gehörenden älteren Vorachlag werden zur Herstellung von gut trocknenden Bindemitteln trocknende oder halbtrocknende Öle partiell epoxydiert, die Epoxygruppen partiell hydroxyliert und die so entstandenen ZwiBchenprodukte durch Umsetzung mit Polyisocyanaten urethanisiert; um diese Bindemittel wasserverdünnbar zu machen können sie noch mit Polyoxyalkylen veräthert werden.According to another, also not part of the known prior art belonging older template are used for production of well-drying Binding agent drying or semi-drying oils partially epoxidized, the epoxy groups partially hydroxylated and the intermediate products formed in this way by reaction with Polyisocyanates urethanized; to make these binders water-thinnable they are still etherified with polyoxyalkylene.
Gemäß einem weiteren nicht zum bekannten Stand der Technik gehörenden, älteren Vorschlag werden die Filmeigenschaften von Anstrichmitteln aus trocknenden und halbtrocknenden Ölen dadurch verbessert, daß ein Teil der Doppelbindungen der Ölmoleküle direkt oder auf dem Umweg über die Epoxydierung zu vicinalen Diolen umgesetzt und diese Diole mit Hilfe von Polyisocyanaten vernetzt werden.According to another not part of the known state of the art, older proposal are the film properties of paints from drying and semi-drying oils improved by the fact that some of the double bonds of the Oil molecules converted to vicinal diols directly or indirectly via epoxidation and these diols are crosslinked with the aid of polyisocyanates.
Die vorliegende Erfindung betrifft eine weitere Verbesserung dieser teils bekannten teil nicht bekannten älteren Vorschlöle die es gestattet, aus trocknenden und nicht trocknenden Ölen Anstrichmittel herzustellen, die mit Wasser verdünnbar, d.h. in Wasser löslich oder emulgierbar sind und Filme mit verbesserten Festigkeitseigenschaften ergeben.The present invention is directed to a further improvement of these partly known partly not known older Vorschlöle which allows drying out and non-drying oils to produce paints that can be thinned with water, i.e. are soluble or emulsifiable in water and films with improved strength properties result.
Erfindungsgemäß werden die Ausgangsöle nach an sich bekannten Reaktionen so mit Oxydationsmitteln umgesetzt, daß unter Erhaltung eines erheblichen Teils der ursprünglich vorhandenen Doppelbindungen ein Teil der Doppelbindungen in viclnalo Diole umgewandelt wird. Diese Bildung vicinaler Diole kann nach verschiedenen hekaunten Reaktionen erfolgen. Beispielßweisa bilden sie sich unter der Einwirkung relativ milder Oxydationsmittel, we Wasserstoffperoxyd in entsprechender Konzentration oder verdünnter, wäßriger alkalischer Permanganatlözung, g, oder durch hydrolytische Aufspaltung von Epoxygruppen. iie ihrerseits durch Einwirkung gewisser Percarbonsäuren auf die Doppelbindungen entstehen, wobei die Persäuren entweder als solche angewendet werden oder während der Reaktion "in-situ", z. B. aus den entsprechenden Carbonsäuren und Wasserstoffperoxyd, gebildet werden. Insbeaondere bei Anwendung schwächerer Percarbonsäuren als Perameisensäure, Es,B. von Peressigsäure, kann die Anwendung von Epoxydierungskatalysatoren, wie Schwefelsäure, Aluminiumhydroxyd, Natriumacetat, Sulfonsäuren, Ionenaustauscherharzen u.ä., nützlich sein. Auch für die Aufspaltung der Epoxygruppen zu den Diolen ist die Anwendung von Säurekataysatoren, beispielsweise Perchlorsäure, Schwefelsäure, Salzsäure, Methansulfonsäure, p-Toluolsulfonsäure etc., vorteilhaft. Dabei wi-cd der Umsetzungsgrad zweckmäßig so eisgestellt, daß das erhaltene Zwischenprodukt 0,2 bis 1,0 freie Hydroxylgruppen je Ölmolektil enthält.According to the invention, the starting oils are prepared according to reactions known per se so reacted with oxidizing agents that while preserving a considerable part of the originally existing double bonds a part of the double bonds in viclnalo Diols is converted. This formation of vicinal diols can occur in various ways Reactions take place. For example, they form relatively under the influence milder oxidizing agent, such as hydrogen peroxide in the appropriate concentration or dilute, aqueous alkaline permanganate solution, g, or by hydrolytic Splitting of epoxy groups. iie in turn through the influence of certain Percarboxylic acids arise on the double bonds, the peracids being either applied as such or "in-situ" during the reaction, e.g. B. from the corresponding carboxylic acids and hydrogen peroxide. In particular when using weaker percarboxylic acids than performic acid, Es, B. of peracetic acid, the use of epoxidation catalysts such as sulfuric acid, aluminum hydroxide, Sodium acetate, sulfonic acids, ion exchange resins, and the like, may be useful. Also for the splitting of the epoxy groups to the diols is the use of acid catalysts, for example perchloric acid, sulfuric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid etc., advantageous. The degree of conversion is expediently set so that the intermediate product obtained contains 0.2 to 1.0 free hydroxyl groups per oil molectile.
Die so erhaltenen partiell hydroxylierten Öle werden an-Schlie#end mit Polyisocyanaten umgesetzt, und zwar zweckmäßig bei einer Temperatur von 60 - 200°C, vorzugsweise in Temperaturbereich von 100 - 1400C. Die Polyisocyanate erden dabei in einer solchen Menge angewendet, daß das Äquivalentverhältnis von Isocyanatgruppen zu Hydroxylgruppen größer als 1 s 1, zweckmäßig bis 1,5 : 1, vorzugsweise bis 1,3 : 1, beträgt. Für diese Urethanisierunbsrekation werden vorzugsweise aromatische Diisocyanate, wie z,B. Toluylendiisocyanat, angewendet.The partially hydroxylated oils obtained in this way are then used reacted with polyisocyanates, expediently at a temperature of 60 - 200 ° C, preferably in a temperature range of 100 - 1400C. Ground the polyisocyanates used in such an amount that the equivalent ratio of isocyanate groups to hydroxyl groups greater than 1 s 1, expediently up to 1.5: 1, preferably up to 1.3 : 1, is. For this urethanization, aromatic ones are preferred Diisocyanates such as e.g. Tolylene diisocyanate, applied.
Dadurch ist sichergestellt, daß in dem nunmehr vorliegenden zweiten Zwischenprodukt ein Uberschuß an freien Isocyanatgruppen enthalten ist. Diese freien Isocyanatgruppen werden erfindungsgemäß anschließend mit Polyoxyalkylenen, vorzugsweise Polyoxyäthylenen in entsprechender Menge umgesetzt.This ensures that in the second Intermediate product contains an excess of free isocyanate groups. These free Isocyanate groups are then, according to the invention, preferably with polyoxyalkylenes Polyoxyethylenes implemented in the appropriate amount.
Die Menge der auf diese Weise eingeführten Polyoxyalkylengruppen richtet sich nach dem gewünschten Grad der Wasser verdünnbarkeit bzw. Wasserlöslichkeit. je höher dieeer Grad ist, desto mehr Polyotyalkylene müssen in das Molekül eingeführt und dementsprechend umso höher muß der Überschuß an Isocyanatgruppen in den filr die Umsetzung mit Polyoxyalkylenen eingesetzten Zwischenprodukten liegen. Im allgemeinen gentigt ein Gehalt der urethanisierton Zwischenprodukte an Isocyanatgruppen von etwa 0,2 bis 2 Gew.-%.The amount of polyoxyalkylene groups introduced in this way is directed depending on the desired degree of water dilutability or water solubility. the higher this level, the more polyoxyalkylenes must be introduced into the molecule and accordingly the higher the excess of isocyanate groups in the filr the reaction with polyoxyalkylenes used intermediates. In general If the urethanized intermediate products contain isocyanate groups of about 0.2 to 2% by weight.
Gute Wasserverdünnbarkeit wird erzielt, wenn diese urethanisierten Öle mit Polyoxyalkylenen in einem solchen Mengenververhältnis umgesetzt werden, daß das Mol.Verhältnis von OH- zu CEO-Gruppen (1,1 bis 4) t 1 beträgt. Das Molekulargewicht der angewendeten Polyoxyalkylene soll zweckmäßig zwischen 200 und 20 000 und vorzugsweise zwischen 200 bis 1 200 liegen, wie dies auch bei bekannten Umsetzungen üblich ist, die zur Verbesserung der Wasserverträglichkeit durchgeführt werden.Good water thinnability is achieved when these are urethanized Oils are reacted with polyoxyalkylenes in such a quantitative ratio, that the molar ratio of OH to CEO groups (1.1 to 4) t is 1. The molecular weight the polyoxyalkylenes used should expediently be between 200 and 20,000 and preferably lie between 200 and 1 200, as is also customary in known reactions, which are carried out to improve the water tolerance.
Die Urethanieierungsreaktion wird vorteilhafterweise in Gegenwart von an sich bekannten Katalysatoren, wie Triäthylamin, Di-n-butylzinndichlorid, Di-n-butylzinndilaurat eto., durchgeführt.The urethanation reaction is advantageously carried out in the presence known catalysts, such as triethylamine, di-n-butyltin dichloride, Di-n-butyltin dilaurate eto., Performed.
Bin besonderer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß es die Einführung der Polyoxyalkylene bei niedrigeren Temperaturen als bisher notwendig erlaubt. Diese Schlu#umsetzung wird erfindungsgemäß im Temperaturbereich von 20 - 2000C, vorzugsweise im Bereich von 80 - 140°C durchgeführt.A particular advantage of the method according to the invention is that that it is the introduction of the polyoxyalkylenes at lower temperatures than before necessary allowed. According to the invention, this final implementation takes place in the temperature range from 20-2000C, preferably in the range from 80-140 ° C.
Das erfindungsgemäße Verfahren ist nachstehend an Hand eines Ausführungsbeispiels näher beschrieben: In einem 2-Liter-Vierhals-rundkolben mit Rührer, Thermometer, Zulauftrichter und Rückflußkühler wurden 1 000 g Lackleinöl (JZ, Wijs = 185,5) mit 13,5 g Ameisensäure auf 550C erwärmt. Unter kräftigem Rühren ließ man 33, 2 g Wasserstoffperoxyd, 60 yig, langsam zutropfen, wobei darauf geachtet wurde, daß die Temperatur im Kolben 700a nicht überschritt. Nach 90 Minuten wurden 50 g Wasser und 3 g Perchlorsäure, 70 %ig, zugesetzt und der Ansatz dann bei 90°C sechs Stunden weitergerührt.The method according to the invention is shown below on the basis of an exemplary embodiment described in more detail: In a 2 liter four-necked round bottom flask with a stirrer, Thermometer, feed funnel and reflux condenser were 1,000 g of linseed oil (JZ, Wijs = 185.5) heated to 550C with 13.5 g of formic acid. The mixture was left with vigorous stirring 33.2 g hydrogen peroxide, 60 yig, slowly add dropwise, taking care to that the temperature in the flask did not exceed 700a. After 90 minutes, 50 g Water and 3 g of perchloric acid, 70%, were added and the batch was then six at 90 ° C Stirred for hours.
Das Reaktionsprodukt wurde mit Wasser gewaschen und unter Vakuum getrocknet. Das erhaltene klare Öl hatte: Hydroxylzahl - 41,5 Epoxy-Sauerstoff = 0,0 % Jodzahl / Wijs = 168,5 viskositT - 1,2 pOISE/20°c Farbzahl (Lovibond, 1 cm) = 1,1 gelb 100 g dieses hydroxylierten Leinöls wurden mit 71 g Toluylendiisocyanat, 48,1 % NCO, berechnet 1,1 Mol.-NCO-Gruppen pro Mol. Hydroxylgruppen, eine Stunde bei 130°C umgesetzt. Das gebildete Öl war Mir (Freie-NCO = 0,82 %, Jodzahl nach Wij3 = 164). 80 g des entstandenen Öles wurden weiter mit 7 g Polyäthylenglykol, Molekulargewicht 300, innerhalb von 1 1/2 Std. bei 1300C umgesetzt.The reaction product was washed with water and dried under vacuum. The clear oil obtained had: hydroxyl number - 41.5 epoxy oxygen = 0.0% iodine number / Wijs = 168.5 viskositT - 1.2 POISE / 20 ° c color number (Lovibond, 1 cm) = 1.1 yellow 100 g of this hydroxylated linseed oil were mixed with 71 g of tolylene diisocyanate, 48.1% NCO, calculated 1.1 mol NCO groups per mol of hydroxyl groups, reacted at 130 ° C. for one hour. The oil formed was Mir (free NCO = 0.82%, iodine number according to Wij3 = 164). 80 g des The resulting oil was further treated with 7 g of polyethylene glycol, molecular weight 300, implemented within 1 1/2 hours at 1300C.
Die Analyse des erhaltenen Öles erbab.The analysis of the oil obtained erbab.
Jodzahl nach Wijs = 148 Viskosität = 23,8 Poise/20°c Farbzahl (Lovibond, 1 cm) = 7 rot, 10 gelb Das muster ergab mit Wasser stabile Emulsionen, die nach Sikkativierung mit 0,2 % Co in 2 Std. trockneten. Wijs iodine number = 148 viscosity = 23.8 poise / 20 ° c color number (Lovibond, 1 cm) = 7 red, 10 yellow The sample resulted in emulsions which were stable with water Desiccation with 0.2% Co dried in 2 hours.
Claims (9)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEU0011450 | 1965-02-17 | ||
| DEU0012283 | 1965-12-16 | ||
| DEU0012361 | 1966-01-12 | ||
| DEU0012366 | 1966-01-13 | ||
| DEU0012409 | 1966-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1645571A1 true DE1645571A1 (en) | 1970-07-09 |
Family
ID=27512323
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19651645539 Expired DE1645539C3 (en) | 1965-02-17 | 1965-02-17 | Process for the production of water-thinnable or emulsifiable binders |
| DE19651645564 Pending DE1645564A1 (en) | 1965-02-17 | 1965-12-16 | Process for the production of binders that dry well |
| DE19661645570 Pending DE1645570A1 (en) | 1965-02-17 | 1966-01-12 | Process for the production of a modified drying or semi-drying oil with improved film properties |
| DE19661645571 Pending DE1645571A1 (en) | 1965-02-17 | 1966-01-13 | Process for the production of a water-dilutable, drying oil with improved film properties |
| DE19661645573 Pending DE1645573A1 (en) | 1965-02-17 | 1966-01-31 | Process for the production of binders that dry well |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19651645539 Expired DE1645539C3 (en) | 1965-02-17 | 1965-02-17 | Process for the production of water-thinnable or emulsifiable binders |
| DE19651645564 Pending DE1645564A1 (en) | 1965-02-17 | 1965-12-16 | Process for the production of binders that dry well |
| DE19661645570 Pending DE1645570A1 (en) | 1965-02-17 | 1966-01-12 | Process for the production of a modified drying or semi-drying oil with improved film properties |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19661645573 Pending DE1645573A1 (en) | 1965-02-17 | 1966-01-31 | Process for the production of binders that dry well |
Country Status (6)
| Country | Link |
|---|---|
| AT (1) | AT292872B (en) |
| CH (1) | CH475330A (en) |
| DE (5) | DE1645539C3 (en) |
| GB (1) | GB1139137A (en) |
| NL (1) | NL6602029A (en) |
| SE (1) | SE333422B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3317194A1 (en) * | 1983-05-11 | 1984-11-15 | Henkel KGaA, 4000 Düsseldorf | POLYURETHANE PREPOLYMERS BASED ON OLEOCHEMICAL POLYOLS, THEIR PRODUCTION AND USE |
| DE3347045A1 (en) * | 1983-12-24 | 1985-07-04 | Henkel KGaA, 4000 Düsseldorf | TWO COMPONENT POLYURETHANE ADHESIVE |
| DE3630422A1 (en) * | 1986-09-06 | 1988-03-10 | Henkel Kgaa | USE OF FAT POLYOLS FOR THE PRODUCTION OF AQUEOUS POLYURETHANE DISPERSIONS |
| JPH04501284A (en) * | 1989-08-09 | 1992-03-05 | バッテレーインスティツウト エ．ファウ． | Method of manufacturing plastic from raw material oils and fats |
| DE4308097A1 (en) * | 1993-03-15 | 1994-09-22 | Henkel Kgaa | Polyol for an isocyanate casting resin and coatings |
| DE19533168A1 (en) | 1995-09-08 | 1997-03-13 | Henkel Kgaa | Fatty chemical polyols as reactive diluents |
| DE19646424A1 (en) | 1996-11-11 | 1998-05-14 | Henkel Kgaa | Use of polyols for isocyanate casting resins and coating compositions |
-
1965
- 1965-02-17 DE DE19651645539 patent/DE1645539C3/en not_active Expired
- 1965-12-16 DE DE19651645564 patent/DE1645564A1/en active Pending
-
1966
- 1966-01-12 DE DE19661645570 patent/DE1645570A1/en active Pending
- 1966-01-13 DE DE19661645571 patent/DE1645571A1/en active Pending
- 1966-01-31 DE DE19661645573 patent/DE1645573A1/en active Pending
- 1966-02-16 GB GB689866A patent/GB1139137A/en not_active Expired
- 1966-02-17 CH CH227766A patent/CH475330A/en not_active IP Right Cessation
- 1966-02-17 NL NL6602029A patent/NL6602029A/xx unknown
- 1966-02-17 AT AT144966A patent/AT292872B/en active
- 1966-02-17 SE SE207266A patent/SE333422B/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH475330A (en) | 1969-07-15 |
| AT292872B (en) | 1971-09-10 |
| DE1645539C3 (en) | 1973-10-25 |
| NL6602029A (en) | 1966-08-18 |
| SE333422B (en) | 1971-03-15 |
| DE1645564A1 (en) | 1970-08-06 |
| DE1645539B2 (en) | 1973-03-22 |
| DE1645539A1 (en) | 1970-09-17 |
| DE1645573A1 (en) | 1971-01-21 |
| GB1139137A (en) | 1969-01-08 |
| DE1645570A1 (en) | 1970-09-24 |
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