DE2250552A1 - Filmogenic quat ammonium copolymers - use as hair fixatives ,in textile treatments etc - Google Patents
Filmogenic quat ammonium copolymers - use as hair fixatives ,in textile treatments etcInfo
- Publication number
- DE2250552A1 DE2250552A1 DE2250552A DE2250552A DE2250552A1 DE 2250552 A1 DE2250552 A1 DE 2250552A1 DE 2250552 A DE2250552 A DE 2250552A DE 2250552 A DE2250552 A DE 2250552A DE 2250552 A1 DE2250552 A1 DE 2250552A1
- Authority
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- Germany
- Prior art keywords
- mol
- alkyl
- process according
- methacrylate
- copolymerization
- 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.)
- Ceased
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Abstract
Description
Verfahren zur Herstellung von quaternären Copolymeren Gegenstand der Stammanmeldung P 21 o3 898.2 ist ein neues quaternäres Polymer, dadurch gekennzeichnet, daß es sich wiederholende Struktureinheiten der Formel besitzt, n welcher n, m und p die Mol-Prozentanteile bedeuten und insgesamt loo betragen, wobei n 20 bis 99 %, m 1 bis 80 %, sowie p 0 bis 50 % bedeutet; y - 0 oder 1, R1 = H oder CH3; R2 I, SO4, HS04 oder CH3SO3; M bedeutet eine Einheit, die sich von einem copolymerisierbaren Vinylmonomer ableitet.Process for the production of quaternary copolymers The subject of the parent application P 21 o3 898.2 is a new quaternary polymer, characterized in that it contains repeating structural units of the formula has, n which n, m and p are the molar percentages and are a total of 100, where n is 20 to 99%, m is 1 to 80%, and p is 0 to 50%; y - 0 or 1, R1 = H or CH3; R2 I, SO4, HS04 or CH3SO3; M represents a unit derived from a copolymerizable vinyl monomer.
Diese neuen synthetischen Polymeren besitzen eine größere Adhäsionskraft, ein größeres Haltevermögen und eine geringere Flokkenbildung bei der Verwendung als Haar-Behandlungsmittel gegenüber den hierfür bisher verwendeten synthetischen Polymeren.These new synthetic polymers have a greater adhesive force, greater retention and less flocculation when in use as a hair treatment agent compared to the synthetic ones previously used for this purpose Polymers.
Cegenstand der vorliegenden Zusatzanmeldung ist die Herstellung von hochmolekularen, filmbildenden quaternären Amonium-Polymeren der folgenden Formel: in welcher n, m und p die Mol-Prozentanteile bedeuten und insgesamt loo betragen, wobei n 20 bis etwa 95 Prozent, m etwa 5 bis 80 % und p o bis etwa 50 % bedeutet; R1 = H oder CH3; R2 eine Alkylen- oder Jlydroxyalkylen-Gruppe mit 2 bis etwa 20 Kohlenstoffatomen; R3 einen niederen Alkylrest, der gleich oder verschieden sein kann; R4 eine Alkyl- oder Aralkyl-Gruppe mit 1 bis 8 Kohlenstoffatomen; X Halogen, S04, HS04 oder CH3SO4; M der Rest eines verschiedenen Vinyl-Monomeren bedeutet. Das erfindungsgemäße Verfahren besteht darin, daß man eine Lösung aus Vinylpyrrolidon und einem di-(niedrig) Alkylamino-alkylacrylat oder -methacrylat oder von einem di-(niedrig)-AlkYlamino hydroxyalkylacrylat oder -methacrylat in einem geeigneten Lösungsmittel in Gegenwart eines freien Radikalstarters bei Temperaturen von etwa So bis looO C eine ausreichend lange Zeit erhitzt, bis die Copolymerisation erfolgt ist, worauf man das Copolymere mit einem Quaternärisierungsmittei vermischt, um das erhaltene Copolymere zu quaternärisieren.The subject of the present additional application is the production of high molecular weight, film-forming quaternary ammonium polymers of the following formula: in which n, m and p are the mole percentages and are a total of 100, where n is 20 to about 95 percent, m is about 5 to 80% and po is about 50%; R1 = H or CH3; R2 is an alkylene or hydroxyalkylene group having 2 to about 20 carbon atoms; R3 is a lower alkyl radical, which can be identical or different; R4 is an alkyl or aralkyl group having 1 to 8 carbon atoms; X halogen, SO4, HS04 or CH3SO4; M is the residue of a different vinyl monomer. The process according to the invention consists in that a solution of vinylpyrrolidone and a di- (lower) alkylamino-alkyl acrylate or methacrylate or of a di- (lower) -alkylamino hydroxyalkyl acrylate or methacrylate in a suitable solvent in the presence of a free radical initiator at temperatures heated from about 50 to 100 ° C. for a sufficiently long time until the copolymerization has taken place, whereupon the copolymer is mixed with a quaternary agent in order to quaternize the resulting copolymer.
Die Verbindungen der obigen Formel sind ebenso wie die der Stammanmeldung besonders brauchbar in Haar-Fixierkompositionen und besitzen eine hervorragende Haltekraft, wobei sie ein ausgezeichnetes Erscheinungsbild des Haars bewirken, ohne die Nachteile der Flockenbildung oder einer Haarversteifung zu besitzen, die die herkömmlichen Polymeren-Kompositionen mit sich bringen. Darüberhinaus bewirken die erfindungsgemäßen Copolymeren, daß die Locken besser erhalten bleiben. Die polymeren Materialien werden auf der Keratin-Oberfläche absorbiert und verbessern hierdurch die Haarstärke und das Haargewicht. Diese Absorption der quaternären Harze ist gleichmäßiger und kontinuierlicher als bei den bislang bekannten Haarfixiermitteln.The compounds of the formula above are like those of the parent application particularly useful in hair-fixing compositions and have excellent properties Holding power, giving the hair an excellent appearance without having the disadvantages of flaking or hair stiffening that the conventional polymer compositions. In addition, the copolymers according to the invention that the curls are better preserved. The polymers Materials are absorbed on the keratin surface and thereby improve the hair thickness and weight. This absorption of the quaternary resins is more uniform and more continuously than with the previously known hair fixatives.
Bringt man die erfindungsgemäßen Polymeren aus ihrer Lösung auf das Haar auf, so werden sie auf der Epi-Cutikel als praktisch kontinuierlicher dünner Film absorbiert, der nach dem Trocknen eine große Flexibilität aufweist. Dieser Film verhält sich beim Befeuchten so, daß er in die Form zurückkehrt, die er während dem Trocknen hatte. Aus diesem Grund bleiben die Locken nach dem Kämmen erhalten. Haare, die mit einer erfindungsgemäßen Haarfixierkomposition besprüht oder feucht behandelt wurden, lassen sich leicht kämmen und aufwickeln. Man erhält eine weiche Welle, die sich im trockenen Zustand leicht kämmen läßt, ohne daß man mit dem Kamm zerren muß; Jedoch kehrt die Locke wieder in die Gestalt zurück, sobald man mit dem Kämmen aufhört.If you bring the polymers according to the invention from their solution to the Hair on, so they become thinner on the epi- cuticle as a practically continuous one Absorbs film, which has great flexibility after drying. This When moistened, the film behaves in such a way that it returns to the form it was during had drying. Because of this, the curls are retained after combing. Hair that has been sprayed or moist with a hair fixative composition according to the invention can be easily combed and rolled up. You get a soft one Wave that can be easily combed when dry without having to use the comb must pull; However, the curl returns to shape as soon as one is with stops combing.
Die erfindungsgemäßen quaternären Ammonium-Copolymeren erhält man durch Copolymerisation von N-Vinylpyrrolidon und di-(niedrig)-Alkylarninoalkyl- (oder Hydroxyalkyl-)-acrylat oder -methacrylat, worauf man das Copolymere quaternäisiert, oder durch Copolymerisation von N-Vinylpyrrolidon mit einem vorher quaternärisierten di-(niedrig)-Alkylaminoalkyl- (oder Hydroxyalkyl-)-acrylat oder -methacrylat. Gegebenenfalls kann man bei der Polymerisation ein weiteres copolymerisierbares Vinyl-Monomer einsetzen. Erfindungsgemäß werden die Monomeren so copolymerisiert, daß bezogen auf loo Mol-% die Vinylpyrrolidon-Einheiten in einer Menge von So bis 9S, die Einheiten des di-(niedrig)-Alkylaminoalkyl-(oder Hydroxyalkyl-)-acrylats oder -methacrylats 5 bis 80% und die Einheiten des weiteren copolymerisierbaren Vinyl-Monomeren O bis So% vorhanden sind.The quaternary ammonium copolymers according to the invention are obtained by copolymerization of N-vinylpyrrolidone and di- (lower) -Alkylarninoalkyl- (or hydroxyalkyl -) - acrylate or methacrylate, whereupon the copolymer is quaternized, or by copolymerization of N-vinylpyrrolidone with a previously quaternized di (lower) alkylaminoalkyl (or hydroxyalkyl) acrylate or methacrylate. Possibly a further copolymerizable vinyl monomer can be used in the polymerization. According to the invention, the monomers are copolymerized so that based on 100 mol% the vinylpyrrolidone units in an amount from So to 9S, the units of the di- (lower) -alkylaminoalkyl- (or Hydroxyalkyl -) - acrylate or methacrylate 5 to 80% and the units furthermore copolymerizable vinyl monomers 0 to 0% are present.
Beispiele für geeignete di-(niedrig)-Alkylaminoalkyl- (oder llydroxyalkyl-)-acrylate oder -methacrylate sowie für Vinyl-Monomere sind in der Stammanmeldung aufgeführt.Examples of suitable di (lower) alkylaminoalkyl (or hydroxyalkyl) acrylates or methacrylates and for vinyl monomers are listed in the parent application.
Die erfindungsgemäße Copolymerisation findet in Lösung statt.The copolymerization according to the invention takes place in solution.
Man kann Jedes polare Lösungsmittel für die Monomeren verwenden, welches die Polymerisation durch Kettenübertragung nicht stört.Any polar solvent can be used for the monomers, which does not interfere with the polymerization through chain transfer.
Typische Lösungsmittel, die man insbesondere für Haarsprays, Haarwellungsmittel etc. verwenden kann, sind niedere Alkohole oder Wasser. Hinsichtlich der übrigen Reaktionsbedingungen wird auf die Stammanmeldung verwiesen.Typical solvents that are used in particular for hairsprays, hair curling agents etc. are lower alcohols or water. As for the rest For reaction conditions, reference is made to the parent application.
Gewünschtenfalls kann man die erfindungsgemäßen Copolymeren dadurch herstellen, daß man Vinylpyrrolidon mit vorher quaternärisierten Monomeren copolymerisiert, z.B. 2-Hydroxy-3-methacryloxy-propyl-trimethylammoniumchlorid, di-methylaminoäthyl-methacrylat, welches mit Dimethyl,sulfat quaternisiert ist, etc.If desired, the copolymers according to the invention can thereby be used produce that one copolymerizes vinylpyrrolidone with previously quaternary monomers, e.g. 2-hydroxy-3-methacryloxy-propyl-trimethylammonium chloride, dimethylaminoethyl methacrylate, which is quaternized with dimethyl, sulfate, etc.
Wie aus der obigen allgemeinen Formel hervorgeht, werden die monomeren Komponenten in einem solchenmolaren Verhältnis polymerisiert, daß das Polymere 20 bis 95 Mol.- Vinylpyrrolidon (vorzugsweise 40 bis 9o Mol.-), 5 bis 80 Mol-°,Ó des di-(niedrig)-Allcylaminoalkyl- (oder HydroxyalkyS)-acrylat oder -methacrylat-Monomeren (vorzugsweise 5 bis 40 Mol-%) und 0 bis 5o Mol-% eines weiteren copolymerisierbaren Vinyl-Monomeren enthält, welches mit dem Vinylpyrrolidon copolymerisiert werden kann.As can be seen from the general formula above, the monomers Components polymerized in such a molar ratio that the polymer 20 to 95 Mol.- Vinylpyrrolidone (preferably 40 to 90 Mol.-), 5 to 80 Mol- °, Ó des di (lower) alkylaminoalkyl (or hydroxyalkyS) acrylate or methacrylate monomers (preferably 5 to 40 mol%) and 0 to 50 mol% of another copolymerizable Contains vinyl monomers which are copolymerized with the vinyl pyrrolidone can.
I)ie erfindungsgemäß hergestellten Copolymeren haben im allgemeinen einen K-Wert nach Finkentscher innerhalb des Bereichs von 19 bis 15o und ein Molekulargewicht von l5.ooo bis l.ooo.ooo.I) The copolymers prepared according to the invention generally have a Finkentscher K value within the range from 19 to 150 and a molecular weight from l5.ooo to l.ooo.ooo.
Das Molekulargewicht kann je nach Auswahl der Komponenten, Starter, Lösungsmittel und Polymerisationsbedingungen, insbesondere der Temperatur, geändert werden; bei niedrigeren Temperaturen bilden sich höher molekulare Polymere.The molecular weight can vary depending on the selection of components, starters, Solvent and polymerization conditions, especially the temperature, changed will; higher molecular weight polymers are formed at lower temperatures.
Zur herstellung der neuen Copolymeren der vorliegenden Erfindung muß man nur die Monomeren in den oben angegebenen Mengenverhältnissen vermischen, so daß man durch Wirkung der freien Radikalstarter unter Vinylpolymerisation ein Copolymeres erhält. Im allgemeinen dauert der Prozeß einige Stunden, meistens etwa lo Stunden.In order to prepare the new copolymers of the present invention, one must you only mix the monomers in the proportions given above, so that by the action of the free radical initiator under vinyl polymerization, a copolymer receives. In general, the process takes a few hours, mostly about ten hours.
In den folgenden Beispielen ist die Erfindung näher erläutert; sofern nicht anders angegeben, beziehen sich alle Prozentzahlen und Teile auf das Gewicht.The invention is explained in more detail in the following examples; provided if not stated otherwise, all percentages and parts are based on weight.
Beispiel 1 In einen 5 Liter-Kolben, der mit einem Rührer, Gaseinlaßrohr, Thermometer, ItUckflußkUhler und Tropftrichter versehen ist, gibt man 2,700 gr destilliertes Wasser, 720 gr Vinylpyrrolidon und 180 gr Dimethylaminoäthyl-methacrylat. Unter Rühren werden nun 3,6 gr tert.-Butyl-peroxypivalat zugegeben. Das Reaktionsgefäß wird sorgfältig mit Stickstoff durchgespült; während der ganzen Reaktion wird ein leichter Stickstoffdruck aufrecht erhalten. Example 1 In a 5 liter flask fitted with a stirrer, gas inlet tube, Thermometer, ItUckflusskUhler and dropping funnel is provided, one gives 2.700 gr of distilled Water, 720 grams of vinyl pyrrolidone and 180 grams of dimethylaminoethyl methacrylate. Under 3.6 g of tert-butyl peroxypivalate are then added with stirring. The reaction vessel is carefully flushed with nitrogen; throughout the reaction becomes a maintain slight nitrogen pressure.
Nun erhitzt man das Reaktionsgemisch auf etwa 70° C. Sobald die lolyerisation begonnen hat, muß man gelegentlich kühlen, um die Temperatur unterhalb von etwa 75°C zu halten. Der Rückstand am Monomeren vermindert sich auf unter o,5 %, wenn man eine weitere Menge Initiator (3,6 gr) zusetzt. Die Polymerenlösung wird dann auf unterhalb 300 C abgekühlt. Nun gibt man in die extrem viskose Lösung 9oo gr destilliertes Wasser, so daß man ausreichend rUhren kann. Anschließend werden 84,5 gr Diäthyl-sulfat zugesetzt und das Gemisch eine weitere Stunde gerührt.Now the reaction mixture is heated to about 70 ° C. As soon as the lolyerisation has begun, one has to cool occasionally to the temperature below about To keep at 75 ° C. The residue on the monomer is reduced to below 0.5% if a further amount of initiator (3.6 g) is added. The polymer solution is then cooled to below 300C. Now add 900 grams to the extremely viscous solution distilled water so that one can stir sufficiently. Then it becomes 84.5 gr diethyl sulfate was added and the mixture was stirred for a further hour.
Eine Analyse des erhaltenen Produkts zeigt einen Feststoffgehalt von 21,87 %. Das Polymere hat eine relative Viskosität von 2,96 (gemessen in einer o,l %-igen Lösung in Wasser) und eine Brookfield-Viskosität von 7700 cps (gemessen in einer lo %-igen lösung in Wasser unter Verwendung einer Spindel Nr. 4 bei 30 rpm).Analysis of the product obtained shows a solids content of 21.87%. The polymer has a relative viscosity of 2.96 (measured in an o, l % solution in water) and a Brookfield viscosity of 7700 cps (measured in a lo% solution in water using a No. 4 spindle at 30 rpm).
Beispiel 2 In einen 1 Liter-Kolben, der mit einem Rührer, Gaseinlaßrohr, Thermometer und Rückflußkühler versehen ist, gibt man 245 gr destilliertes Wasser, 48 gr Vinylpyrrolidon und 54 gr einer 40 -igen wässrigen Lösung von Dimethylaminoäthyl-methacrylat, welches mit Dimethylsulfat quaternisiert ist (1:1 molare Basis) und o,l ml tert.-Butylperoxypivalat. Das quaternärisierte Dimethylaminoäthyl -methacrylat wurde vorher mit 5 gr Aktivkohle behandelt und vor Verwendung filtriert. -Das Gefäß wird nun sorgfältig mit Stickstoff gespült und das Reaktionsmedium auf 70 bis 730 C erhitzt. Example 2 In a 1 liter flask fitted with a stirrer, gas inlet tube, Thermometer and reflux condenser is provided, one gives 245 gr of distilled water, 48 grams of vinyl pyrrolidone and 54 grams of a 40% aqueous solution of dimethylaminoethyl methacrylate, which is quaternized with dimethyl sulfate (1: 1 molar basis) and 0.1 ml of tert-butyl peroxypivalate. The quaternized dimethylaminoethyl -Methacrylate was previously treated with 5 grams of activated charcoal and filtered before use. -The vessel is now purged carefully with nitrogen and the reaction medium heated to 70 to 730.degree.
Nach 2 Stunden bei dieser Temperatur kühlt man das Material auf 53°C ab und gibt o,l ml tert.-Butylperoxypivalat zu. Das Realctionsmedium wird dann erneut auf 70 bis 730 c erhitzt und etwa 6 Stunden bei dieser Temperatur gehalten.After 2 hours at this temperature, the material is cooled to 53 ° C and adds 0.1 ml of tert-butyl peroxypivalate. The Realctionsmedium is then again heated to 70 to 730 c and held at this temperature for about 6 hours.
Die Analyse des Produkts ergibt 19,8 C,o Feststoffe; der plI-Wert des Produkts beträgt 3,8. Die relative Viskosität des Polymeren beläuft sich auf 18,78 (gemessen in einer 1 -igen Lösung in Wasser), die relative Viskosität ist 4,44 (gemessen in einer o,l 7o-igen Lösung in Wasser). Die Brookfield-Viskosität beträgt 5.ooo cps.Analysis of the product shows 19.8 C, o solids; the pI value of the product is 3.8. The relative viscosity of the polymer amounts to 18.78 (measured in a 1% solution in water), which is the relative viscosity 4.44 (measured in a 0.17% solution in water). The Brookfield Viscosity is 5,000 cps.
Außer ihrer Brauchbarkeit als Haarfixiermittel etc. eignen sich die Verfahrensprodukte ebenso wie die der Stammanmeldung als Textilbehandlungsmittel, Antistatika, Deodorantien etc.In addition to their usefulness as hair fixatives, etc. are suitable Process products as well as those of the parent application as textile treatment agents, Antistatic agents, deodorants, etc.
Pat entansprüchePatent claims
Claims (7)
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DE2250552A DE2250552A1 (en) | 1970-01-30 | 1972-10-14 | Filmogenic quat ammonium copolymers - use as hair fixatives ,in textile treatments etc |
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US725070A | 1970-01-30 | 1970-01-30 | |
DE2250552A DE2250552A1 (en) | 1970-01-30 | 1972-10-14 | Filmogenic quat ammonium copolymers - use as hair fixatives ,in textile treatments etc |
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Cited By (17)
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WO2004022667A1 (en) * | 2002-09-06 | 2004-03-18 | Halliburton Energy Services, Inc. | Compositions for and methods of stabilizing subterranean formations containing clays |
US7159656B2 (en) | 2004-02-18 | 2007-01-09 | Halliburton Energy Services, Inc. | Methods of reducing the permeabilities of horizontal well bore sections |
US7182136B2 (en) | 2003-07-02 | 2007-02-27 | Halliburton Energy Services, Inc. | Methods of reducing water permeability for acidizing a subterranean formation |
US7678742B2 (en) | 2006-09-20 | 2010-03-16 | Halliburton Energy Services, Inc. | Drill-in fluids and associated methods |
US7678743B2 (en) | 2006-09-20 | 2010-03-16 | Halliburton Energy Services, Inc. | Drill-in fluids and associated methods |
US7687438B2 (en) | 2006-09-20 | 2010-03-30 | Halliburton Energy Services, Inc. | Drill-in fluids and associated methods |
US7759292B2 (en) | 2003-05-16 | 2010-07-20 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US7934557B2 (en) | 2007-02-15 | 2011-05-03 | Halliburton Energy Services, Inc. | Methods of completing wells for controlling water and particulate production |
US7998910B2 (en) | 2009-02-24 | 2011-08-16 | Halliburton Energy Services, Inc. | Treatment fluids comprising relative permeability modifiers and methods of use |
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US8631869B2 (en) | 2003-05-16 | 2014-01-21 | Leopoldo Sierra | Methods useful for controlling fluid loss in subterranean treatments |
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-
1972
- 1972-10-14 DE DE2250552A patent/DE2250552A1/en not_active Ceased
Cited By (19)
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US7091159B2 (en) | 2002-09-06 | 2006-08-15 | Halliburton Energy Services, Inc. | Compositions for and methods of stabilizing subterranean formations containing clays |
WO2004022667A1 (en) * | 2002-09-06 | 2004-03-18 | Halliburton Energy Services, Inc. | Compositions for and methods of stabilizing subterranean formations containing clays |
US8181703B2 (en) | 2003-05-16 | 2012-05-22 | Halliburton Energy Services, Inc. | Method useful for controlling fluid loss in subterranean formations |
US8962535B2 (en) | 2003-05-16 | 2015-02-24 | Halliburton Energy Services, Inc. | Methods of diverting chelating agents in subterranean treatments |
US8631869B2 (en) | 2003-05-16 | 2014-01-21 | Leopoldo Sierra | Methods useful for controlling fluid loss in subterranean treatments |
US7759292B2 (en) | 2003-05-16 | 2010-07-20 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
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