EP1670837A1 - Polymers based on n,n-diallylamine derivatives, their production and use - Google Patents

Polymers based on n,n-diallylamine derivatives, their production and use

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Publication number
EP1670837A1
EP1670837A1 EP04765386A EP04765386A EP1670837A1 EP 1670837 A1 EP1670837 A1 EP 1670837A1 EP 04765386 A EP04765386 A EP 04765386A EP 04765386 A EP04765386 A EP 04765386A EP 1670837 A1 EP1670837 A1 EP 1670837A1
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European Patent Office
Prior art keywords
acid
acrylate
methacrylate
methyl
hydrogen
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German (de)
French (fr)
Inventor
Stefan Becker
Lysander Chrisstoffels
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F26/02—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 single or double bond to nitrogen
    • C08F26/04—Diallylamine

Definitions

  • amphiphilic molecules which are used as surfactants in many areas of application, occupy a special place.
  • Polyelectrolytes are macromolecular compounds that are wholly or partly made up of ionic or ionizable monomer units. Their property profile is determined both by the chemical structure of the polymer chain as well as by the type, density and strength of the charge as well as the localization of the ionic groups.
  • water-soluble polymers as process aids determine technology.
  • polyquaternary polymers are used in a large number of industrial areas such as paper production, cosmetics, construction chemicals, detergent and cleaning agent formulations, textile processing, pharmacy and surface coating.
  • the polyelectrolytes act as polymeric surfactants, thickeners, solubilizers or dispersion stabilizers.
  • polyelectrolytes are called amphoteric polyelectrolytes or polyampholytes.
  • polyampholytes can occur as polyacids or polybases.
  • cationic charge is permanently present in the form of an aliphatic or aromatic ammonium, sulfonium or phosphonium function and is combined with the basic group in each monomer unit, these zwitterionic compounds are not referred to as polyampholytes, but as polybetaines, since such polymers are different Show behavior in aqueous systems.
  • polysulfobetaines, polyphosphobetaines and polycarbobetaines depending on whether the anionic charge is carried by a sulfonate, phosphonate or carboxylate group.
  • polycarbobetaines can be obtained in two ways. On the one hand through the synthesis of so-called precursor polymers and subsequent polymer-analogous conversion to the corresponding polycarbobetaines [Al-Muallem et al., Polymer 43, 2002, 4285-4295] or by polymerizing already charged betaine monomers.
  • WO 00/14053 describes the synthesis of the polymers from a water-soluble, hydrolysis-stable amphoteric monomer based on dimethylaminopropyl methacrylamide (DMAPMA).
  • DMAPMA dimethylaminopropyl methacrylamide
  • Polymers based on diallyl compounds are primarily polycarbobetaines starting from diallylammonium compounds with subsequent cyclization polymerization [Favresse et al., Polymer 42 (2001) 2755-2766].
  • ampholytic polymers based on diallylamine and substituted diallylamines can be anionic, cationic or zwitterionic.
  • Al-Muallem et al. [Polymer 43 (2002) 1041-1050] describe the synthesis of N, N-diallyl-N-carboethoxymethylamine or pentylamine by reacting diallylamine with chloroacetic acid or 1-chlorohexanoic acid ethyl ester with the addition of potassium carbonate.
  • Laschewsky et al. synthesize ethyl 2- (N, N-diallylamino) valerate by nucleophilic substitution.
  • Polymers based on diallylamine and substituted diallylamines are used, for example, for the production of flocculants and ion exchange resins and in fiber and paper technology.
  • Ammonium salts are polymerized, since the uncharged form cannot be “readily” polymerized under the conditions of free radical polymerization.
  • This further functional group is preferably a proanionic, particularly preferably a carboxyl group.
  • R ⁇ R 2 are independently hydrogen or -CC 4 alkyl with compounds of general formula II, H HR 3rd
  • R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and
  • R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, are reacted and the Michael adducts are then radically polymerized, optionally in the presence of one or more radically copolymerizable monomers.
  • diallylamine derivatives of the formula I in which R 1 , R 2 are, for example, hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl independently of one another the compounds are diallylamine, 2-methylldiallylamine or bis (2-methylallyl) amine, 2-ethyldiallylamine, bis (2-ethylallyl) amine, 2-isopropyldiallylamine, bis (2-isopropylallyl) amine, 2-tert-butyldiallylamine or bis (2-tert-butylallyl) amine is preferred.
  • N, N-diallylamine is particularly preferred.
  • Compounds of the general formula II are, for example, acrylic acid, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and stearyl arylate, furthermore acrylonitrile, acrolein, vinylsulfonic acid, vinylphosphonic acid, acrylamide, naphtha Butylacrylamide and N-octylacrylamide.
  • Preferred compound of the general formula II is acrylic acid.
  • Monomers for copolymerization with the reaction products according to the invention from compounds of the general formula I and compounds of the general formulas II include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride and its half-ester, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl arylate, stearyl methacrylate, N-butyl acrylamide, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxyl acrylate,
  • methyl, ethyl, butyl or dodecyl vinyl ether vinyl formamide, vinyl methylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N- Dimethylaminomethyl methacrylate and N- [3- (dimethylamino) propyl] methacrylamide; 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, methyl sulfate or diethyl sulfate.
  • the monomers bearing amino groups can be present in quaternized form.
  • the present invention furthermore relates to a process for the preparation of the polymers, starting from the compounds of the formulas I and II.
  • the process according to the invention comprises the reaction of a compound of general formula I with at least one compound of general formula II in the sense of a Michael addition.
  • the preferred molar ratio I to II is 1: 1, but an excess of one of the components can also be used.
  • An example of a surplus is 1 to 1, 1 or 1.1 to 1.
  • the Michael addition can take place with or without a solvent, depending on the miscibility of the pure substances.
  • Water alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, aliphatic table hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, ketones such as acetone, amides such as N, N- Dimethylformamide, N, N-dimethylacetamide, chlorinated hydrocarbons such as dichloromethane, chloroform or 1, 1, 2,2-
  • a preferred embodiment is the reaction without a solvent.
  • the products obtained from the Michael addition can be isolated in a manner known per se.
  • Michael addition is usually carried out at temperatures between -20 and + 50 ° C, preferably between -10 and + 30 ° C.
  • the invention furthermore relates to the products of the formula III obtained from this reaction
  • R 1 and R 2 independently of one another are hydrogen or d to C 4 -alkyl
  • R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, it also being possible for the nitrogen to be quaternized by protonation.
  • the inventive method further includes the polymerization of the products of formula III.
  • the compounds of the general formula III according to the invention can be isolated or used for the polymerization without further working up.
  • the compounds of the general formula III according to the invention can be converted into homopolymers or, in the presence of one or more free-radically copolymerizable monomers, into copolymers.
  • the polymerization is a radical polymerization, which is preferably carried out in solution.
  • Possible solvents are all solvents customary for polymerization reactions.
  • the preferred solvent is water.
  • the radical polymerization is carried out in a manner known per se with the exclusion of oxygen, for example by flowing through an inert gas and, if appropriate, under an inert gas atmosphere, nitrogen being preferably used as the inert gas.
  • Water-soluble and water-insoluble initiators can be used as initiators for the radical polymerization.
  • Typical initiators are peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds.
  • Examples include hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl hydroperoxide, acetyl acetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate.
  • Water-soluble azo compounds such as, for example, azobisisobutyronitrile, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2- imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane disulfate dihydrate, 2,2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'- Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 4,4'-azo -bis- (4-cyanvaleric acid), 1, 1 '-azo-bis- (cyclohexanecarboxylic acid nitrile), 2,2'-azobis (isobutyric acid amidine) dihydrochloride, 2,2
  • the initiators can be used alone or as mixtures. Examples of such mixtures are binary mixtures such as e.g. Mixtures of hydrogen peroxide and sodium peroxodisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium.
  • redox initiator systems can be used as polymerization initiators.
  • Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator such as, for example, reducing sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites and tetrahionates of alkali metals and ammonium compounds.
  • peroxodisulfates with alkali metal or ammonium bisulfites can be used, e.g. Ammonium peroxodisulfate and ammonium disulfite.
  • the proportions of peroxide-containing compound to redox coinitiator are in the range from 30: 1 to 0.05: 1.
  • additional transition metal catalysts can be used, for example salts of iron, cobalt, nickel, copper, vanadium and manganese.
  • Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, or copper (I) chloride.
  • the reducing transition metal salt is usually used in a concentration in the range from 0.1 ppm to approx. 1000 ppm.
  • Combinations of hydrogen peroxide with iron (II) salts can be used, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.
  • redox coinitiators and / or transition metal catalysts can be used in combination with the abovementioned initiators, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and Chrome.
  • the amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to about 1000 ppm, based on the amounts of monomers used.
  • water-soluble azo initiators hydrogen peroxide, sodium persulfate, potassium persulfate or ammonium persulfate are used.
  • initiators are water-soluble azo initiators; 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (trade name: VA-044) is very particularly preferred.
  • the amounts of initiator are generally between 0.5 and 10% by weight, based on the total mass of monomer. Preferred amounts are 1 to 6% by weight, particularly preferred are 2 to 4% by weight.
  • the molar proportion of compound III, based on the total amount of monomers is in the range from 5 to 95 mol%, preferably in the range from 20 to 80 mol%. %, particularly preferably in the range from 45 to 55 mol%.
  • the polymerization can be carried out in a temperature range between 30 and 90 ° C., preferably between 40 and 70 ° C., very particularly preferably between 55 and 65 ° C.
  • the homopolymerization of monomers of the general formula III can be carried out without or with the addition of acid. In the absence of hydrolysis-sensitive substituents, it is preferably carried out in the presence of acids.
  • Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoro- acetic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, chloroacetic acid,
  • Hydrochloric acid, sulfuric acid and phosphoric acid are particularly suitable, hydrochloric acid is very particularly suitable.
  • the homopolymerization of monomers of the general formula III in aqueous solution can preferably be carried out at acid concentrations in the range from 0 to 70 mol%. Molar concentrations greater than 5 mol% are particularly preferred, very particularly preferably greater than 30 mol%.
  • copolymerization of monomers of the general formula III with the monomers accessible by hydrolysis is advantageously carried out in a buffered aqueous solution.
  • the sum of the concentrations of the monomers in the solution are between 15 and 85%, preferably between 25 and 75%, particularly preferably between 40 and 60%.
  • the properties such as the molecular weight (M w , M n ) of the polymers according to the invention depend on the reaction conditions chosen.
  • the reaction conditions initiator amount, initiator type, course of initiator addition, use of acid, type and amount of acid, solids content of the polymerization solution, temperature, reaction time, post-polymerization with repeated addition of initiator or duration of the post-polymerization may be mentioned as influencing variables.
  • the yields are between 40 and 95% depending on the reaction conditions chosen.
  • the molecular weights M w are in the range between 10,000 and 300,000, in particular between 30,000 and 200,000.
  • the polymers according to the invention can be used in a variety of ways, for example in cosmetic and pharmaceutical compositions, foods, surfactants and cleaning agents.
  • the polymers according to the invention can be used in the petroleum industry, pulp processing, paint production and textile industry.
  • Example 1 N, N-diallyl-3-aminopropionic acid
  • a monomer solution containing 200 g of N, N-diallyl-3-aminopropionic acid, 67.5 g of 32% hydrochloric acid and 32.5 g of water was heated to 60 ° C. under a nitrogen atmosphere.
  • the polymerization was then started by adding 10% of an 8% aqueous initiator solution of VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride) (the total amount of initiator is 4 wt .-% based on the total amount of monomer).
  • Another 60% initiator solution was added dropwise over 3 hours. After a further 2 hours with stirring, the remaining initiator solution was added over a period of 1 hour, the temperature was finally raised to 80 ° C. and the mixture was stirred for another 3 hours.
  • the polymer was obtained in a yield of 93%.
  • Dependence of the yield of poly (N, N-diallyl-3-aminopropionic acid) on the acid concentration is the total amount of
  • the polymers mentioned in Table 2 were prepared essentially analogously to the reaction described in Example 2, the amount of acid being varied. Further reaction conditions: The concentration of the acid is based on the amount of monomer. Weight fraction of all monomers 50%, weight fraction catalyst VA-0444%, night Polymerization time 1 h, temperature 60 ° C, 10 vol% of the initiator solution added at the beginning of the reaction
  • the polymers mentioned in Table 4 were prepared essentially analogously to the reaction described in Example 2, the temperature being varied. Further reaction conditions: 50% by weight of all monomers, 2% by weight of catalyst VA-044, post-polymerization time 1 h, 25% by volume of the initiator solution added at the start of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer. Table 4:
  • the polymers mentioned in Table 5 were prepared essentially analogously to the reaction described in Example 2, the amount of initiator being varied. Further reaction conditions: weight fraction of all monomers 50%, post-polymerization time 1 h, temperature 60 ° C., 10% by volume of the initiator solution added at the beginning of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer.
  • the polymers mentioned in Table 6 were prepared essentially analogously to the reaction described in Example 2, the temperature and the addition of initiator being varied. Further reaction conditions: weight fraction of the monomers 50%, weight fraction catalyst VA-0442%, post-polymerization time 1 h, amount of acid based on the amount of monomer 50%,
  • a common 50% aqueous solution of 169 g of N, N-diallyl-3-aminopropionic acid and 71 g of acrylamide (molar ratio 1: 1) and a 4% aqueous initiator solution of VA-044 (9.6 g dissolved in 480 ml water) were prepared in a dropping funnel. 20% of the monomer solution was dropped into the reaction vessel and heated to 60 ° C. The reaction was started by adding 20% of the initiator solution. The remaining monomer solution was then added dropwise over four hours, the remaining initiator solution over five hours. The reaction mixture was then stirred at 80 ° C. for another hour. A slightly yellowish solution was obtained with a polymer yield of 85%.
  • DPA N, N-diallyl-3-aminopropionic acid
  • AAM acrylamide

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Abstract

The invention relates to methods for producing novel polymers comprising the following steps: reaction of diallylamine or diallylamine derivatives with olefinically unsaturated compounds in the context of a Michael addition; and the subsequent radical polymerisation of the Michael adducts, optionally in the presence of additional compounds that can be radically polymerised. The invention also relates to the corresponding Michael adducts of diallylamine and its derivatives, in addition to the use of said novel polymers.

Description

Polymerisate auf Basis von N,N-Diallylaminderivaten, deren Herstellung und VerwendungPolymers based on N, N-diallylamine derivatives, their preparation and use
Beschreibungdescription
Die vorliegende Erfindung betrifft neue Homo- und Copolymerisate auf Basis von N,N-Diallylaminderivaten, Verfahren und Zwischenprodukte zu ihrer Herstellung sowie Verfahren zur Herstellung der diesen Homo- und Copolymeren zugrundeliegenden N,N-Diallylaminderivaten durch Michael-Addition von gegebenenfalls substituiertem Diallylamin an aktivierte C=C-Doppelbindungen.The present invention relates to new homopolymers and copolymers based on N, N-diallylamine derivatives, processes and intermediates for their preparation and processes for the preparation of the N, N-diallylamine derivatives on which these homopolymers and copolymers are based, activated by Michael addition of optionally substituted diallylamine C = C-double bonds.
Geladene organische Moleküle spielen in vielen Bereichen der Chemie eine große Rolle. Einen besonderen Platz nehmen die amphiphilen Moleküle ein, die als Tenside in vielen Anwendungsbereichen zum Einsatz kommen.Charged organic molecules play an important role in many areas of chemistry. The amphiphilic molecules, which are used as surfactants in many areas of application, occupy a special place.
Polyelektrolyte sind makromolekulare Verbindungen, die vollständig oder teilweise aus ionischen oder ionisierbaren Monomereinheiten aufgebaut sind. Ihr Eigenschaftsbild wird sowohl durch die chemische Struktur der Polymerkette als auch durch Ladungsart, -dichte und -stärke sowie die Lokalisierung der ionischen Gruppen bestimmt.Polyelectrolytes are macromolecular compounds that are wholly or partly made up of ionic or ionizable monomer units. Their property profile is determined both by the chemical structure of the polymer chain as well as by the type, density and strength of the charge as well as the localization of the ionic groups.
In zahlreichen technischen Anwendungen sind wasserlösliche Polymere als Prozesshilfsmittel technologiebestimmend. Beispielsweise werden polyquarternäre Polymere in einer Vielzahl von industriellen Bereichen wie Papierherstellung, Kosmetik, Bauchemie, Wasch- und Reinigungsmittelformulierung, Textilverarbeitung, Pharmazie und Oberfiächenbeschichtung eingesetzt. Dabei wirken die Polyelektrolyte als polymere Tenside, Verdicker, Solubilisatoren oder Dispersionsstabilisatoren.In numerous technical applications, water-soluble polymers as process aids determine technology. For example, polyquaternary polymers are used in a large number of industrial areas such as paper production, cosmetics, construction chemicals, detergent and cleaning agent formulations, textile processing, pharmacy and surface coating. The polyelectrolytes act as polymeric surfactants, thickeners, solubilizers or dispersion stabilizers.
Liegen funktioneile Gruppen mit Protonendonatoren und -akzeptoren in einem Polymer nebeneinander vor und können die Moleküle demnach in Abhängigkeit vom pH-Wert anionisch oder kationisch auftreten, so nennt man solche Polyelektrolyte amphotere Polyelektrolyte oder Polyampholyte. Polyampholyte können je nach pH-Wert des Mediums als Polysäuren oder Polybasen auftreten.If functional groups with proton donors and acceptors are present next to one another in a polymer and the molecules can accordingly occur anionically or cationically depending on the pH value, such polyelectrolytes are called amphoteric polyelectrolytes or polyampholytes. Depending on the pH of the medium, polyampholytes can occur as polyacids or polybases.
Mumick et al. (Macromolecules 1994, 27, 323-331) beschreiben die Verwendung von ampholytischen Polymeren als Hilfsmittel zur Herabsetzung des Fließwiderstandes.Mumick et al. (Macromolecules 1994, 27, 323-331) describe the use of ampholytic polymers as auxiliaries for reducing the flow resistance.
Ist die kationische Ladung permanent in Form einer aiiphatischen oder aromatischen Ammonium-, Sulfonium- oder Phosphoniumfunktion vorhanden und in jeder Monomereinheit mit der basischen Gruppe vereinigt, so bezeichnet man diese zwitter- ionischen Verbindungen nicht als Polyampholyte, sondern als Polybetaine, da solche Polymere ein anderes Verhalten in wässrigen Systemen zeigen. Man unterscheidet Polysulfobetaine, Polyphosphobetaine und Polycarbobetaine, je nachdem, ob die anionische Ladung von einer Sulfonat-, Phosphonat- oder Carboxylatgruppe getragen wird.If the cationic charge is permanently present in the form of an aliphatic or aromatic ammonium, sulfonium or phosphonium function and is combined with the basic group in each monomer unit, these zwitterionic compounds are not referred to as polyampholytes, but as polybetaines, since such polymers are different Show behavior in aqueous systems. A distinction is made between polysulfobetaines, polyphosphobetaines and polycarbobetaines, depending on whether the anionic charge is carried by a sulfonate, phosphonate or carboxylate group.
Polycarbobetaine können prinzipiell auf zwei Arten erhalten werden. Zum einen durch die Synthese sogenannter Precursorpolymere und anschließende polymeranaloge Umsetzung zu den entsprechenden Polycarbobetainen [Al-Muallem et al., Polymer 43, 2002, 4285-4295] oder durch Polymerisation bereits ladungstragender betainischer Monomere.In principle, polycarbobetaines can be obtained in two ways. On the one hand through the synthesis of so-called precursor polymers and subsequent polymer-analogous conversion to the corresponding polycarbobetaines [Al-Muallem et al., Polymer 43, 2002, 4285-4295] or by polymerizing already charged betaine monomers.
WO 00/14053 beschreibt die Synthese der Polymere aus einem wasserlöslichen hydrolysestabilen amphoteren Monomer auf Basis von Dimethylaminopropylmethacryl- amid (DMAPMA).WO 00/14053 describes the synthesis of the polymers from a water-soluble, hydrolysis-stable amphoteric monomer based on dimethylaminopropyl methacrylamide (DMAPMA).
Oft führt die freie radikalische Polymerisation von solchen Monomeren jedoch nur zu oligomeren und uneinheitlichen Produkten, oder die Polymerisationsgeschwindigkeit ist auf Grund der geringen Reaktivität sehr niedrig.However, the free radical polymerization of such monomers often only leads to oligomeric and inconsistent products, or the polymerization rate is very slow due to the low reactivity.
Polymere auf Basis von Diallylverbindungen sind in erster Linie Polycarbobetaine ausgehend von Diallylammoniumverbindungen mit anschließender Cyclisierungspolymeri- sation [Favresse et al., Polymer 42 (2001) 2755-2766].Polymers based on diallyl compounds are primarily polycarbobetaines starting from diallylammonium compounds with subsequent cyclization polymerization [Favresse et al., Polymer 42 (2001) 2755-2766].
Je nach pH-Wert können ampholytische Polymere auf Basis von Diallylamin und substituierten Diallylaminen anionisch, kationisch oder zwitterionisch vorliegen.Depending on the pH, ampholytic polymers based on diallylamine and substituted diallylamines can be anionic, cationic or zwitterionic.
Neutrale und (zwitterionische) Monomere auf Basis von Diallylamin sind bekannt. So beschreiben Hodgkin et al. in J. Amer. Chem. Soc. 1980 (14) S. 211-233 eine Synthese für Diallylaminmonomere über den Reaktionsmechanismus der Mannich- Reaktion. Des weiteren werden in einer einstufigen Reaktion N-substituierte Diallyl- amin-Monomere durch N-Alkylierung von Diallylamin dargestellt. Die gleichen Autoren beschreiben auch die säurekatalysierte Addition von 2-Vinyl- pyridin an Diallylamin entsprechend der Vorschrift von Reich et al. [JACS, 77 (1955) 4913-4915].Neutral and (zwitterionic) monomers based on diallylamine are known. For example, Hodgkin et al. in J. Amer. Chem. Soc. 1980 (14) pp. 211-233 a synthesis for diallylamine monomers via the reaction mechanism of the Mannich reaction. Furthermore, N-substituted diallylamine monomers are prepared in a one-step reaction by N-alkylation of diallylamine. The same authors also describe the acid-catalyzed addition of 2-vinylpyridine to diallylamine in accordance with the procedure by Reich et al. [JACS, 77 (1955) 4913-4915].
Die Bildung von N-substituiertem 4-Aminopyridin durch Umsetzung von 4-Chlorpyridin mit Diallylamin unter Abspaltung von Chlorwasserstoff beschreiben Mathias et al. [US 4591625]. N-Benzyl- und N-heteroaromatisch-substituierte Diallylamine sind nach Hodgkin und Solomon [J.Macromol. Sei. Chem. A 10 (5), 893-922] ebenfalls über die Mannich- Reaktion zugänglich.Mathias et al. Describe the formation of N-substituted 4-aminopyridine by reacting 4-chloropyridine with diallylamine with elimination of hydrogen chloride. [US 4591625]. Hodgkin and Solomon [J.Macromol. N-benzyl- and N-heteroaromatic-substituted diallylamines. Be. Chem. A 10 (5), 893-922] also accessible via the Mannich reaction.
Al-Muallem et al. [Polymer 43 (2002) 1041-1050] beschreiben die Synthese von N,N- diallyl-N-Carboethoxymethylamin bzw- pentylamin durch Umsetzung von Diallylamin mit Chloressigsäure- bzw. 1-Chlorhexansäureethylester unter Zugabe von Kalium- carbonat. Laschewsky et al. synthetisieren Ethyl-2-(N,N-diallylamino)valerat durch nukleophile Substitution.Al-Muallem et al. [Polymer 43 (2002) 1041-1050] describe the synthesis of N, N-diallyl-N-carboethoxymethylamine or pentylamine by reacting diallylamine with chloroacetic acid or 1-chlorohexanoic acid ethyl ester with the addition of potassium carbonate. Laschewsky et al. synthesize ethyl 2- (N, N-diallylamino) valerate by nucleophilic substitution.
Alle diese bisher bekannten Synthesen von substituierten Diallylaminderivaten, die potentiell anionische Funktionen, insbesondere Carboxylgruppen, enthalten, haben den Nachteil, dass bei der nukleophilen Substitution halogenierte Carbonsäureester eingesetzt werden und dementsprechend Reinigungs- und Verseifungsschritte bis zum Erhalt der Säurefunktion durchgeführt werden müssen. Das bedeutet gleichzeitig höheren Zeit- und Kostenaufwand sowie geringere Ausbeuten.All of these previously known syntheses of substituted diallylamine derivatives which potentially contain anionic functions, in particular carboxyl groups, have the disadvantage that halogenated carboxylic acid esters are used in the nucleophilic substitution and, accordingly, cleaning and saponification steps have to be carried out until the acid function is obtained. At the same time, this means more time and costs as well as lower yields.
Polymere auf Basis von Diallylamin und substituierten Diallylaminen werden beispielsweise zur Herstellung von Flockungsmitteln und lonenaustauscherharzen sowie in der Faser- und Papiertechnologie verwendet.Polymers based on diallylamine and substituted diallylamines are used, for example, for the production of flocculants and ion exchange resins and in fiber and paper technology.
Al-Muallem et. al beschreiben die Synthese eines Polypyrrolidins mit einer Carboxylat- Anion-funktionalisierten Seitenkette in Polymer 43 (2002), S. 4285. Die aufwendigeAl-Muallem et. al describe the synthesis of a polypyrrolidine with a carboxylate anion-functionalized side chain in Polymer 43 (2002), p. 4285. The complex
Synthese führt von der radikalischen Polymerisation des Carboethoxy-methyldiallyl- ammoniumchlorid über eine polymeranaloge Verseifung, eine Dialyse und schließlich eine Deprotonierung mittels NaOH zum Endprodukt. Die Ausbeute an Wertprodukt liegt hier bei unter 50%. Hodgkin et al. weisen in J. Amer. Chem. Soc. 1980 (14) S. 211-233 darauf hin, dassSynthesis leads from the radical polymerization of carboethoxymethyldiallylammonium chloride to a polymer-analogous saponification, dialysis and finally deprotonation by means of NaOH to the end product. The yield of product of value here is less than 50%. Hodgkin et al. point in J. Amer. Chem. Soc. 1980 (14) pp. 211-233 indicate that
Diallylmonomere mit freien Säurefunktionen nur sehr schlecht polymerisierbar seien.Diallyl monomers with free acid functions are very difficult to polymerize.
Die dort beschriebene Polymerisation von 2-Diallylamino-benzoesäure führt nicht zumThe polymerization of 2-diallylamino-benzoic acid described there does not lead to
Erfolg.Success.
Solomon et al. führen in J. Macromol. Sci.-Rev. Macromol. Chem., C15 (1976) S. 143-164 unter anderem aus, dass Diallylamine bevorzugt in Form ihrer quarternärenSolomon et al. lead in J. Macromol. Sci.-Rev. Macromol. Chem., C15 (1976) pp. 143-164 inter alia from that diallylamines preferably in the form of their quaternary
Ammoniumsalze polymerisiert werden, da die ungeladene Form nicht „bereitwillig" unter den Bedingungen der freien radikalischen Polymerisation polymerisierbar ist.Ammonium salts are polymerized, since the uncharged form cannot be "readily" polymerized under the conditions of free radical polymerization.
Aufgabe der vorliegenden Erfindung war es, einfach und in hoher Ausbeute zugäng- liehe Homo- oder Copolymerisate aus ebenfalls einfach und in hohen Ausbeuten zugänglichen Monomeren auf Basis von Diallyamin oder Derivaten davon herzustellen, die zusätzlich zur gegebenenfalls quartemierten Diallylaminogruppe noch mindestens eine funktioneile Gruppe tragen. Diese weitere funktioneile Gruppe ist bevorzugt eine proanionische, besonders bevorzugt eine Carboxylgruppe.It was an object of the present invention to prepare homopolymers or copolymers which are easily and in high yield from monomers based on diallyamine or derivatives thereof which are likewise easily and in high yields and which, in addition to the optionally quaternized diallylamino group, also carry at least one functional group. This further functional group is preferably a proanionic, particularly preferably a carboxyl group.
Es wurde nun überraschend gefunden, dass Polymerisate auf Basis von N,N-Diallyl- amin einfach und in hohen Ausbeuten erhältlich sind, in dem man in einer Michael- Addition N,N-Diallylaminderivate der allgemeinen Formel IIt has now surprisingly been found that polymers based on N, N-diallylamine can be obtained simply and in high yields by using a Michael Addition of N, N-diallylamine derivatives of the general formula I
wobei R\ R2 unabhängig voneinander Wasserstoff oder Cι-C4-Alkyl bedeuten mit Verbindungen der allgemeinen Formel II ,H H R3 where R \ R 2 are independently hydrogen or -CC 4 alkyl with compounds of general formula II, H HR 3rd
wobei R3 COOR4, CN, CHO, SO3H, PO(OH)2 oder CONR5R6 bedeutet undwhere R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and
R4, R5 und R6 unabhängig voneinander Wasserstoff oder Ci bis C18-Alkyl bedeuten, umsetzt und die Michael-Addukte anschließend radikalisch polymerisiert, gegebenenfalls in Gegenwart von einem oder mehreren radikalisch copolymerisierbaren Monomeren.R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, are reacted and the Michael adducts are then radically polymerized, optionally in the presence of one or more radically copolymerizable monomers.
Als Diallylaminderivate der Formel I, in der R1, R2 unabhängig voneinander z.B. Wasserstoff, Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Butyl, 1 -Methylpropyl, 2-Methyl- propyl oder 1 ,1-Dimethylethyl sein können, sind die Verbindungen Diallylamin, 2-Meth- yldiallylamin oder Bis(2-methylallyl)amin, 2-Ethyldiallylamin, Bis(2-ethylallyl)amin, 2-lsopropyldiallylamin, Bis(2-isopropylallyl)amin, 2-Tert-Butyldiallylamin oder Bis(2- Tert-Butylallyl)amin bevorzugt. Besonders bevorzugt ist N,N-Diallylamin.As diallylamine derivatives of the formula I in which R 1 , R 2 are, for example, hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl independently of one another , the compounds are diallylamine, 2-methylldiallylamine or bis (2-methylallyl) amine, 2-ethyldiallylamine, bis (2-ethylallyl) amine, 2-isopropyldiallylamine, bis (2-isopropylallyl) amine, 2-tert-butyldiallylamine or bis (2-tert-butylallyl) amine is preferred. N, N-diallylamine is particularly preferred.
Verbindungen der allgemeinen Formel II sind beispielsweise Acrylsäure, Acrylsäure- ester wie Methylacrylat, Ethylacrylat, Propylacrylat, Butylacrylat, t-Butylacrylat, Iso- butylacrylat, 2-Ethylhexylacrylat und Stearylaerylat, weiterhin Acrylnitril, Acrolein, Vinyl- sulfonsäure, Vinylphosphonsäure, Acrylamid, N-t-Butylacrylamid und N-Octylacrylamid. Bevorzugte Verbindung der allgemeinen Formel II ist Acrylsäure.Compounds of the general formula II are, for example, acrylic acid, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and stearyl arylate, furthermore acrylonitrile, acrolein, vinylsulfonic acid, vinylphosphonic acid, acrylamide, naphtha Butylacrylamide and N-octylacrylamide. Preferred compound of the general formula II is acrylic acid.
Bevorzugt ist demnach die Michael-Addition von Diallylamin und Acrylsäure.Accordingly, Michael addition of diallylamine and acrylic acid is preferred.
Als Monomere zur Copolymerisation mit den erfindungsgemäßen Umsetzungsprodukten aus Verbindungen der allgemeinen Formel I und Verbindungen der allgemeinen Formeln II seien Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Crotonsäure, Itaconsäure, Maleinsäureanhydrid sowie dessen Halbester, Methylacrylat, Methylmeth- acrylat, Ethylacrylat, Ethylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, t-Butyl- acrylat, t-Butylmethacrylat, Isobutylacrylat, Isobutylmethacrylat, 2-Ethylhexylacrylat, Stearylaerylat, Stearylmethacrylat, N-t-Butylacrylamid, N-Octylacryiamid, 2-Hydroxy- ethylacrylat, Hydroxypropylacrylate, 2-Hydroxyethylmethacrylat, Hydroxypropylmeth- acrylate, Alkylenglykol(meth)acrylate, Styrol, ungesättigte Sulfonsäuren wie z.B. Acryl- amidopropansulfonsäure, Vinylpyrrolidon, Vinylcaprolactam, Vinylether (z.B.: Methyl-, Ethyl-, Butyl- oder Dodecylvinylether), Vinylformamid, Vinylmethylacetamid, Vinylamin, 1-Vinylimidazol, 1-Vinyl-2-methylimidazol, N,N-Dimethylaminomethylmethacrylat und N-[3-(dimethylamino)propyl]methacrylamid; 3-Methyl-1 -vinylimidazoliumchlorid, 3-Methyl-1-vinylimidazoliummethylsulfat, N,N-Dimethylaminoethylmethacrylat, N-[3- (dimethylamino)-propyI]methacrylamid, Methylsulfat oder Diethylsulfat genannt. Die aminogruppentragenden Monomere können in quarternierter Form vorliegen.Monomers for copolymerization with the reaction products according to the invention from compounds of the general formula I and compounds of the general formulas II include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride and its half-ester, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl arylate, stearyl methacrylate, N-butyl acrylamide, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxyl acrylate, methacrylate, unsaturated sulfonic acids such as acrylic amidopropanesulfonic acid, vinyl pyrrolidone, vinyl caprolactam, vinyl ether (e.g. methyl, ethyl, butyl or dodecyl vinyl ether), vinyl formamide, vinyl methylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N- Dimethylaminomethyl methacrylate and N- [3- (dimethylamino) propyl] methacrylamide; 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, methyl sulfate or diethyl sulfate. The monomers bearing amino groups can be present in quaternized form.
Gegenstand der vorliegenden Erfindung ist weiterhin ein Verfahren zur Herstellung der Polymerisate, ausgehend von den Verbindungen der Formeln I und II.The present invention furthermore relates to a process for the preparation of the polymers, starting from the compounds of the formulas I and II.
Das erfindungsgemäße Verfahren beinhaltet die Umsetzung einer Verbindung der allgemeinen Formel I mit mindestens einer Verbindung der allgemeinen Formel II im Sinne einer Michael-Addition.The process according to the invention comprises the reaction of a compound of general formula I with at least one compound of general formula II in the sense of a Michael addition.
Das bevorzugte molare Mengenverhältnis I zu II beträgt 1:1 , es kann aber auch mit einem Überschuss an einer der Komponenten gearbeitet werden. Als Beispiel für einen Überschuss seien genannt 1 zu 1 ,1 oder 1,1 zu 1.The preferred molar ratio I to II is 1: 1, but an excess of one of the components can also be used. An example of a surplus is 1 to 1, 1 or 1.1 to 1.
Die Michael-Addition kann je nach Mischbarkeit der Reinstoffe mit oder ohne Lösungs- mittel erfolgen. Als Lösungsmittel können Wasser, Alkohole wie beispielsweise Methanol, Ethanol, 1-Propanol, 2-Propanol, 1-Butanol, 2-.Butanol, tert.-Butanol, Ether wie beispielsweise Diethylether, tert.-Butylmethylether, Tetrahydrofuran, Dioxan, alipha- tische Kohlenwasserstoffe wie beispielsweise Pentan, Hexan, Heptan, Cyclopentan, Cyclohexan, aromatische Kohlenwasserstoffe wie beispielsweise Benzol, Toluol, Ethyl- benzol, o-Xylol, m-Xylol, p-Xylol, Ketone wie beispielsweise Aceton, Amide wie beispielsweise N,N-Dimethylformamid, N,N-Dimethylacetamid, chlorierte Kohlenwasserstoffe wie beispielsweise Dichlormethan, Chloroform oder 1 ,1 ,2,2-Tetrachlorethan, Sulfoxide, Sulfone wie beispielsweise Dimethylsulfoxid, Diethylsulfoxid oder Sulfolan eingesetzt werden.The Michael addition can take place with or without a solvent, depending on the miscibility of the pure substances. Water, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, aliphatic table hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, ketones such as acetone, amides such as N, N- Dimethylformamide, N, N-dimethylacetamide, chlorinated hydrocarbons such as dichloromethane, chloroform or 1, 1, 2,2-tetrachloroethane, sulfoxides, sulfones such as dimethyl sulfoxide, diethyl sulfoxide or sulfolane can be used.
Eine bevorzugte Ausführungsform ist die Umsetzung ohne Lösungsmittel.A preferred embodiment is the reaction without a solvent.
Die aus der Michael-Addition erhaltenen Produkte können auf an sich bekannte Weise isoliert werden.The products obtained from the Michael addition can be isolated in a manner known per se.
Die Michael-Addition erfolgt üblicherweise bei Temperaturen zwischen -20 und +50°C, bevorzugt zwischen -10 und +30°C. Gegenstand der Erfindung sind weiterhin die aus dieser Umsetzung erhaltenen Produkte der Formel IMMichael addition is usually carried out at temperatures between -20 and + 50 ° C, preferably between -10 and + 30 ° C. The invention furthermore relates to the products of the formula III obtained from this reaction
in derin the
R1 und R2 unabhängig voneinander Wasserstoff oder d bis C4-Alkyl bedeuten, R3 COOR4, CN, CHO, SO3H, PO(OH)2 oder CONR5R6 bedeutet und R4, R5 und R6 unabhängig voneinander Wasserstoff oder Ci bis C18 -Alkyl bedeuten, wobei auch eine Quarternisierung des Stickstoffs durch Protonierung vorliegen kann.R 1 and R 2 independently of one another are hydrogen or d to C 4 -alkyl, R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, it also being possible for the nitrogen to be quaternized by protonation.
Das erfindungsgemäße Verfahren beinhaltet des weiteren die Polymerisation der Produkte der Formel III. Die erfindungsgemäßen Verbindungen der allgemeinen Formel III können isoliert werden oder ohne weitere Aufarbeitung zur Polymerisation eingesetzt werden.The inventive method further includes the polymerization of the products of formula III. The compounds of the general formula III according to the invention can be isolated or used for the polymerization without further working up.
Die erfindungsgemäßen Verbindnungen der allgemeinen Formel III können zu Homo- polymeren oder in Gegenwart von einem oder mehreren radikalisch copolymerisier- baren Monomeren zu Copolymeren umgesetzt werden.The compounds of the general formula III according to the invention can be converted into homopolymers or, in the presence of one or more free-radically copolymerizable monomers, into copolymers.
Bei der Polymerisation handelt es sich um eine radikalische Polymerisation, die vorzugsweise in Lösung durchgeführt wird.The polymerization is a radical polymerization, which is preferably carried out in solution.
Mögliche Lösungsmittel sind alle für Polymerisationsreaktionen üblichen Lösungsmittel. Bevorzugtes Lösungsmittel ist Wasser. Die radikalische Polymerisation wird auf an sich bekannte Weise unter Ausschluss von Sauerstoff, beispielsweise durch Durchströmen von Inertgas und gegebenenfalls unter Inertgasatmosphäre, wobei als Inertgas bevorzugt Stickstoff eingesetzt wird, durchgeführt.Possible solvents are all solvents customary for polymerization reactions. The preferred solvent is water. The radical polymerization is carried out in a manner known per se with the exclusion of oxygen, for example by flowing through an inert gas and, if appropriate, under an inert gas atmosphere, nitrogen being preferably used as the inert gas.
Als Initiatoren für die radikalische Polymerisation können wasserlösliche und wasserunlösliche Initiatoren eingesetzt werden.Water-soluble and water-insoluble initiators can be used as initiators for the radical polymerization.
Übliche Initiatoren sind Peroxide, Hydroperoxide, Peroxodisulfate, Percarbonate, Peroxidester, Wasserstoffperoxid und Azoverbindungen. Beispielsweise seien Wasserstoffperoxid, Dibenzoylperoxid, Dicyclohexylperoxidi- carbonat, Dilauroylperoxid, Methylethylketonperoxid, Di-tert.-Butylhydroperoxid, Acetyl- acetonperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert-Butylperneodecanoat, tert.-Amylperpivalat, tert.-Butylperpivalat, tert.-Butyl-perbenzoat, Lithium-, Natrium-, Kalium- und Ammoniumperoxodisulfat genannt.Typical initiators are peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds. Examples include hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl hydroperoxide, acetyl acetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate.
Als Initiatoren können auch wasserlösliche Azoverbindungen wie beispielsweise Azo- bisisobutyronitril, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propan]dihydrochlorid, 2,2'- Azobis[2-(2-imidazolin-2-yl)propan] dihydrochlorid , 2,2'-Azobis[2-(2-imidazolin-2-yl)pro- pandisulfatdihydrat, 2,2'-Azobis(2-methylpropionamid)dihydrochlorid, 2,2'-Azobis[2- (3,4,5,6-tetrahydropyrimidin-2-yl)propan]dihydrochlohd, 2,2'-Azobis[2-(2-imidazolin-2- yl)propan],4,4'-Azo-bis-(4-cyanvaleriansäure), 1 ,1 '-Azo-bis-(cyclohexancarbonsäure- nitril), 2,2'-Azobis(isobuttersäureamidin)dihydrochlorid, 2,2'-Azobis[N-(2-carboxy- ethyl)-2-methylpropionamidin]tetrahydrat, 2,2'-Azobis{2-[1 -(2-hydroxyethyl)-2-imi- dazolin-2-yl]propan}dihydrochlorid, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2- hydroxyethyl] propionamid, 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybuthyl)]propionamid}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamid] und in organischen Lösungsmitteln lösliche Azoverbindungen wie beispielsweise, 2,2'-Azobis(4-methoxy-2,4-di- methyl valeronitril), 2,2'-Azobis(2,4-dimethyl valeronitril), Dimethyl 2,2'-azobis(2 methyl- propionat), 2,2'-Azobis(2-methylbutyronitril), 1 , 1 '-Azobis(cyclohexan-1 -carbonitril), 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamid], 1-[(cyano-1-methylethyl)azo] form- amid, 2,2'-Azobis(N-butyl-2-methylpropionamid), 2,2'-Azobis(N-cyclohexyl-2-methyl- propionamid) eingesetzt werden.Water-soluble azo compounds such as, for example, azobisisobutyronitrile, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2- imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane disulfate dihydrate, 2,2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'- Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 4,4'-azo -bis- (4-cyanvaleric acid), 1, 1 '-azo-bis- (cyclohexanecarboxylic acid nitrile), 2,2'-azobis (isobutyric acid amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxy-ethyl ) -2-methylpropionamidine] tetrahydrate, 2,2'-azobis {2- [1 - (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis {2-methyl-N- [2- (1-hydroxybuthyl)] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] and azo compounds which are soluble in organic solvents, for example, 2 , 2'-azobis (4-methoxy-2,4-dimethyl valeronitrile), 2,2'-azobis (2,4-dimethyl valeronitrile), dimethyl 2,2'-azobis (2 methyl propionate), 2 , 2'-azobis (2-methylbutyronitrile), 1, 1 '-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 1 - [(cyano -1-methylethyl) azo] form amide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) can be used.
Die Initiatoren können allein oder als Mischungen angewendet werden. Beispiele für solche Mischungen sind binäre Mischungen wie z.B. Mischungen aus Wasserstoffperoxid und Natriumperoxodisulfat. Für die Polymerisation in wässrigem Medium werden bevorzugt wasserlösliche Initia- toren eingesetzt.The initiators can be used alone or as mixtures. Examples of such mixtures are binary mixtures such as e.g. Mixtures of hydrogen peroxide and sodium peroxodisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium.
Des Weiteren können Redox-Initiatorsysteme als Polymerisationsinitiatoren verwendet werden. Solche Redox-Initiatorsysteme enthalten mindestens eine peroxidhaltige Verbindung in Kombination mit einem Redox-Coinitiator wie beispielsweise reduzierend wirkende Schwefelverbindungen wie Bisulfite, Sulfite, Thiosulfate, Dithionite und Tetra- thionate von Alkalimetallen und Ammoniumverbindungen.Furthermore, redox initiator systems can be used as polymerization initiators. Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator such as, for example, reducing sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites and tetrahionates of alkali metals and ammonium compounds.
So kann man Kombinationen von Peroxodisulfaten mit Alkalimetall- oder Ammoniumhydrogensulfiten einsetzen, z.B. Ammoniumperoxodisulfat und Ammoniumdisulfit. Die Mengenverhältnisse von peroxidhaltiger Verbindung zu Redox-Coinitiator liegen im Bereich von 30 : 1 bis 0,05 : 1.For example, combinations of peroxodisulfates with alkali metal or ammonium bisulfites can be used, e.g. Ammonium peroxodisulfate and ammonium disulfite. The proportions of peroxide-containing compound to redox coinitiator are in the range from 30: 1 to 0.05: 1.
In Kombination mit den Initiatoren bzw. den Redoxinitiatorsystemen können zusätzlich Übergangsmetallkatalysatoren eingesetzt werden, beispielsweise Salze von Eisen, Kobalt, Nickel, Kupfer, Vanadium und Mangan. Geeignete Salze sind beispielsweise Eisen(ll)sulfat, Kobalt(ll)chlorid, Nickel(ll)sulfat, oder Kupfer(l)chlorid. Bezogen auf die Monomeren wird das reduzierend wirkende Übergangsmetallsalz üblicherweise in einer Konzentration im Bereich von 0,1 ppm bis ca. 1000 ppm eingesetzt. So kann man Kombinationen von Wasserstoffperoxid mit Eisen(ll)-Salzen einsetzen, wie beispielsweise 0,5 bis 30 % Wasserstoffperoxid und 0,1 bis 500 ppm Mohrsches Salz.In combination with the initiators or the redox initiator systems, additional transition metal catalysts can be used, for example salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, or copper (I) chloride. Based on the monomers, the reducing transition metal salt is usually used in a concentration in the range from 0.1 ppm to approx. 1000 ppm. Combinations of hydrogen peroxide with iron (II) salts can be used, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.
Bei der Polymerisation in organischen Lösungsmitteln können in Kombination mit den oben genannten Initiatoren Redox-Coinitiatoren und/oder Übergangsmetallkatalysatoren mitverwendet werden, beispielsweise Benzoin, Dimethylanilin, Ascorbin- säure sowie organisch lösliche Komplexe von Schwermetallen, wie Kupfer, Cobalt, Eisen, Mangan, Nickel und Chrom.When polymerizing in organic solvents, redox coinitiators and / or transition metal catalysts can be used in combination with the abovementioned initiators, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and Chrome.
Die üblicherweise verwendeten Mengen an Redox-Coinitiatoren bzw. Übergangsmetallkatalysatoren betragen etwa 0,1 bis ca. 1000 ppm, bezogen auf die eingesetzten Mengen an Monomeren.The amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to about 1000 ppm, based on the amounts of monomers used.
In einer bevorzugten Ausführungsform werden wasserlösliche Azoinitiatoren, Wasserstoffperoxid, Natriumpersulfat, Kaliumpersulfat oder Ammoniumpersulfat eingesetzt.In a preferred embodiment, water-soluble azo initiators, hydrogen peroxide, sodium persulfate, potassium persulfate or ammonium persulfate are used.
Besonders bevorzugte Initiatoren sind wasserlösliche Azoinitiatoren, ganz besonders bevorzugt ist 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochlorid (Handelsname: VA-044).Particularly preferred initiators are water-soluble azo initiators; 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (trade name: VA-044) is very particularly preferred.
Die Initiatormengen liegen im allgemeinen zwischen 0,5 und 10 Gew.-% bezogen auf die Gesamtmasse an Monomer. Bevorzugte Mengen sind 1 bis 6 Gew.-%, besonders bevorzugt sind 2 bis 4 Gew.-%.The amounts of initiator are generally between 0.5 and 10% by weight, based on the total mass of monomer. Preferred amounts are 1 to 6% by weight, particularly preferred are 2 to 4% by weight.
Im Fall der Copolymerisation von Verbindungen der Formel III mit einem oder mehreren radikalisch polymerisierbaren Monomeren liegt der molare Anteil an Verbindung III bezogen auf die Gesamtmenge an Monomeren im Bereich von 5 bis 95 Mol-%, bevor- zugt im Bereich von 20 bis 80 Mol-%, besonders bevorzugt im Bereich von 45 bis 55 Mol-%.In the case of the copolymerization of compounds of the formula III with one or more radically polymerizable monomers, the molar proportion of compound III, based on the total amount of monomers, is in the range from 5 to 95 mol%, preferably in the range from 20 to 80 mol%. %, particularly preferably in the range from 45 to 55 mol%.
Die Polymerisation kann in einem Temperaturbereich zwischen 30 und 90°C, bevorzugt zwischen 40 und 70°C, ganz besonders bevorzugt zwischen 55 und 65°C durch- geführt werden.The polymerization can be carried out in a temperature range between 30 and 90 ° C., preferably between 40 and 70 ° C., very particularly preferably between 55 and 65 ° C.
Die Homopolymerisation von Monomeren der allgemeinen Formel III kann ohne oder mit Zusatz von Säure durchgeführt werden. Bei Abwesenheit von hydrolyseempfindlichen Substituenten wird sie bevorzugt in Gegenwart von Säuren durchgeführt.The homopolymerization of monomers of the general formula III can be carried out without or with the addition of acid. In the absence of hydrolysis-sensitive substituents, it is preferably carried out in the presence of acids.
Geeignete Säuren sind Salzsäure, Schwefelsäure, Phosphorsäure, Salpetersäure, Perchlorsäure, Methansulfonsäure, p-Toluolsulfonsäure, Benzolsulfonsäure, Trifluor- essigsaure, Trifluormethansulfonsäure, Ameisensäure, Essigsäure, Chloressigsäure,Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoro- acetic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, chloroacetic acid,
Dichloressigsäure und Trichloressigsäure.Dichloroacetic acid and trichloroacetic acid.
Besonders geeignet sind Salzsäure, Schwefelsäure und Phosphorsäure, ganz besonders geeignet ist Salzsäure.Hydrochloric acid, sulfuric acid and phosphoric acid are particularly suitable, hydrochloric acid is very particularly suitable.
Die Homopolymerisation von Monomeren der allgemeinen Formel III in wässriger Lösung kann vorzugsweise bei Säure-Konzentrationen im Bereich von 0 und 70 Mol-% durchgeführt werden. Besonders bevorzugt sind molare Konzentrationen größer als 5 Mol-%, ganz besonders bevorzugt größer als 30 Mol-%.The homopolymerization of monomers of the general formula III in aqueous solution can preferably be carried out at acid concentrations in the range from 0 to 70 mol%. Molar concentrations greater than 5 mol% are particularly preferred, very particularly preferably greater than 30 mol%.
Die Copolymerisation von Monomeren der allgemeinen Formel III mit der Hydrolyse zugänglichen Monomeren wie beispielsweise Vinylformamid wird vorteilhaft in gepufferter wässriger Lösung durchgeführt.The copolymerization of monomers of the general formula III with the monomers accessible by hydrolysis, such as, for example, vinylformamide, is advantageously carried out in a buffered aqueous solution.
Die Summe der Konzentrationen der Monomere in der Lösung liegen zwischen 15 und 85 %, bevorzugt zwischen 25 und 75 %, besonders bevorzugt zwischen 40 und 60 %.The sum of the concentrations of the monomers in the solution are between 15 and 85%, preferably between 25 and 75%, particularly preferably between 40 and 60%.
Die Eigenschaften wie beispielsweise das Molekulargewicht (Mw, Mn) der erfindungsgemäßen Polymerisate hängen von den gewählten Reaktionsbedingungen ab. Bei- spielsweise seien als Einflussgrößen die Reaktionsbedingungen Initiatormenge, Initiatortyp, Verlauf der Initiatorzugabe, Verwendung von Säure, Typ und Menge der Säure, Feststoffgehalt der Polymerisationslösung, Temperatur, Reaktionsdauer, Nachpolymerisation mit wiederholter Initiatorzugabe oder Dauer der Nachpolymerisation genannt. Die Ausbeuten liegen je nach gewählten Reaktionsbedingungen zwischen 40 und 95 %. Die Molekulargewichte Mw liegen im Bereich zwischen 10000 und 300000, insbesondere zwischen 30000 und 200000.The properties such as the molecular weight (M w , M n ) of the polymers according to the invention depend on the reaction conditions chosen. For example, the reaction conditions initiator amount, initiator type, course of initiator addition, use of acid, type and amount of acid, solids content of the polymerization solution, temperature, reaction time, post-polymerization with repeated addition of initiator or duration of the post-polymerization may be mentioned as influencing variables. The yields are between 40 and 95% depending on the reaction conditions chosen. The molecular weights M w are in the range between 10,000 and 300,000, in particular between 30,000 and 200,000.
So erhält man beispielsweise bei der Herstellung von Poly(N,N-Diallyl-3-amino- propionsäure) im salzsauren Medium bei einem Feststoffgehalt (Gesamtkonzentration der Monomere) von 50 % und Initiatorkonzentrationen von 3 % Ausbeuten von 90 %. Die Lösungen der erfindungsgemäßen Polymere zeigen betainisches Verhalten.For example, in the production of poly (N, N-diallyl-3-aminopropionic acid) in hydrochloric acid medium with a solids content (total monomer concentration) of 50% and initiator concentrations of 3% yields of 90%. The solutions of the polymers according to the invention show betaine behavior.
Die erfindungsgemäßen Polymerisate können vielfältig eingesetzt werden, zum Beispiel in kosmetischen und pharmazeutischen Mittel, Lebensmitteln, Tensiden und Reinigungsmitteln. Die erfindungsgemäßen Polymerisate können Verwendung finden in der Erdölindustrie, Zellstoffverarbeitung, Lackherstellung und Textilindustrie.The polymers according to the invention can be used in a variety of ways, for example in cosmetic and pharmaceutical compositions, foods, surfactants and cleaning agents. The polymers according to the invention can be used in the petroleum industry, pulp processing, paint production and textile industry.
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert ohne sie darauf einzuschränken: Beispiel 1: N,N-Diallyl-3-AminopropionsäureThe invention is illustrated by the following examples without restricting it: Example 1: N, N-diallyl-3-aminopropionic acid
250 g Diallylamin wurden bei 0°C unter Stickstoffatmosphäre gerührt. 185,5 g Acrylsäure (Molverhältnis 1:1) wurden während zwei Stunden zugetropft. Der Ansatz wurde auf 40°C erwärmt und für weitere vier Stunden gerührt. Man erhält als Reaktionsprodukt in quantitativer Ausbeute eine braune, viskose Flüssigkeit . Der pH-Wert einer 1 %igen (Molprozent) wässrigen Lösung beträgt ca. 5,8.250 g of diallylamine were stirred at 0 ° C under a nitrogen atmosphere. 185.5 g of acrylic acid (molar ratio 1: 1) were added dropwise over two hours. The mixture was heated to 40 ° C. and stirred for a further four hours. A brown, viscous liquid is obtained as a reaction product in quantitative yield. The pH of a 1% (mole percent) aqueous solution is approximately 5.8.
Strukturaufklärung mittels NMR-Spektroskopie: H NMR (500 MHz, Lösungsmittel CDCI3): Tabelle 1:Structure elucidation by means of NMR spectroscopy: H NMR (500 MHz, solvent CDCI 3 ): Table 1:
13C NMR (500 MHz, Lösungsmittel D2O): δ = 34, 52.5, 58, 129, 130 and 181 ppm. 13 C NMR (500 MHz, solvent D 2 O): δ = 34, 52.5, 58, 129, 130 and 181 ppm.
Beispiel 2: Poly(N,N-Diallyl-3-aminopropionsäure)Example 2: Poly (N, N-diallyl-3-aminopropionic acid)
Eine Monomerlösung, enthaltend 200 g N,N-Diallyl-3-Aminopropionsäure, 67,5 g 32 %ige Salzsäure und 32,5 g Wasser wurde unter Stickstoffatmosphäre auf 60°C erwärmt. Danach wurde die Polymerisation durch Zugabe von 10 % einer 8 %igen wässrigen Initiatorlösung von VA-044 (2,2'-Azobis[2-(2-imidazolin-2-yl)propan]di- hydrochlorid) gestartet (die Gesamtmenge Initiator beträgt 4 Gew.-% bezogen auf die Gesamtmenge Monomer). Weitere 60 % Initiatorlösung wurden tropfenweise über 3 Stunden zugegeben. Nach weiteren 2 Stunden unter Rühren wurde die restliche Initiatorlösung während einer Stunde zugegeben, schließlich die Temperatur auf 80°C erhöht und nochmals 3 Stunden gerührt. Man erhielt das Polymerisat in einer Ausbeute von 93 %. Abhängigkeit der Ausbeute an Poly(N,N-Diallyl-3-aminopropionsäure) von der Säurekonzentration:A monomer solution containing 200 g of N, N-diallyl-3-aminopropionic acid, 67.5 g of 32% hydrochloric acid and 32.5 g of water was heated to 60 ° C. under a nitrogen atmosphere. The polymerization was then started by adding 10% of an 8% aqueous initiator solution of VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride) (the total amount of initiator is 4 wt .-% based on the total amount of monomer). Another 60% initiator solution was added dropwise over 3 hours. After a further 2 hours with stirring, the remaining initiator solution was added over a period of 1 hour, the temperature was finally raised to 80 ° C. and the mixture was stirred for another 3 hours. The polymer was obtained in a yield of 93%. Dependence of the yield of poly (N, N-diallyl-3-aminopropionic acid) on the acid concentration:
Die in Tabelle 2 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 2 beschriebenen Reaktion hergestellt, wobei die Säuremenge variiert wurde. Weitere Reaktionsbedingungen: Die Konzentration der Säure ist bezogen auf die Monomermenge. Gewichtsanteil aller Monomere 50 %, Gewichtsanteil Katalysator VA-0444%, Nach- polymerisationszeit 1 h, Temperatur 60°C, 10 Vol-% der Initiatorlösung zu Beginn der Reaktion zugegebenThe polymers mentioned in Table 2 were prepared essentially analogously to the reaction described in Example 2, the amount of acid being varied. Further reaction conditions: The concentration of the acid is based on the amount of monomer. Weight fraction of all monomers 50%, weight fraction catalyst VA-0444%, night Polymerization time 1 h, temperature 60 ° C, 10 vol% of the initiator solution added at the beginning of the reaction
Tabelle 2:Table 2:
Ausbeute und Molekulargewicht Mw von Poly(N,N-Diallyl-3-Aminopropionsäure) in Abhängigkeit vom Feststoffgehalt der Monomerlösung (Gew.-%) Die in Tabelle 3 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 2 beschriebenen Reaktion hergestellt, wobei die vorgelegte Monomermenge variiert wurde. Weitere Reaktionsbedingungen: Nachpolymerisationszeit 1 h, Temperatur 60°C, 10 Vol-% der Initiatorlösung zu Beginn der Reaktion zugegeben, Salzsäure, Säurekonzentration 50 % bezogen auf Mono- mermenge, Gewichtsanteil Katalysator VA-044 2 %. Yield and molecular weight M w of poly (N, N-diallyl-3-aminopropionic acid) as a function of the solids content of the monomer solution (% by weight). The polymers mentioned in Table 3 were prepared essentially analogously to the reaction described in Example 2, the submitted amount of monomer was varied. Further reaction conditions: post-polymerization time 1 h, temperature 60 ° C., 10% by volume of the initiator solution added at the start of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer, weight percentage of catalyst VA-044 2%.
Tabelle 3:Table 3:
Abhängigkeit der Ausbeute und des Molekulargewichts Mw von Poly(N,N-Diallyl-3- Aminopropionsäure) von der Reaktionstemperatur Dependence of the yield and the molecular weight M w of poly (N, N-diallyl-3-aminopropionic acid) on the reaction temperature
Die in Tabelle 4 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 2 beschriebenen Reaktion hergestellt, wobei die Temperatur variiert wurde. Weitere Reaktionsbedingungen: Gewichtsanteil aller Monomere 50 %, Gewichtsanteil Katalysator VA-044 2 %, Nachpolymerisationszeit 1 h, 25 Vol-% der Initiatorlösung zu Beginn der Reaktion zugegeben, Salzsäure, Säurekonzentration 50% bezogen auf Monomermenge. Tabelle 4:The polymers mentioned in Table 4 were prepared essentially analogously to the reaction described in Example 2, the temperature being varied. Further reaction conditions: 50% by weight of all monomers, 2% by weight of catalyst VA-044, post-polymerization time 1 h, 25% by volume of the initiator solution added at the start of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer. Table 4:
Abhängigkeit der Ausbeute an Poly(N,N-Diallyl-3-Aminopropionsäure) von der Initiatormenge (Gew.-% bezogen auf Monomer) Dependence of the yield of poly (N, N-diallyl-3-aminopropionic acid) on the amount of initiator (% by weight based on monomer)
Die in Tabelle 5 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 2 beschriebenen Reaktion hergestellt, wobei die Initiatormenge variiert wurde. Weitere Reaktionsbedingungen: Gewichtsanteil aller Monomere 50 %, Nachpolymerisationszeit 1 h, Temperatur 60°C, 10 Vol-% der Initiatorlösung zu Beginn der Reaktion zugegeben, Salzsäure, Säurekonzentration 50 % bezogen auf Monomermenge.The polymers mentioned in Table 5 were prepared essentially analogously to the reaction described in Example 2, the amount of initiator being varied. Further reaction conditions: weight fraction of all monomers 50%, post-polymerization time 1 h, temperature 60 ° C., 10% by volume of the initiator solution added at the beginning of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer.
Tabelle 5:Table 5:
Ausbeuten und Molekulargewichte Mw von Poly(N,N-Diallyl-3-Aminopropionsäure) in Abhängigkeit von verschiedenen PolymerisationsbedingungenYields and molecular weights M w of poly (N, N-diallyl-3-aminopropionic acid) depending on various polymerization conditions
Die in Tabelle 6 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 2 beschriebenen Reaktion hergestellt, wobei die Temperatur und die Initiatorzugabe variiert wurden. Weitere Reaktionsbedingungen: Gewichtsanteil der Monomere 50 %, Gewichtsanteil Katalysator VA-0442 %, Nachpolymerisationszeit 1 h, Säuremenge bezogen auf Monomermenge 50 %,The polymers mentioned in Table 6 were prepared essentially analogously to the reaction described in Example 2, the temperature and the addition of initiator being varied. Further reaction conditions: weight fraction of the monomers 50%, weight fraction catalyst VA-0442%, post-polymerization time 1 h, amount of acid based on the amount of monomer 50%,
Tabelle 6Table 6
Beispiel 4: Poly(N,N-Diallyl-3-Aminopropionsäure-co-Acrylamid)Example 4: Poly (N, N-diallyl-3-aminopropionic acid-co-acrylamide)
Eine gemeinsame 50 %ige wässrige Lösung aus 169 g N,N-Diallyl-3-Aminopropion- säure und 71 g Acrylamid (Molverhältnis 1 :1) und eine auf die Monomermenge bezogene 4 %ige wässrige Initiatorlösung von VA-044 (9,6 g gelöst in 480 ml Wasser) wurden in je einem Tropftrichter vorbereitet. 20 % der Monomeriösung wurden in das Reaktionsgefäß getropft und auf 60°C erwärmt. Durch Zugabe von 20 % der Initiatorlösung wurde die Reaktion gestartet. Die verbleibende Monomerlösung wurde dann während vier, die restliche Initiatoriösung während fünf Stunden zugetropft. Danach wurde die Reaktionsmischung noch eine Stunde bei 80°C gerührt. Man erhielt eine leicht gelbliche Lösung bei einer Polymerausbeute von 85 %.A common 50% aqueous solution of 169 g of N, N-diallyl-3-aminopropionic acid and 71 g of acrylamide (molar ratio 1: 1) and a 4% aqueous initiator solution of VA-044 (9.6 g dissolved in 480 ml water) were prepared in a dropping funnel. 20% of the monomer solution was dropped into the reaction vessel and heated to 60 ° C. The reaction was started by adding 20% of the initiator solution. The remaining monomer solution was then added dropwise over four hours, the remaining initiator solution over five hours. The reaction mixture was then stirred at 80 ° C. for another hour. A slightly yellowish solution was obtained with a polymer yield of 85%.
Ausbeuten bei der Herstellung von Poly(N,N-Diallyl-3-aminopropionsäure-co-Acryl- amid) unter verschiedenen Reaktionsbedingungen Die in Tabelle 7 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 4 beschriebenen Reaktion hergestellt, wobei die einzelnen Reaktionsbedingungen der Tabelle 6 zu entnehmen sind.Yields in the preparation of poly (N, N-diallyl-3-aminopropionic acid-co-acrylamide) under various reaction conditions. The polymers mentioned in Table 7 were prepared essentially analogously to the reaction described in Example 4, the individual reaction conditions in the table 6 can be seen.
DPA: N,N-Diallyl-3-Aminopropionsäure AAM: AcrylamidDPA: N, N-diallyl-3-aminopropionic acid AAM: acrylamide
Tabelle 7Table 7
Beispiel 6: Poly(N,N-Diallyl-3-aminopropionsäure-co-Vinylformamid) Example 6: Poly (N, N-diallyl-3-aminopropionic acid-co-vinylformamide)
Eine gemeinsame 25 %ige wässrige Lösung aus N,N-Diallyl-3-Aminopropionsäure und Vinylformamid (Molverhältnis 1:1) und eine auf die Monomermenge bezogene 4 gew.-%ige wässrige Initiatorlösung von VA-044 wurden in je einem Tropftrichter vorbereitet. 20 % der Monomerlösung wurden in das Reaktionsgefäß getropft und auf 60°C erwärmt. Als Puffer wurden 4.8g NaH2PO *2H2O zugegeben. Durch Zugabe von 20 % der Initiatorlösung wurde die Reaktion gestartet. Die verbleibende Monomer- lösung wurde dann während vier, die restliche Initiatorlösung während fünf Stunden zugetropft. Danach wurde die Reaktionsmischung noch eine Stunde bei 80°C gerührt. Die Polymerausbeute betrug 94 %. Ausbeuten bei der Herstellung von Poly(N,N-Diallyl-3-aminopropionsäure-co-Vinyl- formamid) unter verschiedenen ReaktionsbedingungenA common 25% aqueous solution of N, N-diallyl-3-aminopropionic acid and vinylformamide (molar ratio 1: 1) and a 4% by weight aqueous initiator solution of VA-044, based on the amount of monomer, were each prepared in a dropping funnel. 20% of the monomer solution was dropped into the reaction vessel and heated to 60 ° C. 4.8 g of NaH 2 PO * 2H 2 O were added as a buffer. The reaction was started by adding 20% of the initiator solution. The remaining monomer solution was then added dropwise over four hours, the remaining initiator solution over five hours. The reaction mixture was then stirred at 80 ° C. for another hour. The polymer yield was 94%. Yields in the production of poly (N, N-diallyl-3-aminopropionic acid-co-vinylformamide) under different reaction conditions
Die in Tabelle 8 genannten Polymerisate wurden im wesentlichen analog der in Beispiel 4 beschriebenen Reaktion hergestellt, wobei die einzelnen Reaktions- bedingungen der Tabelle 8 zu entnehmen sind.The polymers mentioned in Table 8 were prepared essentially analogously to the reaction described in Example 4, the individual reaction conditions being shown in Table 8.
VFA: VinylformamidVFA: vinyl formamide
Tabelle 8:Table 8:

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Polymerisaten dadurch gekennzeichnet, dass man N,N-Diallylaminderivate der allgemeinen Formel I1. A process for the preparation of polymers, characterized in that N, N-diallylamine derivatives of the general formula I
wobei R\ R2 unabhängig voneinander Wasserstoff oder d-C4-Alkyl bedeuten, im Sinne einer Michael-Addition mit Verbindungen der allgemeinen Formel II where R \ R 2 independently of one another denote hydrogen or dC 4 alkyl, in the sense of a Michael addition with compounds of the general formula II
H H κ s I I H R3 wobei R3 COOR4, CN, CHO, SO3H, PO(OH)2 oder CONR5R6 bedeutet, R4, R5, R6 unabhängig voneinander Wasserstoff oder C-i bis C18-Alkyl bedeuten, umsetzt und die Michael-Addukte anschließend radikalisch polymerisiert, gegebenenfalls in Gegenwart von einem oder mehreren radikalisch copolymerisierbaren Monomeren.HH κ s IIHR 3 where R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 , R 4 , R 5 , R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl , and the Michael adducts are then radically polymerized, optionally in the presence of one or more radically copolymerizable monomers.
2. Verfahren nach Anspruch 1 , wobei R1 und R2 Wasserstoff bedeuten.2. The method according to claim 1, wherein R 1 and R 2 are hydrogen.
3. Verfahren nach den Ansprüchen 1 oder 2, wobei R3 COOH bedeutet.3. The method according to claims 1 or 2, wherein R 3 is COOH.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass man die Polymerisation in Gegenwart eines oder mehrerer der Monomere ausgewählt aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure, Fumar- säure, Crotonsäure, Itaconsäure, Maleinsäureanhydrid sowie dessen Halbester, Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, t-Butylacrylat, t-Butylmethacrylat, Isobutylacrylat, Isobutyl- methacrylat, 2-Ethylhexylacrylat, Stearylaerylat, Stearylmethacrylat, Acrylamid, N-t-Butylacryiamid, N-Octylacrylamid, 2-Hydroxyethylacrylat, Hydroxypropyl- acrylate, 2-Hydroxyethylmethacrylat, Hydroxypropylmethacrylate, Alkylenglykol- (meth)acrylate, Styrol, ungesättigte Sulfonsäuren wie z.B. Acrylamidopropan- sulfonsäure, Vinylpyrrolidon, Vinylcaprolactam, Vinylether (z.B.: Methyl-, Ethyl-, Butyl- oder Dodecylvinylether), Vinylformamid, Vinylmethylacetamid, Vinylamin, 1-Vinylimidazol, 1-Vinyl-2-methylimidazol, N,N-Dimethylaminomethylmeth- acrylat und N-[3-(dimethyiamino)propyl]methacrylamid, 3-Methyl-1 -vinyl- imidazoliumchlorid, 3-Methyl-1 -vinylimidazoliummethylsulfat, N,N-Dimethyl- aminoethylmethacrylat, N-[3-(dimethylamino)-propyl]methacrylamid quaterni- siert mit Methylchlorid, Methylsulfat oder Diethylsulfat vornimmt.4. The method according to claims 1 to 3, characterized in that the polymerization in the presence of one or more of the monomers selected from the group acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride and its half ester, methyl acrylate, methyl methacrylate , Ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, stearyl methacrylate, acrylamide, nt-butyl acrylyl acrylate, hydroxyl acrylate, hydroxyl acrylate, - acrylates, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylates, alkylene glycol (meth) acrylates, styrene, unsaturated sulfonic acids such as acrylamidopropanesulfonic acid, vinyl pyrrolidone, vinyl caprolactam, vinyl ether (e.g. methyl, ethyl, Butyl or dodecyl vinyl ether), vinyl formamide, vinyl methylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N-dimethylaminomethyl methacrylate and N- [3- (dimethyiamino) propyl] methacrylamide, 3-methyl-1 - vinyl imidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide quaternized with methyl chloride, methyl sulfate or diethyl sulfate.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass die Polymerisation in Gegenwart einer Säure ausgewählt aus der Gruppe Salz- säure, Schwefelsäure, Phosphorsäure, Salpetersäure erfolgt.5. Process according to claims 1 to 4, characterized in that the polymerization is carried out in the presence of an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass die Reaktionstemperatur zwischen 30 und 90°C liegt.6. The method according to claims 1 to 5, characterized in that the reaction temperature is between 30 and 90 ° C.
7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, dass die Reaktionstemperatur zwischen 40 und 70°C liegt.7. The method according to claims 1 to 6, characterized in that the reaction temperature is between 40 and 70 ° C.
8. Polymerisate erhältlich nach einem Verfahren gemäß der Ansprüche 1 bis 7.8. Polymers obtainable by a process according to claims 1 to 7.
9. N,N-Diallylaminderivate der allgemeinen Formel IM9. N, N-diallylamine derivatives of the general formula IM
in der R1, R2 unabhängig voneinander Wasserstoff oder d bis C4-Alkyl bedeuten, R3 COOR4, CN, CHO, SO3H, PO(OH)2 oder CONR5R6 bedeutet und R4, R5, R6 unabhängig voneinander Wasserstoff oder d bis C18 -Alkyl bedeuten, wobei auch eine Quartämisierung des Stickstoffs durch Protonierung vorliegen kann. in which R 1 , R 2 independently of one another are hydrogen or d to C 4 -alkyl, R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and R 4 , R 5 , R 6 independently of one another are hydrogen or d to C 18 -alkyl, and a quaternization of the nitrogen by protonation can also be present.
10. N,N-Diallylaminderivate nach Anspruch 9, wobei R1 und R2 Wasserstoff bedeuten.10. N, N-diallylamine derivatives according to claim 9, wherein R 1 and R 2 are hydrogen.
11. N,N-Diallylaminderivate nach den Ansprüchen 9 und 10, wobei R3 COOH bedeutet. 11. N, N-diallylamine derivatives according to claims 9 and 10, wherein R 3 is COOH.
12. Verfahren zur Herstellung von substituierten N,N-Diallylaminderivaten der allgemeinen Formel III gemäß den Ansprüchen 9 bis 11 , dadurch gekennzeichnet, dass man eine Michael-Addition zwischen N,N-Diallyiaminderivaten der allgemeinen Formel I12. A process for the preparation of substituted N, N-diallylamine derivatives of the general formula III according to claims 9 to 11, characterized in that a Michael addition between N, N-diallyiamine derivatives of the general formula I
wobei R1, R2 unabhängig voneinander Wasserstoff oder Cι-C4-Alkyl bedeuten und Verbindungen der allgemeinen Formel II where R 1 , R 2 are independently hydrogen or -CC 4 alkyl and compounds of the general formula II
H H / ,C=C \ -> I III H R3 wobei R3 COOR4, CN, CHO, SO3H, PO(OH)2 oder CONR5R6 bedeutet und R4, R5, R6 unabhängig voneinander Wasserstoff oder d bis C18-Alkyl bedeuten, vornimmt.HH /, C = C \ -> I III HR 3 where R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and R 4 , R 5 , R 6 are independently hydrogen or d is C to C 18 alkyl.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass kein Lösungsmittel verwendet wird.13. The method according to claim 12, characterized in that no solvent is used.
14. Verwendung der Polymerisate gemäß Anspruch 8 zur Herstellung kosmetischer und pharmazeutischer Mittel.14. Use of the polymers according to claim 8 for the production of cosmetic and pharmaceutical agents.
15. Verwendung der Polymerisate gemäß Anspruch 8 zur Herstellung von Fixier- und Flockungsmitteln.15. Use of the polymers according to claim 8 for the production of fixatives and flocculants.
16. Verwendung der Polymerisate gemäß Anspruch 8 zur Herstellung von Wasch- und Reinigungsmitteln.16. Use of the polymers according to claim 8 for the production of detergents and cleaning agents.
17. Verwendung der Polymerisate gemäß Anspruch 8 in Polymerdispersionen. 17. Use of the polymers according to claim 8 in polymer dispersions.
EP04765386A 2003-09-29 2004-09-18 Polymers based on n,n-diallylamine derivatives, their production and use Withdrawn EP1670837A1 (en)

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