EP2225309A1 - Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendung - Google Patents
Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendungInfo
- Publication number
- EP2225309A1 EP2225309A1 EP08864640A EP08864640A EP2225309A1 EP 2225309 A1 EP2225309 A1 EP 2225309A1 EP 08864640 A EP08864640 A EP 08864640A EP 08864640 A EP08864640 A EP 08864640A EP 2225309 A1 EP2225309 A1 EP 2225309A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymers
- graft
- acid
- graft polymers
- side chains
- 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.)
- Withdrawn
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/065—Polyamides; Polyesteramides; Polyimides
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Definitions
- the invention relates to graft polymers which contain exclusively oligoalkyleneimine side chains as side chains and whose graft base is selected from the group comprising polymers comprising vinylamine units, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids, processes for the preparation of graft polymers having oligoalkyleneimine side chains, one of the said grafting bases grafting at least one oligoalkyleneimine which contains a terminal aziridine group and the use of the graft polymers obtainable as process chemicals in the production of paper, as antimicrobial coating agents, as builders in detergents and for the treatment of metal surfaces.
- graft polymers of ethyleneimine on polyacrylic acid and / or polymethacrylic acid are known. These are comb polymers containing as side chains Ethyleniminiseren. The molecular weight distribution of the formed PfropfITAe is wide.
- the grafted branches may, for example, consist of only one ethyleneimine unit or of several alkyleneimine units.
- a serious disadvantage of the grafting of polymers with ethyleneimine is the very long reaction time necessary to suppress the formation of homopolymers of ethyleneimine.
- the graft polymers are used in the manufacture of paper as a wet strength agent.
- polyalkyleneimines having molecular weights of 300 to 3000 which have an intact terminal aziridine ring. They are prepared by polymerizing alkyleneimines in the presence of aluminum trialkyls, an acid or a Lewis acid as catalyst in a virtually anhydrous solvent such as benzene, toluene, n-heptane, cyclohexane or 2-ethylhexane.
- the polymers can be used as bactericides or as curing agents for epoxy resins.
- H 9 C CCO [Al] - H • nHY 2 m known in which R is hydrogen or C 1 to C 4 alkyl, - [Al] m is a linear or branched oligoalkyleneimine chain having m alkyleneimine units, m is an integer in the range from 1 to 20, and the number average m in the
- Oligoalkyleniminketten at least 1, 5, Y is the anion equivalent of a mineral acid and n is a number of 1 ⁇ n ⁇ m.
- Monomers or monomer mixtures in which the number average of m in the above formula is at least 2.1, usually 2.1 to 8, are preferred. They are obtainable by reacting an ethylenically unsaturated carboxylic acid with an oligoalkyleneimine, preferably in the form of an oligomer mixture. The resulting product may optionally be converted with a mineral acid HY in the acid addition salt.
- Such monomers can be polymerized in an aqueous medium in the presence of an initiator which initiates a radical polymerization to homo- and copolymers, which are used as auxiliaries in papermaking.
- dendritic macromonomers and polymers prepared therefrom are known from EP-A 1 524 314.
- the macromonomers are prepared, for example, by reacting an addition product of ethylene oxide with polyethyleneimine with allyl glycidyl ether. Copolymers of these macromonomers with acrylic acid are used as builders in detergents.
- n is a linear or branched oligoalkyleneimine chain having n alkyleneimine units, n is a number of at least 1, and
- X represents a straight-chain or branched C 2 - to C 6 -alkylene group and also salts of the monomers I with mineral acids or organic acids and quaternization products of the monomers I with alkyl halides or dialkyl sulfates.
- Polymers which comprise copolymerized monomers of the formula I are used, for example, as fixing agents in the production of paper, as antimicrobial coating agents, in detergents and for the treatment of metal surfaces.
- the invention has for its object to provide more Alkyleniminawaen having polymers available.
- graft polymers which contain alkyleneimine units as side chains and whose base polymer is selected from the group of polymers containing vinylamine units, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids, if they contain exclusively oligoalkyleneimine side chains as alkyleneimine units.
- oligoalkyleneimine side chains contain, for example, 2 to 50 alkyleneimine units, generally 3 to 30 alkyleneimine units, preferably 3 to 15 alkyleneimine units. Oligoalkylenimininsulketten containing 5 to 10 Alkyleniminhimen are particularly preferred. Linear oligoalkyleneimine side chains [Al] n can be prepared, for example, by the following formula
- n is a number of at least 2 and R ' and R "are monovalent organic radicals such as C 1 to C 4 alkyl, phenyl or hydrogen, R ' and R " are preferably hydrogen.
- R ' and R " are preferably hydrogen.
- branched Oligoalkyleniminttingketten [Al] n come into consideration. For example, you can use the following formula
- p is 0 or a non-zero integer 1, 2, 3, etc.
- the formula III symbolizes a singly branched oligoalkylenimine unit [Al] n , but multiple branching is also possible.
- graft polymers whose Oligoalkyleniminsurketten consist of Ethyleniminiseren.
- the Oligoalkyleniminurbanketten can be in the form of the free bases or as salts.
- salt formation are, for example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acid or nitric acid and saturated organic acids such as formic acid, acetic acid, propionic acid, benzenesulfonic acid, sulfamic acid or p-toluenesulfonic into consideration.
- the nitrogen atoms of the silk Chain can be completely or partially neutralized with an acid. In addition, it is possible that they are present in quaternized form.
- methyl chloride ethyl chloride, n-propyl chloride, isopropyl chloride, n-butyl chloride, sec-butyl chloride, n-hexyl chloride, cyclohexyl chloride, benzyl chloride, methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, dimethyl sulfate or diethyl sulfate.
- the graft polymers according to the invention contain, for example per functional monomer unit in the base polymer 1 to 100 mol%, usually 20 to 80 mol%, preferably 30 to 60 mol% of at least one Oligoalkylenimins.
- functional monomer units in the base polymer are vinylamine units in the polymers comprising vinylamine units or primary or secondary amino groups in the case of the amines or polyamidoamines and acid groups, preferably carboxyl groups, in the polymers comprising acid groups.
- the invention also provides a process for preparing graft polymers having oligoalkyleneimine side chains, wherein at least one oligalkylenimine which contains a terminal aziridine group is grafted onto a graft base selected from the group of polymers comprising vinylamine units, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids.
- Oligoethyleneimines which contain a terminal aziridine group are preferably used as the oligoalkyleneimine. Together with the aziridine group, the ongoalkyleneimines consist of 2 to 50 alkyleneimine units, generally 3 to 30, preferably 3 to 15 and in particular 5 to 10 alkyleneimine units. The preparation of such compounds is known, cf. US 3,492,289 mentioned above in the prior art.
- Suitable grafting bases to which at least one oligoalkyleneimine having an intact aziridine group is grafted include, for example, vinylamine units containing polymers, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids.
- the molecular weight M w (determined by means of gel permeation chromatography) of these polymers is, for example, 500 to 1 million, preferably 1,000 to 500,000, in particular 2,000 to 350,000.
- Vinylamine-containing polymers are obtainable by hydrolysis of vinylformamide units containing polymers.
- Polyvinylamines are prepared for example by hydrolysis of homopolymers of N-vinylformamide, wherein the degree of hydrolysis, for example, up to 100%, usually 70 to 95%.
- Copolymers of N-vinylformamide with other ethylenically unsaturated monomers such as vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, acrylamide, acrylonitrile and / or methacrylonitrile can also be hydrolyzed to vinylamine units and used according to the invention as a graft base.
- the HIV nylamineinomme containing polymers are cationic.
- polyamidoamines come into consideration as the graft base. They are known to be prepared by condensing polycarboxylic acids, preferably dicarboxylic acids, with polyamines. For example, at least one dicarboxylic acid having 4 to 10 carbon atoms in the molecule is condensed with at least one polyalkylene polyamine which contains 3 to 10 basic nitrogen atoms in the molecule.
- suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid.
- polyalkylenepolyamines examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
- polyamidoamines it is of course also possible to use mixtures of polycarboxylic acids or mixtures of polyalkylenepolyamines.
- At least one dicarboxylic acid and at least one polyalkylenepolyamine are heated to higher temperatures, for example to a temperature in the range from 120 to 220 ° C., usually in the range from 130 to 180 ° C.
- the water formed during the condensation is removed from the Removed reaction mixture.
- lactones or lactams of carboxylic acids having 4 to 8 carbon atoms can also be used in the condensation.
- from 0.8 to 1.4 moles of a polyalkylenepolyamine are used per mole of a dicarboxylic acid.
- modified polyamidoamines can be used as a grafting base.
- the modified polyamidoamines include, for example, crosslinked polyamidoamines obtainable by reaction of polyamidoamines with at least one crosslinker to form water-soluble products.
- Suitable crosslinkers are, for example, epichlorohydrin or bis-chlorohydrin ethers of alkylene glycols and / or polyalkylene glycols.
- the polyalkylene glycols may e.g. Contain 2 to 100 alkylene oxide units.
- modified polyamidoamines are polyethyleneamines grafted with ethyleneimine and reacted with at least one crosslinker to give water-soluble products.
- graft the polyamidoamines with ethyleneimine they are added For example, in the presence of sulfuric acid or Bortrifluoridetheraten as a catalyst in an aqueous medium with ethyleneimine at temperatures of 80 to 100 0 C to.
- sulfuric acid or Bortrifluoridetheraten as a catalyst in an aqueous medium with ethyleneimine at temperatures of 80 to 100 0 C to.
- Compounds of this type are described for example in DE-B 24 34 816.
- polyalkylenepolyamines e.g. Polyalkylenepolyamines having molecular weights Mw of, for example, 300 to 15,000, preferably 1,000 to 12,000, and polyethylene imines.
- Suitable graft bases are also homopolymers and / or copolymers of ethylenically unsaturated acids.
- examples thereof are polymers of ethylenically unsaturated C 3 - to C 8 -carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid, vinyllactic acid or vinylacetic acid, acrylamidomethylpropanesulfonic acid or vinylphosphonic acid.
- Polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid and copolymers of acrylic acid and maleic acid are preferably suitable from this group of polymers.
- graft polymerization for example, per functional monomer unit in the graft base 1 to 100 mol%, usually 20 to 80 mol% and preferably 30 to 60 mol% of at least one Oligoalkylenimins containing an intact aziridine ring.
- the preparation of the products according to the invention is preferably carried out in an aqueous medium in the presence of a catalyst, for example a mineral acid such as hydrochloric acid or sulfuric acid.
- a catalyst for example a mineral acid such as hydrochloric acid or sulfuric acid.
- the pH of the reaction mixture is in the range of 5.5 to 12, preferably 6 to 11.
- the reaction is carried out, for example, by first adding the catalyst to an aqueous solution of the graft base, heating the mixture to the reaction temperature, and then metering in the oligoalkyleneimine, which has an intact terminal aziridine group, continuously or in portions.
- the reaction temperature is, for example, in the range of 55 to 1 10 0 C, preferably at 85 to 100 0 C.
- the duration of the reaction is mainly from the so-size of the batch as the reaction temperature dependent. For example, it is in the range of 30 minutes to 2 hours.
- the end point of the reaction ie the time at which aziridine groups can no longer be detected in the reaction mixture, can be determined with the aid of the reaction of aziridines with 4- (4-nitrobenzyl) pyridine, cf.
- reaction tion mixture can be used directly. However, it is also possible to isolate the graft products according to the invention from the reaction mixture.
- the graft polymers according to the invention which contain exclusively oligoalkyleneimine side chains as alkyleneimine units are used, for example, in the production of paper as process chemicals. Graft polymers having molecular weights M w (determined by means of gel permeation chromatography) of up to 30,000 are particularly suitable as fixing agents for contaminants and fines in papermaking.
- the graft polymers according to the invention can also be used as antimicrobial coating agents, as builders in detergents and for the treatment of metal surfaces.
- the characterization of the polymers was carried out by gel permeation chromatography (GPC) and partially coupled with multi-angle light scattering (GPC-MALLS).
- the amine number was determined by potentiometric titration according to DIN 53176.
- Dropping funnel 500 mL dropping funnel and gassing with N2 connection was provided, 150 g of completely desalinated water were submitted and heated to 55 0 C. Within 1 hour, 450 g of a 60% aqueous solution of ethyleneimine and a mixture of 6.5 g of 37% strength hydrochloric acid and 152 g of completely desalted water were then added in parallel. Thereafter, the reaction mixture was stirred for another 4 hours at 55 0 C then the mixture was cooled to 15 0 C and treated with 1 1, 6 g of a 25% aqueous sodium hydroxide solution. The product was bottled in a glass jar and stored therein at 5 0 C. The degree of oligomerization n (determined by means of 1 H NMR spectroscopy) was 6.84.
- the reaction mixture was then stirred for 2 hours at a temperature of 95 0 C. The reaction was then ended (Preussmann test negative). The pH of the reaction mixture was 1 1.
- the polymer had an amine number of 293 mg KOH / g, a molar mass M n (GPC) of 4900 gmoh 1 and a molecular weight M w (GPC) of 10,500 gmoh 1
- M n (GPC) 1370 gmoh 1
- a 500 ml four-necked flask with reflux condenser, dropping funnel and thermometer was charged with 26.2 g of a 17% strength aqueous solution of a 95% hydrolysed polyvinylformamide containing 95 mol% vinylamine and 5 mol% vinylformamide units, one molecular weight M n (GPC) of 3100 gmoh 1 and a molecular weight M w (GPC) of 8100 gmoh 1 had, adjusted by the addition of 1, 06 g of 37% hydrochloric acid to pH 6.0 and heated to a temperature of 95 0 C.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Detergent Compositions (AREA)
- Polyamides (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08864640A EP2225309A1 (de) | 2007-12-20 | 2008-12-16 | Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendung |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07150232 | 2007-12-20 | ||
EP08864640A EP2225309A1 (de) | 2007-12-20 | 2008-12-16 | Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendung |
PCT/EP2008/067619 WO2009080613A1 (de) | 2007-12-20 | 2008-12-16 | Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendung |
Publications (1)
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EP2225309A1 true EP2225309A1 (de) | 2010-09-08 |
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EP08864640A Withdrawn EP2225309A1 (de) | 2007-12-20 | 2008-12-16 | Pfropfpolymere mit oligoalkyleniminseitenketten, verfahren zu ihrer herstellung und ihre verwendung |
Country Status (5)
Country | Link |
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US (2) | US9249240B2 (ja) |
EP (1) | EP2225309A1 (ja) |
JP (1) | JP5693230B2 (ja) |
CA (1) | CA2707815C (ja) |
WO (1) | WO2009080613A1 (ja) |
Families Citing this family (10)
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US9249240B2 (en) * | 2007-12-20 | 2016-02-02 | Basf Se | Graft polymers having oligoalkylenimine side chains, process for their preparation and their use |
CN102066451B (zh) * | 2008-04-11 | 2014-08-06 | 巴斯夫欧洲公司 | 作为环氧树脂的固化剂的包含末端氨基的超支化聚合物和低聚物 |
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- 2008-12-16 CA CA2707815A patent/CA2707815C/en not_active Expired - Fee Related
- 2008-12-16 EP EP08864640A patent/EP2225309A1/de not_active Withdrawn
- 2008-12-16 JP JP2010538648A patent/JP5693230B2/ja not_active Expired - Fee Related
- 2008-12-16 WO PCT/EP2008/067619 patent/WO2009080613A1/de active Application Filing
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Also Published As
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US9127093B2 (en) | 2015-09-08 |
US9249240B2 (en) | 2016-02-02 |
US20100280203A1 (en) | 2010-11-04 |
CA2707815A1 (en) | 2009-07-02 |
WO2009080613A1 (de) | 2009-07-02 |
JP2011506728A (ja) | 2011-03-03 |
JP5693230B2 (ja) | 2015-04-01 |
US20140316072A1 (en) | 2014-10-23 |
CA2707815C (en) | 2017-01-24 |
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